WO2010095842A2 - Multifunctional adsorbent using sewage sludge or ashes, and livestock environment-improving agent - Google Patents

Multifunctional adsorbent using sewage sludge or ashes, and livestock environment-improving agent Download PDF

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WO2010095842A2
WO2010095842A2 PCT/KR2010/000959 KR2010000959W WO2010095842A2 WO 2010095842 A2 WO2010095842 A2 WO 2010095842A2 KR 2010000959 W KR2010000959 W KR 2010000959W WO 2010095842 A2 WO2010095842 A2 WO 2010095842A2
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adsorbent
sulfuric acid
phosphoric acid
hours
powdered
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PCT/KR2010/000959
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French (fr)
Korean (ko)
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WO2010095842A3 (en
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최진호
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주식회사비케이
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/3078—Thermal treatment, e.g. calcining or pyrolizing
    • C—CHEMISTRY; METALLURGY
    • C05—FERTILISERS; MANUFACTURE THEREOF
    • C05B—PHOSPHATIC FERTILISERS
    • C05B17/00—Other phosphatic fertilisers, e.g. soft rock phosphates, bone meal
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2220/00—Aspects relating to sorbent materials
    • B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
    • B01J2220/48—Sorbents characterised by the starting material used for their preparation
    • B01J2220/4806—Sorbents characterised by the starting material used for their preparation the starting material being of inorganic character
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2220/00—Aspects relating to sorbent materials
    • B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
    • B01J2220/48—Sorbents characterised by the starting material used for their preparation
    • B01J2220/4875—Sorbents characterised by the starting material used for their preparation the starting material being a waste, residue or of undefined composition
    • B01J2220/4887—Residues, wastes, e.g. garbage, municipal or industrial sludges, compost, animal manure; fly-ashes

Definitions

  • the present invention relates to an adsorbent for adsorbing odor-causing substances and fine dust and the like, and pig mortar reducing agent, manure fertilizer additive, activated carbon substitute, and industrial deodorant including the adsorbent.
  • the present invention relates to a multifunctional adsorbent that can be applied to various sites manufactured by mixing purified sludge or ash with waste sulfuric acid and waste phosphoric acid. More specifically, the adsorbent according to the present invention reduces pig mortality and improves the growth environment, pig mortar reducing agent, manure additive additive to control the smell of peculiar odor, activated carbon substitute used for filter in dust collection equipment, various odor induction It can be applied to industrial deodorant which controls odor by applying to facility.
  • Sewage sludge has been recycled to pollen materials, land improvers, landfill materials, bricks, etc., but it is known that wastewater is difficult to sell or commercialize due to the low treatment cost.
  • Sow sludge is composed of allium-based components, silicon, and organic materials, so that various types of applications are possible, and it is a waste with high need for recycling.
  • the present invention by applying the adsorbent in a variety of fields, firstly, by controlling the ammonia generated in pigs and collecting fine dust to reduce the pig mortality at the same time, and secondly, as a good raw material of fertilizer To solve the problem that the range of application is limited due to the bad smell of poultry, it provides additives necessary to produce manure fertilizer with excellent efficacy. Third, it is difficult to secure raw materials and provides substitute of activated carbon which is continuously increasing in price. By saving foreign currency and providing cheaper products to consumers, Fourth, industrial deodorants that control various types of odors generated from environmental foundations, food processing plants and other odor-producing facilities, and control odors generated from refrigerators and vehicles. It is to provide.
  • the sludge having undergone physical dehydration has a cake state, it is difficult to expect a decrease in moisture content anymore.
  • the pore water, chemical bonding water, surface water, etc. distributed in the constant sludge is dissociated to bring additional water content reduction.
  • the mixture of purified water sludge and phosphoric acid has a structure of Poriferous Multiple Cylinder (PMC), and afterwards, it is possible to provide a multifunctional adsorbent by maximizing the specific surface area through a drying process.
  • PMC Poriferous Multiple Cylinder
  • the adsorbent according to the present invention can adsorb various harmful substances and dusts, which is understood to be due to the superior specific surface area by the PMC structure.
  • control the odor generated in pigs from the next day to reduce the mortality rate of pigs and improve the growth environment, and consequently easy to livestock wastewater treatment It will increase the income of livestock farmers and improve the work of pig workers.
  • the flour is continuously produced a large amount of odor, even though it is composed of an excellent component as a fertilizer, it is difficult to control the odor is difficult to resource the compost.
  • the manure fertilizer additive containing the adsorbent according to the present application can effectively control the malodor can be actively utilized manure fertilizer.
  • control of the malodor is started after about 3 hours, and at least 98% of the malodor generated after 24 hours can be controlled, and at the same time, it is possible to prepare a manure fertilizer having an excellent fertilizer component.
  • manure fertilizers are less odor than the fermentation compost and excellent fertilizer components can contribute to the generation of a side income of farmers operating the poultry farm, and also helps to operate the sewage treatment facilities.
  • the adsorbent according to the present invention has a specific surface area of 2 to 4 times larger than that of activated carbon, which shows that the physical adsorption capacity is excellent.
  • activated carbon is not known to adsorb various odorous substances, but the adsorbent according to the present invention can control not only the field of application of activated carbon, but also the odorous substances that activated carbon does not control, and can sufficiently replace the existing activated carbon.
  • food waste and slaughter residues are generally known as representative aversive odor-causing substances that cause thousands of odors including polymer-based odors such as aldehydes, sulfides, and amines.
  • adsorbent When adsorbent is mixed with 10 ⁇ 30% by weight of copper, it starts controlling odor after 1 hour and controls more than 98% of generated odor after 24 hours, improving working conditions, blocking civil complaints, It will be effective in establishing recycling plan.
  • Figure 1 is a 9,000 times magnification of the PMC SEM (electron microscope), confirming that the porous homogeneous surface has a large specific surface area.
  • PMC is the main component of the adsorbent made by the present invention.
  • the adsorbent according to the present application uses constant sludge dried cold with stirring.
  • the adsorbent is pulverized in this way, the dried sludge and 5-15 parts by weight of phosphoric acid source are mixed and stirred with respect to the crushed purified sludge and stirred for 10 to 30 hours, and aged at 100 ° C to 300 ° C.
  • the phosphoric acid source or sulfuric acid source is preferably phosphoric acid or sulfuric acid.
  • the phosphoric acid concentration is 60 to 90%, waste phosphoric acid or regenerative phosphoric acid can also be used. Waste phosphoric acid which has been used after etching can also be used.
  • sulfuric acid source can be used sulfuric acid, regeneration sulfuric acid if the sulfuric acid concentration is 30 ⁇ 70%.
  • the adsorbent may use ash, which is a byproduct of thermal power generation, instead of the above-mentioned constant sludge.
  • Ash is an essential by-product of thermal power plants.
  • One thermal power plant generates a large amount of about 80,000 to 100,000 tons per year, but it is buried more than 90% because proper recycling plan is not provided.
  • ash can be recycled to have useful characteristics for the environmental industry without causing environmental problems as a result of various experiments, and it is expected that the value of its use will increase in the future, but its utilization is very small at present.
  • the present invention by utilizing such an ash, it is possible to provide an adsorbent excellent in adsorption capacity as well as contributing to pollution prevention.
  • Another aspect of the present invention relates to an adsorbent produced by using a constant sludge or ash as a main raw material, and the adsorbent is characterized in that it is versatile, which can be applied to various fields such as pig sand, manure fertilizer, odor inducing facilities, and dust collecting facilities.
  • the adsorbent according to the present invention is a highly functional recycled product made using only by-products, and although the manufacturing cost is very low, the adsorption effect is much better than that of the conventional adsorbent.
  • the adsorbent of the present invention can be applied as a pig mortality reducing agent, manure fertilizer additive, activated carbon substitute, industrial deodorant and the like.
  • the adsorbent according to the present invention is a multi-functional Can have A photograph of an adsorbent according to the present invention with an SEM of 9000 magnification is shown in FIG. 1.
  • the adsorbent according to the present invention has a multilayer porous cylindrical structure, the shape is powder or pellets, the hardness is characterized in that 92% or more.
  • Sludge sludge used as the main raw material of the present invention is a final product generated in the course of water treatment, and refers to a microbial mass separated by physicochemically floating or sedimenting after being propagated by ingesting nutrients dissolved in the constant water.
  • a constant sludge is hardly made into resources, and the dumping and reclamation are mainly carried out, and thus the problem of environmental pollution has emerged.
  • the constant sludge can be recycled to possess useful characteristics for the environmental industry without causing environmental problems as a result of various experiments, and thus the utilization value is expected to increase in the future, but its utilization is very small at present.
  • the present invention by utilizing such a constant water sludge, it is possible to provide an adsorbent which can not only contribute to pollution prevention but also has excellent adsorption capacity.
  • the adsorbent according to the present application uses constant sludge dried cold with stirring.
  • the adsorbent is pulverized in this way, the dried sludge and 5-15 parts by weight of phosphoric acid source are mixed and stirred with respect to the crushed purified sludge and stirred for 10 to 30 hours, and aged at 100 to 300 for 5 to 15 hours.
  • It comprises a 100 ⁇ 200 mesh powdered phosphoric acid material aged by heating, and further mixed and stirred 5-15 parts by weight of sulfuric acid source with respect to the crushed purified sludge and the constant sludge, stirred and aged for 10-30 hours, and 100 °C It contains 100 to 200 mesh powdered sulfuric acid material aged by heating at ⁇ 300 ° C. for 5 to 15 hours.
  • the phosphoric acid source or sulfuric acid source is preferably phosphoric acid or sulfuric acid.
  • the phosphoric acid concentration is 60 to 90%, waste phosphoric acid or regenerative phosphoric acid can also be used. Waste phosphoric acid which has been used after etching can also be used.
  • sulfuric acid source can be used sulfuric acid, regeneration sulfuric acid if the sulfuric acid concentration is 30 ⁇ 70%.
  • the adsorbent may use ash, which is a byproduct of thermal power generation, instead of the above-mentioned constant sludge.
  • Ash is an essential by-product of thermal power plants.
  • One thermal power plant generates a large amount of about 80,000 to 100,000 tons per year, but it is buried more than 90% because proper recycling plan is not provided.
  • ash can be recycled to have useful characteristics for the environmental industry without causing environmental problems as a result of various experiments, and it is expected that the value of its use will increase in the future, but its utilization is very small at present.
  • the present invention by utilizing such an ash, it is possible to provide an adsorbent excellent in adsorption capacity as well as contributing to pollution prevention.
  • Another aspect of the present invention relates to an adsorbent produced by using a constant sludge or ash as a main raw material, and the adsorbent is characterized in that it is versatile, which can be applied to various fields such as pig sand, manure fertilizer, odor inducing facilities, and dust collecting facilities.
  • the adsorbent according to the present invention is a highly functional recycled product made using only by-products, and although the manufacturing cost is very low, the adsorption effect is much better than that of the conventional adsorbent.
  • Adsorbents of the present invention can be applied as a pig mortality reducing agent, manure fertilizer additives, activated carbon substitutes, industrial deodorants, etc., to present a field application example obtained by the field application experiments over the years.
  • Pigs regardless of location or season, have intense breathing gas on their eyes and nose, making it difficult for the average person to breathe and keep their eyes open. Pigs are always congested in their eyes, and their eyes are pinched, and they lie down almost except when they eat. This is a phenomenon that is poisoned by a large amount of ammonia gas generated in the manure, ammonia is inhaled into the body through the respiratory organs of pigs to the dust in the air, which acts as a major cause of death of pigs, but there is still a commercial product that efficiently controls ammonia gas There is no way to burn the children of the farm.
  • ammonia concentration begins to decrease after about 3 hours and ammonia is effectively reduced after 24 hours.
  • the day after the spray you can feel the disappearance of the gas from your eyes and nose, you can see the redness of the pig's eyeballs begin to relieve, and the pig who has been lying down You will see that.
  • the manure fertilizer additive containing the adsorbent according to the present invention When the manure is produced as a fertilizer using the manure fertilizer additive containing the adsorbent according to the present invention, it was confirmed through field tests that a good fertilizer can be made without using sawdust.
  • concrete cases are mixed, when 100 weight of poultry is mixed with 10 weights of quicklime, the quicklime absorbs the moisture in the poultry, causing hydration reactions and exothermic heat from room temperature 25 to 40. do. If the type of odor generated in this process is changed and reacted for about 1 hour, and then the manure additive is added and stirred, 95% of the odor generated after 24 hours starts to control the odor. The control is reduced. You can also see white mold on the surface, which means that the ripening process takes place.
  • manure fertilizer produced in this way was tested to meet the legal requirements as a compost through the fertilizer process standard test, and lettuce cultivation experiments showed that the lettuce yield between the manure spreading and non-spraying was about 30%. Furthermore, these manure fertilizers are added with quicklime to improve the soil, and the inherent fertilizer effect and calcium, the main ingredient of lime, enhance the crop's structure and increase the absorption of nutrients in the land, resulting in an increase in crop quality and yield.
  • Activated carbon is mainly palm-based activated carbon and coal-based activated carbon, which is dependent on imports.
  • the main source of import of coal-based activated carbon is China.
  • Incheon Port was 700,000 won per ton, and currently imports at 1.5 million won per ton.
  • the price has risen more than twice, increasing the burden on the company.
  • the development of alternative materials is urgent given that the Chinese government is gradually reducing the export of natural resources.
  • most plant facilities operating in Korea require dust collection facilities and odor prevention facilities in accordance with the related laws.
  • Most of them use activated carbon as adsorbent and the market size is estimated to be about 1 trillion won per year.
  • the adsorbent according to the present invention has a specific surface area of about 2 to 4 times larger than that of coal-based activated carbon, which is due to the above-described PMC structure. Can be replaced sufficiently.
  • activated carbon is known to be effective for adsorption of a particular malodorous substance, and the adsorbent according to the present invention can absorb and control a malodorous substance that activated carbon cannot control in addition to the specific malodorous substance.
  • the iodine adsorption test results were measured at more than 1,050g / g, the hardness was measured at more than 92% was confirmed to meet the specifications of the existing activated carbon.
  • the adsorbent according to the present invention is evaluated to have the same or superior adsorption capacity with activated carbon by the PMC.
  • the present inventors prepare the adsorbent according to the present invention in powder form and pellets, and process the leather processing plant and food waste.
  • the application of on-site applications in facilities, composting plants, slaughterhouses, etc. confirmed the potential as an activated carbon substitute.
  • a granular adsorbent prepared according to the invention is shown in FIG. 2.
  • the adsorbent according to the present application can be applied as an industrial deodorant and the inventors have confirmed this through several routes.
  • Representative examples include food waste and slaughter residues. They contain aldehydes, amines, sulfides and many other odorous substances, and there is no deodorant that can effectively control such odorous substances. It is also causing another problem such as deterioration.
  • the adsorbent industrial deodorant
  • the odor generated after 24 hours is reduced by more than 98% to improve the working environment of workers, It will be useful as an industrial deodorant by bringing various effects such as securing a recycling point and solving odor complaints.
  • the adsorbent according to the present invention comprises: a first step of air drying with stirring the purified sludge; A second step of crushing the cold-dried purified sludge; A third step of mixing and stirring the phosphate material selected from the group consisting of waste phosphoric acid, regenerated phosphoric acid and phosphoric acid and stirring the crushed purified sludge for 10 to 30 hours; A fourth step of mixing and stirring a sulfuric acid material selected from the group consisting of waste sulfuric acid, regenerated sulfuric acid and sulfuric acid and the crushed purified sludge for 10 to 30 hours; A fifth step of powdering the resultant of the third and fourth steps by heating at 100 ° C. to 300 ° C.
  • the result of the third step and the fourth step through the sixth step may be prepared by a method consisting of the seventh step of mixing the mixing ratio (A) to 55%: 45% ⁇ A ⁇ 100: 0%.
  • the above method it is possible to mix the sludge with phosphate and sulfuric acid at the same time.
  • the above system and the system can be carried out by mixing the crushed sludge with the phosphate and sulfate. Do.
  • the deodorant of the present invention is preferably a phosphate material selected from the group consisting of waste phosphoric acid, regenerated phosphoric acid, phosphoric acid and a sulfuric acid material selected from the group consisting of a first deodorant, waste sulfuric acid, regenerative sulfuric acid, sulfuric acid It can be prepared by a method of preparing a second deodorant mixed with the water sludge, and a third deodorant mixed with the first deodorant and the second deodorant, the first deodorant and the second deodorant forming the third deodorant in the present invention
  • the content ratio (A) of preferably satisfies the range of 55:45 ⁇ A ⁇ 100: 0.
  • the first step of preparing the adsorbent is to perform cold air drying while stirring the purified sludge. While stirring may be used a general stirrer used in the art, it is preferred to use a rotary stirrer. In addition, it is preferable to carry out cold air drying or room temperature drying at the time of drying, and it is preferable to carry out drying for about 1 day-2 days or more preferably the period beyond.
  • the purified sludge After drying the purified sludge, it is crushed using a crusher, and then mixed with a mixture of waste phosphoric acid or regenerated phosphoric acid or phosphoric acid, and aged for 10 to 30 hours. In this case, ash may be used instead of the dried constant sludge.
  • the amount of waste phosphoric acid or regenerative phosphoric acid or phosphoric acid is preferably added in an amount of 5 parts by weight to 15 parts by weight based on the total mass of the purified sludge or ash.
  • the amount thereof is preferably about 5 parts by weight to 15 parts by weight based on the total amount of the purified sludge or ash.
  • the mixture is pulverized to 100 to 200 mesh, and then a mixture of purified sludge and / or ash and waste phosphoric acid (first deodorant), and a mixture of purified sludge and / or ash and waste sulfuric acid (second deodorant) Are mixed with each other to produce a final deodorant (third deodorant), the mixing ratio A of which is preferably 50:50 ⁇ A ⁇ 100: 10 by mass.
  • a total of four kinds of adsorbents can be produced as described above, and each of these adsorbents can be specialized for each application.
  • the sludge and / or ash was cold-dried for 1 day and then crushed using a crusher.
  • the sludge and / or ash was then mixed with waste phosphoric acid at a concentration of 63% or spent sulfuric acid at a concentration of 50% and heated at 200 for 10 hours, which was then ground to 200 mesh.
  • the amount of purified sludge, ash, waste phosphoric acid and waste sulfuric acid, and a detailed manufacturing method are shown in Table 1 below.
  • Table 1 Water purifier Ash Waste phosphate Spent sulfuric acid quite
  • Example 1 125 g 12g Prepared by mixing 125g of purified water with 12g of waste phosphoric acid and heating at 200 °C for 10 hours.
  • Example 2 125 g 12g Prepared by mixing 125g of purified water with 12g of waste sulfuric acid and heating at 200 °C for 10 hours.
  • Example 3 125 g 6.25 g 6.25 g Prepared by mixing 62.5g of purified water sludge with 6.25g of waste phosphoric acid and heating it at 200 °C for 10 hours, by mixing 62.5g of purified water with 6.25g of waste sulfuric acid and heating it at 200 °C for 10 hours
  • Example 4 62.5 g 62.5 g 12.5 g 62.5 g of purified water sludge and 62.5 g of ash were mixed first, and then mixed with 12.5 g of waste phosphoric acid and heated at 200 ° C. for 10 hours.
  • Example 5 62.5 g 62.5 g 12.5 g 62.5 g of purified water sludge and 62.5 g of ash are mixed first, and then mixed with 12.5 g of waste sulfuric acid and heated at 200 ° C. for 10 hours.
  • Example 6 62.5 g 62.5 g 62.5 g 62.5 g Prepared by mixing 62.5g of purified water sludge with 6.25g of waste phosphoric acid and heating it at 200 °C for 10 hours, by mixing 62.5g of purified water with 6.25g of waste sulfuric acid and heating it at 200 °C for 10 hours
  • Test Example 1 is applied to pig mortality reducing agent
  • Test Example 2 is applied to fertilizer additives
  • Test Example 3 is applied to activated carbon substitutes.
  • Example 4 shows an application example for the industrial deodorant, the adsorbent according to the present invention has a versatility that can be applied to various fields in addition to.
  • the deodorization experiment was performed using the pig mortality reducing agent prepared in Examples 1-6. 10 kg of pig powder was mixed in a mixed digestion reactor, mixed for 5 minutes, and mixed evenly. After 2 minutes of stirring with 2 kg of pig mortality reducing agent, the ammonia concentration was first measured by a detection tube. Are recorded and presented in Table 2.
  • Pig mortality reducing agent Elapsed time (minutes) Money (ppm) Pig meal + pig lung mortality reduction (ppm) Ammonia Control Rate (%)
  • Example 1 5 150 25 149 70 53.02 185 150 15 90.00 365 147 7 95.24 725 145 5 96.55 1445 140 2 98.57
  • Deodorization experiments were carried out using the fertilizer additives prepared in Examples 1-6. 10kg of the mixture is put into the mixed digestion reactor, mixed by stirring for 5 minutes, and then mixed with 1kg of quicklime and allowed to react for 1 hour to allow the hydration reaction to occur, and then 30 minutes after stirring with 2kg of the fertilizer additive. After measuring the ammonia concentration with a detector tube from the beginning, a total of 5 times was measured and the results were recorded and shown in Table 3.
  • Activated carbon substitutes were molded into pellets having a diameter of 5 mm, and then the adsorption amount and hardness of iodine were checked.
  • Adsorption experiments were performed using the industrial deodorant prepared in Examples 1-6.
  • the industrial deodorant (adsorbent) was molded into pellets with a diameter of 5 mm, and then put into a bag filter and installed in a odor prevention facility with a capacity of 20 cc / cm 2 / sec installed in the slaughterhouse. Presented in 5.
  • the adsorbent according to the present invention has excellent adsorptive power, and shows extremely excellent application as a pig lung deadener, manure fertilizer additive, activated carbon substitute, and industrial deodorant. It can be seen that the product has high economical efficiency.

Abstract

Provided is a multifunctional adsorbent containing sewage sludge (or ashes), sulfuric acid material, and phosphoric acid material. The adsorbent of the present invention uses, as a main material, sewage sludge or ashes, waste phosphoric acid or waste sulfuric acid, and removes ammonia gas and hydrogen sulfide, polymeric compounds such as amines, sulfides, aldehydes or the like, and/or dust, and thus can be used for multiple functions such as agents for reducing the death of pigs, additives to poultry waste fertilizer, activated carbon substitutes, deodorizers, etc.

Description

상수오니 또는 애쉬류를 이용한 다기능성 흡착제 및 축사환경개선제Multifunctional Sorbent and Barn Enviroment Enhancer Using Water Sludge or Ash
본 발명은 악취원인물질 및 미세먼지 등을 흡착하는 흡착제 및 이 흡착제를 포함하는 돼지폐사저감제, 계분비료첨가제, 활성탄 대체제 및 산업용 탈취제에 관한 것이다. 구체적으로 본 발명은, 상수오니 또는 애쉬류(類)와 폐황산과 폐인산을 혼합하여 제조된 다양한 현장에 적용이 가능한 다기능성 흡착제에 관한 것이다. 보다 구체적으로, 본 발명에 따른 흡착제는 돼지폐사율을 줄여주고 생육환경을 개선하는 돼지폐사저감제, 계분 특유의 악취를 제어하는 계분비료첨가제, 집진설비에 필터용으로 사용하는 활성탄 대체재, 각종 악취유발시설에 적용하여 악취를 제어하는 산업용 탈취제 등에 적용이 가능하다. The present invention relates to an adsorbent for adsorbing odor-causing substances and fine dust and the like, and pig mortar reducing agent, manure fertilizer additive, activated carbon substitute, and industrial deodorant including the adsorbent. Specifically, the present invention relates to a multifunctional adsorbent that can be applied to various sites manufactured by mixing purified sludge or ash with waste sulfuric acid and waste phosphoric acid. More specifically, the adsorbent according to the present invention reduces pig mortality and improves the growth environment, pig mortar reducing agent, manure additive additive to control the smell of peculiar odor, activated carbon substitute used for filter in dust collection equipment, various odor induction It can be applied to industrial deodorant which controls odor by applying to facility.
상수오니는 그 동안 화분재, 토지개량제, 성토재, 벽돌 등으로 재활용되어 왔으나 상수오니의 처리비가 저렴하여 현실적으로 유상판매나 상업화가 어려운 폐기물인 것으로 알려져 있다. 그러나 상수오니는 알럼 계열의 성분과 규소, 유기물 등으로 구성되어 있어 다양한 형태의 응용이 가능하여, 재활용의 필요성이 높은 폐기물에 속한다.Sewage sludge has been recycled to pollen materials, land improvers, landfill materials, bricks, etc., but it is known that wastewater is difficult to sell or commercialize due to the low treatment cost. However, Sow sludge is composed of allium-based components, silicon, and organic materials, so that various types of applications are possible, and it is a waste with high need for recycling.
상수오니에 대한 재활용의 요구는 증가하고 있는 반면, 상수오니는 케익과 같은 성상을 가지고 있기 때문에 함수율 저감에 한계가 있어서, 상용화에 문제점이 있었다. 본원 발명자들은 상기 문제점에 대하여 실험과 분석을 반복한 결과, 인산 또는 황산을 사용하여 함수율을 극적으로 저하시키는 방법을 개발하여 상수오니를 흡착제로 완성하게 된 것이며, 유사한 방법을 애쉬류에도 적용하여 흡착제로 완성하게 된 것이다.While the demand for recycling of purified water sludge is increasing, the purified water sludge has the same properties as cakes, so there is a limit in reducing the moisture content, which causes problems in commercialization. The inventors of the present invention repeated the experiment and analysis of the above problems, and developed a method of dramatically reducing the water content using phosphoric acid or sulfuric acid to complete the purified sludge as an adsorbent, and similar methods were applied to ashes to adsorbents. It was completed as.
한편, 본 발명은 상기 흡착제를 다양한 분야에 적용함으로써, 첫째, 돈사에서 발생하는 암모니아를 제어하고 미세먼지를 집진함으로써 돼지폐사율을 저감시키면서 동시에 생육환경을 개선시키고, 둘째, 비료의 원료로서 훌륭한 소재인 계분이 심한 악취로 인해 활용범위가 제한되어 있는 점을 해결하여 우수한 효능을 가진 계분비료를 생산하는데 필요한 첨가제를 제공하며, 셋째, 원료의 확보가 어렵고 가격이 지속적으로 상승하고 있는 활성탄의 대체재를 제공함으로써 외화를 절약하고 보다 저렴한 제품을 소비자에게 제공하고, 넷째, 환경기초시설 및 식품가공공장 및 기타 악취유발시설에서 발생하는 다양한 형태의 악취를 제어하고 냉장고와 차량 등에서 발생하는 악취를 제어하는 산업용 탈취제를 제공하기 위한 것이다.On the other hand, the present invention by applying the adsorbent in a variety of fields, firstly, by controlling the ammonia generated in pigs and collecting fine dust to reduce the pig mortality at the same time, and secondly, as a good raw material of fertilizer To solve the problem that the range of application is limited due to the bad smell of poultry, it provides additives necessary to produce manure fertilizer with excellent efficacy. Third, it is difficult to secure raw materials and provides substitute of activated carbon which is continuously increasing in price. By saving foreign currency and providing cheaper products to consumers, Fourth, industrial deodorants that control various types of odors generated from environmental foundations, food processing plants and other odor-producing facilities, and control odors generated from refrigerators and vehicles. It is to provide.
물리적 탈수를 마친 상수오니는 케익 상태의 성상을 가지기 때문에, 더 이상 함수율의 저감을 기대하기 어렵다. 하지만 본원 발명에 따라, 인산류 또는 황산류를 적당량 혼합하여 일정 시간 교반시킨 후 숙성공정을 거치면, 상수오니 속에 분포되어 있는 공극수, 화학적 결합수, 표면수 등이 해리되어 추가적인 함수율 저감을 가져옴으로써, 상수오니 및 인산류 등의 혼합물은 복층다공형원통(PMC: Poriferous Multiple Cylinder) 구조를 가지게 되며, 이후 건조공정을 거쳐 비표면적을 극대화킴으로써 다기능성의 흡착제를 제공할 수 있게 된다.Since the sludge having undergone physical dehydration has a cake state, it is difficult to expect a decrease in moisture content anymore. However, according to the present invention, by mixing an appropriate amount of phosphoric acid or sulfuric acid and stirring for a predetermined time, after the aging process, the pore water, chemical bonding water, surface water, etc. distributed in the constant sludge is dissociated to bring additional water content reduction, The mixture of purified water sludge and phosphoric acid has a structure of Poriferous Multiple Cylinder (PMC), and afterwards, it is possible to provide a multifunctional adsorbent by maximizing the specific surface area through a drying process.
본 발명에 의한 흡착제는 각종 유해 물질 및 먼지류를 흡착할 수 있으며, 이는 PMC 구조에 의한 월등한 비표면적에 기인하는 것으로 이해된다. 특히, 돈사 330m2를 기준으로 본 발명에 따른 흡착제를 10kg을 살포하는 경우, 익일부터 돈사 내에서 발생하는 악취를 제어하여 돼지의 폐사율을 줄이고 생육환경을 개선시키게 되며, 결과적으로 축산폐수처리가 용이해지며, 축산농가의 소득을 증대하고 돈사 작업자의 작업개선효과를 가져오게 된다.The adsorbent according to the present invention can adsorb various harmful substances and dusts, which is understood to be due to the superior specific surface area by the PMC structure. In particular, when spraying 10kg of the adsorbent according to the present invention on the basis of pig 330m2, control the odor generated in pigs from the next day to reduce the mortality rate of pigs and improve the growth environment, and consequently easy to livestock wastewater treatment It will increase the income of livestock farmers and improve the work of pig workers.
또한, 계분은 다량의 악취를 지속적으로 생성시키기 때문에, 비료로서 우수한 성분으로 이루어져 있음에도 불구하고, 악취의 제어가 어려워 퇴비로 자원화 하는데 어려움을 겪고 있다. 그러나 본원에 따른 흡착제를 포함하는 계분비료첨가제를 사용할 경우 악취를 유효하게 제어할 수 있어 계분비료를 적극 활용할 수 있다. 계분에 생석회를 중량비 10%를 투입하여 교반하면 생석회의 수화 반응에 의해 계분 내 수분이 감소되고 온도가 약 40℃로 상승하면서 PH가 알칼리로 바뀌게 되며, 1시간 경과 후에 본원에 따른 흡착제를 첨가하여 교반하면, 약 3시간 후부터 악취를 제어하기 시작하여 24시간 경과 후 발생 악취의 98%이상을 제어됨과 동시에 우수한 비료성분을 가지는 계분 비료를 제조할 수 있게 된다. 이러한 계분 비료는 돈분 발효 퇴비 보다 악취가 적고, 비료성분이 우수하여 계사를 운영하는 농민의 부수익 창출에 기여할 수 있으며, 계사의 폐수처리시설 운용에도 도움이 된다.In addition, since the flour is continuously produced a large amount of odor, even though it is composed of an excellent component as a fertilizer, it is difficult to control the odor is difficult to resource the compost. However, when using the manure fertilizer additive containing the adsorbent according to the present application can effectively control the malodor can be actively utilized manure fertilizer. When 10% by weight of quicklime is added to the system for stirring, the moisture in the system decreases due to the hydration reaction of the quicklime, and the pH changes to alkali as the temperature rises to about 40 ° C. After 1 hour, the adsorbent according to the present invention is added. When stirred, control of the malodor is started after about 3 hours, and at least 98% of the malodor generated after 24 hours can be controlled, and at the same time, it is possible to prepare a manure fertilizer having an excellent fertilizer component. These manure fertilizers are less odor than the fermentation compost and excellent fertilizer components can contribute to the generation of a side income of farmers operating the poultry farm, and also helps to operate the sewage treatment facilities.
본 발명에 의한 흡착제는 활성탄보다 비표면적이 2~4배가량 큰 것으로 관찰되었으며, 이는 물리적 흡착능력이 우수함을 반증하는 것이다. 일반적으로 활성탄의 경우 다양한 악취물질을 흡착하지는 못하는 것으로 알려져 있으나, 본 발명에 의한 흡착제는 활성탄의 적용분야 뿐 아니라 활성탄이 제어하지 못하는 악취물질까지 제어하게 되어, 기존의 활성탄을 충분히 대체할 수 있다. It is observed that the adsorbent according to the present invention has a specific surface area of 2 to 4 times larger than that of activated carbon, which shows that the physical adsorption capacity is excellent. In general, activated carbon is not known to adsorb various odorous substances, but the adsorbent according to the present invention can control not only the field of application of activated carbon, but also the odorous substances that activated carbon does not control, and can sufficiently replace the existing activated carbon.
또한, 음식물쓰레기, 도축잔재물은 일반적으로 알데하이드, 설파이드, 아민 등 고분자 계열의 악취를 비롯하여 수천가지의 악취를 유발하는 대표적인 혐오성 악취유발물질로 알려져 있다. 동 물질에 흡착제를 중량비 10~30%를 혼합하여 교반시키면 1시간 경과 시부터 악취를 제어하기 시작하여 24시간을 경과하게 되면 발생악취의 98%이상을 제어하여 작업여건개선, 민원유발차단, 다양한 재활용방안 수립 등의 효과를 보게 된다.In addition, food waste and slaughter residues are generally known as representative aversive odor-causing substances that cause thousands of odors including polymer-based odors such as aldehydes, sulfides, and amines. When adsorbent is mixed with 10 ~ 30% by weight of copper, it starts controlling odor after 1 hour and controls more than 98% of generated odor after 24 hours, improving working conditions, blocking civil complaints, It will be effective in establishing recycling plan.
도1 은 PMC를 SEM(전자현미경)으로 9,000배 확대한 사진으로, 다공성의 균질한 표면이 넓은 비표면적을 가지고 있음을 확인시켜 준다. PMC는 본 발명에 의해 만들어지는 흡착제의 주요 성분이다.Figure 1 is a 9,000 times magnification of the PMC SEM (electron microscope), confirming that the porous homogeneous surface has a large specific surface area. PMC is the main component of the adsorbent made by the present invention.
본원에 따른 흡착제는 교반하면서 냉풍 건조된 상수 오니를 사용한다. 흡착제는, 이와 같이 건조된 오니를 파쇄하고, 상기 파쇄된 상수오니와 상기 상수오니에 대하여 5~15중량부의 인산 공급원을 혼합 교반하여 10~30 시간 교반 숙성하고, 100℃~300℃에서 5~15 시간 가열하여 숙성된 100~200 메쉬의 분말 인산 물질을 포함하며, 또한, 상기 파쇄된 상수오니와 상기 상수 오니에 대하여 5~15중량부의 황산 공급원을 혼합 교반하여 10~30 시간 교반 숙성하고, 100℃~300℃에서 5~15시간 가열하여 숙성된 100~200 메쉬의 분말 황산 물질을 포함한다. The adsorbent according to the present application uses constant sludge dried cold with stirring. The adsorbent is pulverized in this way, the dried sludge and 5-15 parts by weight of phosphoric acid source are mixed and stirred with respect to the crushed purified sludge and stirred for 10 to 30 hours, and aged at 100 ° C to 300 ° C. 100 to 200 mesh powdered phosphoric acid material aged by heating for 15 hours, and mixed with 5-15 parts by weight of sulfuric acid source to the crushed purified sludge and the constant sludge, stirred and aged for 10-30 hours, Powdered sulfuric acid material of 100 ~ 200 mesh aged by heating for 5 to 15 hours at 100 ℃ ~ 300 ℃.
이때, 인산 공급원이나 황산 공급원은 바람직하게는 인산이나 황산이다. 그러나 고가의 인산이나 황산을 반드시 사용할 필요는 없으며, 저가의 재활용 인산이나 황산을 사용할 수 있다 구체적으로, 인산 농도가 60~90%인 것이면 폐인산, 재생인산도 사용할 수 있으며, 또한 반도체 제조공정 등에서 에칭액으로 사용 후 나오는 폐인산을 사용할 수도 있다. 한편 황산 공급원은 황산 농도 30~70%인 것이면 폐황산, 재생황산도 사용할 수 있다. At this time, the phosphoric acid source or sulfuric acid source is preferably phosphoric acid or sulfuric acid. However, it is not necessary to use expensive phosphoric acid or sulfuric acid, and inexpensive recycled phosphoric acid or sulfuric acid can be used. Specifically, if the phosphoric acid concentration is 60 to 90%, waste phosphoric acid or regenerative phosphoric acid can also be used. Waste phosphoric acid which has been used after etching can also be used. On the other hand, sulfuric acid source can be used sulfuric acid, regeneration sulfuric acid if the sulfuric acid concentration is 30 ~ 70%.
본 발명의 다른 양태에 있어서, 흡착제는 상술한 상수 오니 대신에 화력 발전의 부산물인 애쉬류를 사용할 수 있다. 애쉬는 화력발전소에서 필수적으로 발생하는 부산물로서, 화력발전소 1 개소는 연간 약 80,000톤에서 100,000톤에 이르는 많은 양을 발생 시키지만, 적절한 재활용 방안이 마련되지 않아 90%이상 매립돼 버리는 실정이다.In another embodiment of the present invention, the adsorbent may use ash, which is a byproduct of thermal power generation, instead of the above-mentioned constant sludge. Ash is an essential by-product of thermal power plants. One thermal power plant generates a large amount of about 80,000 to 100,000 tons per year, but it is buried more than 90% because proper recycling plan is not provided.
그러나 애쉬는 다양한 실험결과 환경문제를 발생 시키지 않고, 환경 산업에 유용한 특성을 보유할 수 있도록 재활용 할 수 있어, 활용가치가 향후 증대될 것으로 보이지만 현재는 그 활용도가 극히 미미한 실정이다. 본 발명에 따르면 이와 같은 애쉬를 활용함으로써, 공해 방지에 이바지 할 뿐 아니라 흡착능이 우수한 흡착제를 제공할 수 있다.However, ash can be recycled to have useful characteristics for the environmental industry without causing environmental problems as a result of various experiments, and it is expected that the value of its use will increase in the future, but its utilization is very small at present. According to the present invention, by utilizing such an ash, it is possible to provide an adsorbent excellent in adsorption capacity as well as contributing to pollution prevention.
본 발명의 또 다른 양태는 상수 오니 또는 애쉬를 주원료로 하여 제조되는 흡착제에 관한 것으로, 이 흡착제는 돈사, 계분비료, 악취유발시설, 집진시설 등 다양한 현장 적용이 가능한 다기능성인 것을 특징으로 한다. Another aspect of the present invention relates to an adsorbent produced by using a constant sludge or ash as a main raw material, and the adsorbent is characterized in that it is versatile, which can be applied to various fields such as pig sand, manure fertilizer, odor inducing facilities, and dust collecting facilities.
본 발명에 의한 흡착제는 부산물만을 활용하여 만든 고기능성 재활용제품으로서, 제조원가가 매우 낮음에도 불구하고 그 흡착효과는 기존의 흡착제보다 월등히 우수하다. 본 발명의 흡착제는 돼지폐사저감제, 계분비료첨가제, 활성탄 대체제, 산업용 탈취제 등으로 적용될 수 있다.The adsorbent according to the present invention is a highly functional recycled product made using only by-products, and although the manufacturing cost is very low, the adsorption effect is much better than that of the conventional adsorbent. The adsorbent of the present invention can be applied as a pig mortality reducing agent, manure fertilizer additive, activated carbon substitute, industrial deodorant and the like.
본 발명에 의한 흡착제를 SEM(전자현미경)으로 관찰해보면, 복층다공형원통(PMC: Poriferous Multiple Cylinder) 구조가 다량 함유되어 있음을 확인할 수 있으며, 이러한 구조에 의하여 본 발명에 의한 흡착제는 다기능성을 가질 수 있다. 본 발명에 따른 흡착제를 9000 배율의 SEM으로 촬영한 것을 도 1에 나타내었다. 도 1에서 확인할 수 있는 것처럼, 본원에 따른 흡착제는 복층다공형원통 구조를 가지는 것으로서, 그 형상은 분말 또는 펠렛이며, 경도는 92% 이상인 것을 특징으로 한다. Observing the adsorbent according to the present invention by SEM (electron microscope), it can be seen that the structure contains a large amount of Poriferous Multiple Cylinder (PMC), the adsorbent according to the present invention is a multi-functional Can have A photograph of an adsorbent according to the present invention with an SEM of 9000 magnification is shown in FIG. 1. As can be seen in Figure 1, the adsorbent according to the present invention has a multilayer porous cylindrical structure, the shape is powder or pellets, the hardness is characterized in that 92% or more.
본 발명의 하나의 태양에 있어서, 상수오니를 포함하는 흡착제에 대하여 상술한다. 본 발명의 주원료로 이용되는 상수오니는 통상 상수 처리과정에서 발생하는 최종산물로서, 미생물이 상수 속에 용존되어 있는 영양물질을 섭취하여 증식된 후 이화학적으로 부상 또는 침전시켜 분리된 미생물덩어리를 말한다. 그런데 이와 같은 상수오니는 자원화가 거의 이루어지고 있지 않아, 해양투기 및 매립을 주로 하고 있으며, 이에 따른 환경 오염의 문제가 대두되고 있다.In one aspect of the present invention, an adsorbent containing a purified sludge is described in detail. Sludge sludge used as the main raw material of the present invention is a final product generated in the course of water treatment, and refers to a microbial mass separated by physicochemically floating or sedimenting after being propagated by ingesting nutrients dissolved in the constant water. By the way, such a constant sludge is hardly made into resources, and the dumping and reclamation are mainly carried out, and thus the problem of environmental pollution has emerged.
상수 오니는 다양한 실험결과 환경문제를 발생 시키지 않고, 환경 산업에 유용한 특성을 보유할 수 있도록 재활용 할 수 있어, 활용가치가 향후 증대될 것으로 보이지만 현재는 그 활용도가 극히 미미한 실정이다. 본 발명에 의하면 이와 같은 상수오니를 활용함으로써, 공해 방지에 이바지 할 수 있을뿐더러 흡착능이 우수한 흡착제를 제공할 수 있다.The constant sludge can be recycled to possess useful characteristics for the environmental industry without causing environmental problems as a result of various experiments, and thus the utilization value is expected to increase in the future, but its utilization is very small at present. According to the present invention, by utilizing such a constant water sludge, it is possible to provide an adsorbent which can not only contribute to pollution prevention but also has excellent adsorption capacity.
본원에 따른 흡착제는 교반하면서 냉풍 건조된 상수 오니를 사용한다. 흡착제는, 이와 같이 건조된 오니를 파쇄하고, 상기 파쇄된 상수오니와 상기 상수오니에 대하여 5~15중량부의 인산 공급원을 혼합 교반하여 10~30 시간 교반 숙성하고, 100~300에서 5~15 시간 가열하여 숙성된 100~200 메쉬의 분말 인산 물질을 포함하며, 또한, 상기 파쇄된 상수오니와 상기 상수 오니에 대하여 5~15중량부의 황산 공급원을 혼합 교반하여 10~30 시간 교반 숙성하고, 100℃~300℃에서 5~15시간 가열하여 숙성된 100~200 메쉬의 분말 황산 물질을 포함한다. The adsorbent according to the present application uses constant sludge dried cold with stirring. The adsorbent is pulverized in this way, the dried sludge and 5-15 parts by weight of phosphoric acid source are mixed and stirred with respect to the crushed purified sludge and stirred for 10 to 30 hours, and aged at 100 to 300 for 5 to 15 hours. It comprises a 100 ~ 200 mesh powdered phosphoric acid material aged by heating, and further mixed and stirred 5-15 parts by weight of sulfuric acid source with respect to the crushed purified sludge and the constant sludge, stirred and aged for 10-30 hours, and 100 ℃ It contains 100 to 200 mesh powdered sulfuric acid material aged by heating at ˜300 ° C. for 5 to 15 hours.
이때, 인산 공급원이나 황산 공급원은 바람직하게는 인산이나 황산이다. 그러나 고가의 인산이나 황산을 반드시 사용할 필요는 없으며, 저가의 재활용 인산이나 황산을 사용할 수 있다 구체적으로, 인산 농도가 60~90%인 것이면 폐인산, 재생인산도 사용할 수 있으며, 또한 반도체 제조공정 등에서 에칭액으로 사용 후 나오는 폐인산을 사용할 수도 있다. 한편 황산 공급원은 황산 농도 30~70%인 것이면 폐황산, 재생황산도 사용할 수 있다. At this time, the phosphoric acid source or sulfuric acid source is preferably phosphoric acid or sulfuric acid. However, it is not necessary to use expensive phosphoric acid or sulfuric acid, and inexpensive recycled phosphoric acid or sulfuric acid can be used. Specifically, if the phosphoric acid concentration is 60 to 90%, waste phosphoric acid or regenerative phosphoric acid can also be used. Waste phosphoric acid which has been used after etching can also be used. On the other hand, sulfuric acid source can be used sulfuric acid, regeneration sulfuric acid if the sulfuric acid concentration is 30 ~ 70%.
본 발명의 다른 양태에 있어서, 흡착제는 상술한 상수 오니 대신에 화력 발전의 부산물인 애쉬류를 사용할 수 있다. 애쉬는 화력발전소에서 필수적으로 발생하는 부산물로서, 화력발전소 1 개소는 연간 약 80,000톤에서 100,000톤에 이르는 많은 양을 발생 시키지만, 적절한 재활용 방안이 마련되지 않아 90%이상 매립돼 버리는 실정이다.In another embodiment of the present invention, the adsorbent may use ash, which is a byproduct of thermal power generation, instead of the above-mentioned constant sludge. Ash is an essential by-product of thermal power plants. One thermal power plant generates a large amount of about 80,000 to 100,000 tons per year, but it is buried more than 90% because proper recycling plan is not provided.
그러나 애쉬는 다양한 실험결과 환경문제를 발생 시키지 않고, 환경 산업에 유용한 특성을 보유할 수 있도록 재활용 할 수 있어, 활용가치가 향후 증대될 것으로 보이지만 현재는 그 활용도가 극히 미미한 실정이다. 본 발명에 따르면 이와 같은 애쉬를 활용함으로써, 공해 방지에 이바지 할 뿐 아니라 흡착능이 우수한 흡착제를 제공할 수 있다.However, ash can be recycled to have useful characteristics for the environmental industry without causing environmental problems as a result of various experiments, and it is expected that the value of its use will increase in the future, but its utilization is very small at present. According to the present invention, by utilizing such an ash, it is possible to provide an adsorbent excellent in adsorption capacity as well as contributing to pollution prevention.
본 발명의 또 다른 양태는 상수 오니 또는 애쉬를 주원료로 하여 제조되는 흡착제에 관한 것으로, 이 흡착제는 돈사, 계분비료, 악취유발시설, 집진시설 등 다양한 현장 적용이 가능한 다기능성인 것을 특징으로 한다. Another aspect of the present invention relates to an adsorbent produced by using a constant sludge or ash as a main raw material, and the adsorbent is characterized in that it is versatile, which can be applied to various fields such as pig sand, manure fertilizer, odor inducing facilities, and dust collecting facilities.
본 발명에 의한 흡착제는 부산물만을 활용하여 만든 고기능성 재활용제품으로서, 제조원가가 매우 낮음에도 불구하고 그 흡착효과는 기존의 흡착제보다 월등히 우수하다. 본 발명의 흡착제는 돼지폐사저감제, 계분비료첨가제, 활성탄 대체제, 산업용 탈취제 등으로 적용될 수 있으며, 수년에 걸친 현장 적용 실험 결과 얻어진 현장 적용예를 제시하고자 한다. The adsorbent according to the present invention is a highly functional recycled product made using only by-products, and although the manufacturing cost is very low, the adsorption effect is much better than that of the conventional adsorbent. Adsorbents of the present invention can be applied as a pig mortality reducing agent, manure fertilizer additives, activated carbon substitutes, industrial deodorants, etc., to present a field application example obtained by the field application experiments over the years.
먼저, 본 발명에 따른 흡착제를 포함하는 돼지폐사저감제 적용예에 대해 설명한다. 양돈사는 지역이나 계절에 관계 없이, 눈과 코를 찌르는 강렬한 가스로 인해 일반 사람의 경우 호흡이 곤란하고 눈을 계속 뜨고 있기 어려울 정도이다. 돼지의 경우 항상 눈이 충혈되어 있고 눈곱이 끼어 있으며 먹을 때를 제외하고는 거의 누워서 지내는 형편이다. 이는 분뇨 속에 발생하는 다량의 암모니아가스에 중독되어 나타나는 현상으로서, 암모니아는 대기 중의 먼지까지 돼지의 호흡기를 통해 체내에 흡입되어 돼지 폐사의 주요인으로 작용하고 있으나 아직 효율적으로 암모니아가스를 제어하는 상용제품이 없어 농가의 애를 태우고 있는 실정이다. First, the application example of the pig lung mortality reducing agent containing the adsorbent according to the present invention will be described. Pigs, regardless of location or season, have intense breathing gas on their eyes and nose, making it difficult for the average person to breathe and keep their eyes open. Pigs are always congested in their eyes, and their eyes are pinched, and they lie down almost except when they eat. This is a phenomenon that is poisoned by a large amount of ammonia gas generated in the manure, ammonia is inhaled into the body through the respiratory organs of pigs to the dust in the air, which acts as a major cause of death of pigs, but there is still a commercial product that efficiently controls ammonia gas There is no way to burn the children of the farm.
본 발명에 의한 흡착제를 포함하는 돼지폐사저감제를 돈사 면적 33m2당 1kg씩 바닥에 살포하고 나면, 약 3시간 후부터 암모니아농도가 줄어들기 시작하여 24시간 경과 후 암모니아가 우효하게 감소 제어된다. 살포한 다음 날에 돈사에 들어가 보면, 사람의 눈과 코를 찌르는 가스가 사라진 것을 느낄 수가 있으며, 돼지 안구의 충혈상태가 완화되기 시작하는 것을 볼 수 있고, 늘 누워 있던 돼지가 일어서서 활동을 하는 것을 목격하게 된다. After the pig mortar reducing agent containing the adsorbent according to the present invention is sprayed on the floor by 1 kg per pig area 33 m 2 , ammonia concentration begins to decrease after about 3 hours and ammonia is effectively reduced after 24 hours. The day after the spray, you can feel the disappearance of the gas from your eyes and nose, you can see the redness of the pig's eyeballs begin to relieve, and the pig who has been lying down You will see that.
이는 결과적으로 돼지의 폐사율을 줄이면서 생육환경을 개선하여 축산 농가의 소득증대를 가져오게 하며, 작업자의 작업환경을 개선하여 경쟁력 강화 및 축산농가 삶의 질 향상에도 기여하는 것으로 판단된다.As a result, it is believed that it contributes to raising the income of livestock farmers by reducing the mortality rate of pigs and improving the growth environment, and contributing to enhancing the competitiveness of workers and improving the quality of life of livestock farmers by improving the working environment of workers.
다음으로, 계분의 경우 질소와 인, 유기물 등을 함유하고 있어 우수한 비료의 원료로 인정받고 있으나, 요산과 기타 원인물질에 의한 다량의 악취는 비료작업능률의 저하, 2차 가스 발생에 의한 작물의 고사 등 여러 가지 문제점으로 인해 비료공장과 농가에서 이용을 기피하고 있는 것이 현실이다. 한편 우분이나 돈분을 활용한 퇴비의 경우, 톱밥 가격의 지속적인 상승과 공급부족으로 인해 채산성이 점점 떨어지고 있다. Next, in the case of chicken flour, it contains nitrogen, phosphorus, organic matter, etc., but it is recognized as an excellent raw material of fertilizer. However, a large amount of odor by uric acid and other causative substances is caused by deterioration of fertilizer working efficiency and secondary gas generation. Due to various problems such as dead-ends, the reality is that they are avoiding use in fertilizer factories and farms. On the other hand, composts made from dairy or pig meals are becoming less profitable due to the continuous rise in sawdust prices and supply shortages.
본 발명에 의한 흡착제를 포함하는 계분비료첨가제를 사용하여 계분을 비료로 생산할 경우, 톱밥을 사용하지 않고 양질의 비료를 만들 수 있음이 현장 테스트를 통해 확인되었다. 구체적인 사례를 적시해보면, 계분 100중량에 생석회10중량을 혼합교반하게 되면 생석회가 계분 속에 있는 수분을 흡수하면서 수화반응을 일으켜 상온 25에서 40이상 발열을 하게 되며, 계분은 산성에서 알칼리성으로 물성이 변화된다. 이 과정에서 발생하는 악취의 종류가 바뀌게 되고 1시간 정도 반응을 시킨 후 상기 계분비료첨가제를 투입 교반하게 되면 약 3시간 경과 시부터 악취를 제어하기 시작하여 24시간이 경과하게 되면 발생 악취의 95%이상을 절감 제어하게 된다. 이후 표면에 흰곰팡이가 피는 것을 목도 할 수 있는 바, 이는 후숙 과정이 일어나는 것을 의미한다. When the manure is produced as a fertilizer using the manure fertilizer additive containing the adsorbent according to the present invention, it was confirmed through field tests that a good fertilizer can be made without using sawdust. When concrete cases are mixed, when 100 weight of poultry is mixed with 10 weights of quicklime, the quicklime absorbs the moisture in the poultry, causing hydration reactions and exothermic heat from room temperature 25 to 40. do. If the type of odor generated in this process is changed and reacted for about 1 hour, and then the manure additive is added and stirred, 95% of the odor generated after 24 hours starts to control the odor. The control is reduced. You can also see white mold on the surface, which means that the ripening process takes place.
이렇게 생산된 계분 비료는 비료공정규격 테스트를 거쳐 퇴비로서의 법적 조건을 충족하는 것을 확인하였으며, 상추재배실험을 통해 계분비료 살포지와 비살포지의 상추 수확량이 30%정도 차이가 있음을 확인할 수 있었다. 더욱이 이러한 계분비료는 생석회가 첨가되어 토양개량효과를 주고 계분 고유의 비료효능과 석회의 주성분인 칼슘이 작물의 조직 강화와 토지 속 영양분 흡수능을 증대시켜 작물의 품질 상승, 수확량 증대를 가져오게 된다.The manure fertilizer produced in this way was tested to meet the legal requirements as a compost through the fertilizer process standard test, and lettuce cultivation experiments showed that the lettuce yield between the manure spreading and non-spraying was about 30%. Furthermore, these manure fertilizers are added with quicklime to improve the soil, and the inherent fertilizer effect and calcium, the main ingredient of lime, enhance the crop's structure and increase the absorption of nutrients in the land, resulting in an increase in crop quality and yield.
그 다음으로, 본 발명에 따른 흡착제는 활성탄 대체재로도 활용될 수 있다. 활성탄은 야자계 활성탄과 석탄계 활성탄이 주로 사용되고 있으며, 전량 수입에 의존하고 있는 실정이다. 석탄계 활성탄의 주 수입원은 중국으로, 2006년 인천항 도착도가 톤당 70만원이던 것이 현재 톤당 150만원에 수입되고 있으며, 가격이 두 배 이상 급증하여 업체의 부담이 가중되고 있다. 게다가, 중국 정부에서 천연자원의 해외수출을 점차 줄이고 있는 실정임을 감안하면 대체재 개발이 시급한 실정이다. 또한 국내에서 가동 중인 대부분의 공장시설은 관련법에 의거 집진시설 및 악취방지시설을 해야 하는데, 대부분 흡착제로 활성탄을 사용하고 있으며 시장 규모는 연간 1조원 정도로 추산되고 있다. Next, the adsorbent according to the present invention can also be utilized as an alternative to activated carbon. Activated carbon is mainly palm-based activated carbon and coal-based activated carbon, which is dependent on imports. The main source of import of coal-based activated carbon is China. In 2006, the arrival of Incheon Port was 700,000 won per ton, and currently imports at 1.5 million won per ton. The price has soared more than twice, increasing the burden on the company. In addition, the development of alternative materials is urgent given that the Chinese government is gradually reducing the export of natural resources. In addition, most plant facilities operating in Korea require dust collection facilities and odor prevention facilities in accordance with the related laws. Most of them use activated carbon as adsorbent and the market size is estimated to be about 1 trillion won per year.
본 발명에 의한 흡착제는 석탄계 활성탄보다 비표면적이 2~4배 가량 큰 것으로 관찰되며, 이는 상술한 PMC 구조에 기인하는 것으로, 본 발명에 따른 흡착제의 물리적 흡착능력이 활성탄 보다 우수하기 때문에 기존의 활성탄을 충분히 대체할 수 있다. 일반적으로 활성탄의 경우 특정 악취 물질의 흡착에 효과적인 것으로 알려져 있고, 본 발명에 의한 흡착제는 상기 특정 악취 물질 외에도 활성탄이 제어하지 못하는 악취물질까지 흡수, 제어할 수 있기 때문이다. 또한, 요오드 흡착량 테스트 결과 1,050g/g이상으로 측정되었으며, 경도는 92%이상으로 측정되어 기존 활성탄의 규격에도 부합함을 확인할 수 있었다. It is observed that the adsorbent according to the present invention has a specific surface area of about 2 to 4 times larger than that of coal-based activated carbon, which is due to the above-described PMC structure. Can be replaced sufficiently. In general, activated carbon is known to be effective for adsorption of a particular malodorous substance, and the adsorbent according to the present invention can absorb and control a malodorous substance that activated carbon cannot control in addition to the specific malodorous substance. In addition, the iodine adsorption test results were measured at more than 1,050g / g, the hardness was measured at more than 92% was confirmed to meet the specifications of the existing activated carbon.
본 발명에 의한 흡착제는 상기 PMC에 의해 활성탄과 대등 또는 우월한 흡착능력을 갖고 있는 것으로 평가되고 있으며, 이에 본 발명자는 본원에 따른 흡착제를 분말상과 입상(Pellet)으로 제조하여 피혁가공공장, 음식물쓰레기처리시설, 퇴비공장, 도축장 등에서 현장 적용을 통해 활성탄대체재로서의 가능성을 확인하였다. 본 발명에 따라 제조된 입상 흡착제를 도 2에 도시하였다. The adsorbent according to the present invention is evaluated to have the same or superior adsorption capacity with activated carbon by the PMC. Thus, the present inventors prepare the adsorbent according to the present invention in powder form and pellets, and process the leather processing plant and food waste. The application of on-site applications in facilities, composting plants, slaughterhouses, etc. confirmed the potential as an activated carbon substitute. A granular adsorbent prepared according to the invention is shown in FIG. 2.
구체적인 적용예로, 부산 소재 한 피혁공장에서 다량의 악취가 발생하여 민원을 유발시키면서 작업자의 작업능률에도 지대한 부정적 영향을 미치고 있어 본 흡착제를 이용하여 주 발생 원인인 배수조 주변에 살포한 결과, 12시간 경과 시부터 악취의 발생이 줄기 시작하여 48시간이 경과하자 관능법에 의한 탐지가 어려울 정도로 악취가 제어됐음을 확인할 수 있었다.As a specific application, a large amount of odor was generated in a leather factory in Busan, which caused civil complaints and had a great negative effect on worker's work efficiency. Occurrence of odor began to elapse after 48 hours, and it was confirmed that the odor was controlled so that detection by sensory method was difficult.
마지막으로, 본원에 따른 흡착제는 산업용 탈취제로 적용될 수 있으며 본원 발명자는 이를 여러 경로를 통해 확인하였다. 대표적인 예로는, 음식물쓰레기와 도축잔재물에 관한 것을 들 수 있다. 이들은 알데하이드, 아민, 설파이드와 기타 다양한 악취물질을 함유하고 있고, 이와 같은 악취원인물질을 유효하게 제어할 수 있는 탈취제는 아직까지 없는 실정이며, 이는 쓰레기 처리장이나 도축장 주변지역에서의 민원제기 및 작업능률저하 등의 또 다른 문제를 불러오고 있다. Finally, the adsorbent according to the present application can be applied as an industrial deodorant and the inventors have confirmed this through several routes. Representative examples include food waste and slaughter residues. They contain aldehydes, amines, sulfides and many other odorous substances, and there is no deodorant that can effectively control such odorous substances. It is also causing another problem such as deterioration.
그러나 동 물질 100중량부에 본 발명에 의한 흡착제(산업용 탈취제)를 10~30중량부를 혼합 교반하여 상온에서 숙성시키면, 24시간 경과 후 발생 악취를 98%이상 절감 제어하여 작업자의 작업환경개선, 다양한 재활용처 확보, 악취민원의 해결 등 다양한 효과를 가져와, 산업용 탈취제로 유용하게 기능할 수 있는 것이다.However, by mixing 10-30 parts by weight of the adsorbent (industrial deodorant) according to the present invention to 100 parts by weight of copper material and aging at room temperature, the odor generated after 24 hours is reduced by more than 98% to improve the working environment of workers, It will be useful as an industrial deodorant by bringing various effects such as securing a recycling point and solving odor complaints.
본원에 따른 흡착제를 제조하는 바람직한 방법을 상술한다. Preferred methods of preparing the adsorbent according to the invention are detailed.
바람직하게 본 발명에 의한 흡착제는, 상수오니를 교반시키면서 냉풍건조하는 제1단계; 냉풍건조한 상수오니를 파쇄하는 제2단계; 폐인산, 재생인산, 인산으로 이루어지는 군으로부터 선택되는 인산물질과 상기 파쇄된 상수오니를 혼합교반하여 10시간 내지 30시간 교반하여 숙성하는 제3단계; 폐황산, 재생황산, 황산으로 이루어지는 군으로부터 선택되는 황산물질과 상기 파쇄된 상수오니를 혼합교반하여 10시간 내지 30시간 교반하여 숙성하는 제4단계; 상기 제3단계 및 제4단계의 결과물을 100℃~300℃에서 5시간 내지 15시간동안 가열하여 분말화하는 제5단계; 상기 제5단계의 결과물을 100~150 메쉬로 분쇄하는 제6단계; 상기 제6단계를 거친 제3단계 및 제4단계의 결과물을 혼합비(A)를 55%:45%<A<100:0% 가 되도록 혼합하는 제 7단계로 이루어진 방법으로 제조될 수 있다. Preferably, the adsorbent according to the present invention comprises: a first step of air drying with stirring the purified sludge; A second step of crushing the cold-dried purified sludge; A third step of mixing and stirring the phosphate material selected from the group consisting of waste phosphoric acid, regenerated phosphoric acid and phosphoric acid and stirring the crushed purified sludge for 10 to 30 hours; A fourth step of mixing and stirring a sulfuric acid material selected from the group consisting of waste sulfuric acid, regenerated sulfuric acid and sulfuric acid and the crushed purified sludge for 10 to 30 hours; A fifth step of powdering the resultant of the third and fourth steps by heating at 100 ° C. to 300 ° C. for 5 to 15 hours; A sixth step of grinding the resultant product of the fifth step into 100 to 150 meshes; The result of the third step and the fourth step through the sixth step may be prepared by a method consisting of the seventh step of mixing the mixing ratio (A) to 55%: 45% <A <100: 0%.
위 방법에 있어서 선택적으로, 상수오니와 인산 물질과 황산 물질을 동시에 혼합힐 수 있으며, 이 경우 위 제 계 및 제 계는 파쇄된 상수오니와 인산 물질 및 황산 물질을 함께 혼합하는 형태로 실시가 가능하다.In the above method, it is possible to mix the sludge with phosphate and sulfuric acid at the same time. In this case, the above system and the system can be carried out by mixing the crushed sludge with the phosphate and sulfate. Do.
또한 본 발명의 탈취제는 바람직하게, 폐인산, 재생인산, 인산으로 이루어지는 군으로부터 선택되는 인산물질과 상수오니를 혼합한 제1탈취제, 폐황산, 재생황산, 황산으로 이루어지는 군으로부터 선택되는 황산물질과 상수오니를 혼합한 제2탈취제, 그리고 제1탈취제와 제2탈취제를 혼합한 제3탈취제를 준비하는 방법으로 제조될 수 있으며, 본 발명에 있어서의 제 3탈취제를 이루는 제1탈취제와 제 2탈취제의 함량비(A)는 55:45<A<100:0의 범위를 만족하는 것이 바람직하다.In addition, the deodorant of the present invention is preferably a phosphate material selected from the group consisting of waste phosphoric acid, regenerated phosphoric acid, phosphoric acid and a sulfuric acid material selected from the group consisting of a first deodorant, waste sulfuric acid, regenerative sulfuric acid, sulfuric acid It can be prepared by a method of preparing a second deodorant mixed with the water sludge, and a third deodorant mixed with the first deodorant and the second deodorant, the first deodorant and the second deodorant forming the third deodorant in the present invention The content ratio (A) of preferably satisfies the range of 55:45 <A <100: 0.
이하 본 발명에 따른 흡착제를 제조하는 방법을 단계별로 보다 상세히 설명한다. Hereinafter, the method of preparing the adsorbent according to the present invention will be described in more detail step by step.
본 발명에서는 흡착제를 제조하는 첫 단계는 상수오니를 교반하면서 냉풍건조를 시키는 것이다. 교반시에는 본 기술분야에 사용되는 일반적인 교반기를 사용할 수 있지만, 로타리식 교반기를 사용하는 것이 바람직하다. 또한, 건조시에는 냉풍건조 또는 상온건조를 하는 것이 바람직하며, 약 1일 내지 2일 또는 더욱 바람직하게는 그 이상의 기간 동안 건조를 행하는 것이 바람직하다.In the present invention, the first step of preparing the adsorbent is to perform cold air drying while stirring the purified sludge. While stirring may be used a general stirrer used in the art, it is preferred to use a rotary stirrer. In addition, it is preferable to carry out cold air drying or room temperature drying at the time of drying, and it is preferable to carry out drying for about 1 day-2 days or more preferably the period beyond.
상수오니를 건조한 후에는, 파쇄기를 사용해서 이를 파쇄하고, 이어서 여기에 폐인산 또는 재생인산 또는 인산을 혼합하여 교반하고, 10시간 내지 30시간 숙성시킨다. 이때 선택적으로 건조된 상수 오니 대신에 애쉬를 사용할 수도 있다. After drying the purified sludge, it is crushed using a crusher, and then mixed with a mixture of waste phosphoric acid or regenerated phosphoric acid or phosphoric acid, and aged for 10 to 30 hours. In this case, ash may be used instead of the dried constant sludge.
폐인산 또는 재생인산 또는 인산을 투입하는 양은 상수오니 또는 애쉬류의 전체 질량에 대해서 5중량부 내지 15중량부를 투입하는 것이 바람직하다. 마찬가지로 상수오니를 건조후, 폐황산 또는 재생황산 또는 황산물질을 첨가하는 경우에도 그 투입량은 상수오니 또는 애쉬류의 전체량에 대해서 5중량부 내지 15중량부 정도가 바람직하다. The amount of waste phosphoric acid or regenerative phosphoric acid or phosphoric acid is preferably added in an amount of 5 parts by weight to 15 parts by weight based on the total mass of the purified sludge or ash. Similarly, in the case of adding spent sulfuric acid, regenerated sulfuric acid or sulfuric acid after drying the sludge, the amount thereof is preferably about 5 parts by weight to 15 parts by weight based on the total amount of the purified sludge or ash.
이어서, 이들을 100 내지 300에서 10시간 내지 15시간 반응시켜, 상기 혼합물들을 반응시킨다. 이때, 상수오니 및/또는 애쉬류와 폐인산(내지는 재생인산 또는 인산)의 혼합물과, 상수오니 및/또는 애쉬류와 폐황산(내지는 재생황산 또는 황산)의 혼합물을 각각 따로 가열하여, 이 두가지 결과물을 각각 따로따로 사용하거나 또는 이를 적절히 배합하는 것도 가능하다. Then, these are reacted at 100 to 300 for 10 to 15 hours to react the mixtures. At this time, the mixture of purified sludge and / or ash and waste phosphoric acid (or recycled phosphoric acid or phosphoric acid) and the mixture of purified sludge and / or ash and waste sulfuric acid (or recycled sulfuric acid or sulfuric acid) are separately heated. It is also possible to use the results separately or to combine them properly.
이어서 이들을 100~200메쉬로 분쇄한 후, 상수오니 및/또는 애쉬류와 폐인산등의 혼합물(제1탈취제), 그리고, 상수오니 및/또는 애쉬류와 폐황산과의 혼합물(제2탈취제)을 서로 혼합하여 최종 탈취제(제3탈취제)를 생산하는데, 그 혼합비율(A)은 바람직하게는 질량 기준 50 : 50 < A < 100 : 0 이다.Subsequently, the mixture is pulverized to 100 to 200 mesh, and then a mixture of purified sludge and / or ash and waste phosphoric acid (first deodorant), and a mixture of purified sludge and / or ash and waste sulfuric acid (second deodorant) Are mixed with each other to produce a final deodorant (third deodorant), the mixing ratio A of which is preferably 50:50 <A <100: 10 by mass.
바람직한 양태에 있어서, 위와 같이 총 4종의 흡착제를 생산할 수 있으며, 이들 각 흡착제는 적용분야 별로 특화될 수 있다.In a preferred embodiment, a total of four kinds of adsorbents can be produced as described above, and each of these adsorbents can be specialized for each application.
이하, 본 발명의 구체적인 실시형태에 대해서 기술한다. 다만, 하기의 실시형태는 본 발명의 바람직한 태양을 소개하는 것일 뿐, 본 발명이 이들 실시예에 나타난 태양으로 한정되는 것은 아니다.Hereinafter, specific embodiment of this invention is described. However, the following embodiment only introduces the preferable aspect of this invention, and this invention is not limited to the aspect shown in these Examples.
실시예 1~실시예 6Example 1-Example 6
상수오니 및/또는 애쉬류를 1일 냉풍건조시킨 후, 파쇄기를 이용해서 이를 파쇄했다. 이어서, 상수오니 및/또는 애쉬류를 농도 63%의 폐인산 또는 농도 50%의 폐황산과 섞어서 200에서 10시간 가열한 후, 이를 200메쉬로 분쇄하였다. 상수오니, 애쉬류, 폐인산 및 폐황산의 투입량, 그리고, 자세한 제조방법은 하기의 표 1과 같다.The sludge and / or ash was cold-dried for 1 day and then crushed using a crusher. The sludge and / or ash was then mixed with waste phosphoric acid at a concentration of 63% or spent sulfuric acid at a concentration of 50% and heated at 200 for 10 hours, which was then ground to 200 mesh. The amount of purified sludge, ash, waste phosphoric acid and waste sulfuric acid, and a detailed manufacturing method are shown in Table 1 below.
표 1
상수오니 애쉬류 폐인산 폐황산 제법
실시예 1 125g 12g 상수오니 125g을 폐인산 12g과 혼합하여 200℃에서 10시간 가열하여 제조함.
실시예 2 125g 12g 상수오니 125g을 폐황산 12g과 혼합하여 200℃에서 10시간 가열하여 제조함.
실시예 3 125g 6.25g 6.25g 상수오니 62.5g을 폐인산 6.25g와 혼합하여 200℃에서 10시간 가열하여 제조하고, 상수오니62.5g을 폐황산 6.25g와 혼합하여 200℃에서 10시간 가열하여 제조한 것을 혼합하여 제조
실시예 4 62.5g 62.5g 12.5g 상수오니62.5g과 애쉬류62.5g을 먼저 혼합한 후, 폐인산 12.5g과 혼합하여 200℃에서 10시간 가열하여 제조
실시예 5 62.5g 62.5g 12.5g 상수오니62.5g과 애쉬류62.5g을 먼저 혼합한 후, 폐황산 12.5g과 혼합하여 200℃에서 10시간 가열하여 제조
실시예 6 62.5g 62.5g 62.5g 62.5g 상수오니 62.5g을 폐인산 6.25g와 혼합하여 200℃에서 10시간 가열하여 제조하고, 상수오니62.5g을 폐황산 6.25g와 혼합하여 200℃에서 10시간 가열하여 제조한 것을 혼합하여 제조
Table 1
Water purifier Ash Waste phosphate Spent sulfuric acid quite
Example 1 125 g 12g Prepared by mixing 125g of purified water with 12g of waste phosphoric acid and heating at 200 ℃ for 10 hours.
Example 2 125 g 12g Prepared by mixing 125g of purified water with 12g of waste sulfuric acid and heating at 200 ℃ for 10 hours.
Example 3 125 g 6.25 g 6.25 g Prepared by mixing 62.5g of purified water sludge with 6.25g of waste phosphoric acid and heating it at 200 ℃ for 10 hours, by mixing 62.5g of purified water with 6.25g of waste sulfuric acid and heating it at 200 ℃ for 10 hours
Example 4 62.5 g 62.5 g 12.5 g 62.5 g of purified water sludge and 62.5 g of ash were mixed first, and then mixed with 12.5 g of waste phosphoric acid and heated at 200 ° C. for 10 hours.
Example 5 62.5 g 62.5 g 12.5 g 62.5 g of purified water sludge and 62.5 g of ash are mixed first, and then mixed with 12.5 g of waste sulfuric acid and heated at 200 ° C. for 10 hours.
Example 6 62.5 g 62.5 g 62.5 g 62.5 g Prepared by mixing 62.5g of purified water sludge with 6.25g of waste phosphoric acid and heating it at 200 ℃ for 10 hours, by mixing 62.5g of purified water with 6.25g of waste sulfuric acid and heating it at 200 ℃ for 10 hours
다음은 실제 시험한 예를 제시한 것으로 시험예 1은 돼지폐사저감제에 대한 적용 예를, 시험예 2는 계분비료첨가제에 대한 적용 예를, 시험예 3은 활성탄 대체재에 대한 적용 예를, 시험예 4는 산업용 탈취제애 대한 적용 예를 적시한 것으로, 본 발명에 따른 흡착제는 이외에도 다양한 분야에 적용할 수 있는 다능성을 가진다.The following is an example of the actual test. Test Example 1 is applied to pig mortality reducing agent, Test Example 2 is applied to fertilizer additives, and Test Example 3 is applied to activated carbon substitutes. Example 4 shows an application example for the industrial deodorant, the adsorbent according to the present invention has a versatility that can be applied to various fields in addition to.
시험예 1Test Example 1
실시예 1~6에서 제조된 돼지폐사저감제를 이용하여 탈취실험을 행했다. 돈분 10kg를 혼합소화반응기에 넣고 5분간 교반하여 골고루 혼합한 다음, 돼지폐사저감제를 2kg투입교반한 후 20분 경과시부터 검지관으로 암모니아 농도를 최초 측정한 후 총 5회를 더 측정하여 결과를 기록하여 표 2에 제시하였다. The deodorization experiment was performed using the pig mortality reducing agent prepared in Examples 1-6. 10 kg of pig powder was mixed in a mixed digestion reactor, mixed for 5 minutes, and mixed evenly. After 2 minutes of stirring with 2 kg of pig mortality reducing agent, the ammonia concentration was first measured by a detection tube. Are recorded and presented in Table 2.
표 2
돼지폐사저감제 경과시간(분) 돈분(ppm) 돈분+돼지폐사저감제(ppm) 암모니아 제어율 (%)
실시예 1 5 150
25 149 70 53.02
185 150 15 90.00
365 147 7 95.24
725 145 5 96.55
1445 140 2 98.57
TABLE 2
Pig mortality reducing agent Elapsed time (minutes) Money (ppm) Pig meal + pig lung mortality reduction (ppm) Ammonia Control Rate (%)
Example 1 5 150
25 149 70 53.02
185 150 15 90.00
365 147 7 95.24
725 145 5 96.55
1445 140 2 98.57
시험예 2Test Example 2
실시예 1~6에서 제조된 계분비료첨가제를 이용하여 탈취실험을 행했다. 계분 10kg를 혼합소화반응기에 넣고 5분간 교반하여 골고루 혼합한 다음, 생석회 1kg을 투입교반한 후 1시간동안 수화반응이 일어나도록 반응시간을 둔 후, 계분비료첨가제를 2kg투입교반한 후 30분경과 시부터 검지관으로 암모니아 농도를 최초 측정한 후 총 5회를 더 측정하여 결과를 기록하여 표 3에 제시하였다.Deodorization experiments were carried out using the fertilizer additives prepared in Examples 1-6. 10kg of the mixture is put into the mixed digestion reactor, mixed by stirring for 5 minutes, and then mixed with 1kg of quicklime and allowed to react for 1 hour to allow the hydration reaction to occur, and then 30 minutes after stirring with 2kg of the fertilizer additive. After measuring the ammonia concentration with a detector tube from the beginning, a total of 5 times was measured and the results were recorded and shown in Table 3.
표 3
계분비료첨가제 경과시간(분) 계분+생석회(ppm) 계분+생석회+계분비료첨가제(ppm) 암모니아 제어율 (%)
실시예 2 5 340
65 450 420 06.67
95 430 370 13.95
185 425 174 59.60
725 410 57 86.10
1445 370 8 97.84
TABLE 3
Fertilizer Additives Elapsed time (minutes) Total meal + quicklime (ppm) Poultry + quicklime + fertilizer additives (ppm) Ammonia Control Rate (%)
Example 2 5 340
65 450 420 06.67
95 430 370 13.95
185 425 174 59.60
725 410 57 86.10
1445 370 8 97.84
시험예 3Test Example 3
실시예 1~6에서 제조된 흡착제를 이용하여 활성탄 대체재로서 적용가능여부에 대한 실험을 행했다. 활성탄 대체재(흡착제)를 직경 5mm의 Pellet으로 성형한 후, 요오드 흡착량과 경도를 확인한 결과 표 4와 같다.Experiments were carried out using the adsorbents prepared in Examples 1-6 for applicability as activated carbon substitutes. Activated carbon substitutes (adsorbents) were molded into pellets having a diameter of 5 mm, and then the adsorption amount and hardness of iodine were checked.
표 4
항 목 1급 2급 3급 활성탄 대체재
건조감량(%) 5이하 5이하 5이하 5
경도(%) 90이상 90이상 90이상 92
충전밀도(g/ml) 0.48이하 0.52이하 0.56이하 0.53
요오드흡착력(mg/g) 1,100이상 1,000이상 900이상 1,050
벤젠평형흡착성능(%) 35이상 33이상 30이상 33
입도(%) 95이상 90이상 90이상 93
Table 4
Item 1st grade 2nd class Level 3 Activated Carbon Alternatives
Loss on Drying (%) 5 or less 5 or less 5 or less 5
Hardness(%) over 90 over 90 over 90 92
Filling density (g / ml) 0.48 or less 0.52 or less 0.56 or less 0.53
Iodine Adsorption (mg / g) 1,100 or more 1,000 or more More than 900 1,050
Benzene equilibrium adsorption performance (%) 35 or more 33 or more 30 or more 33
Particle size (%) 95 or more over 90 over 90 93
시험예 4Test Example 4
실시예 1~6에서 제조된 산업용 탈취제를 이용하여 흡착실험을 행했다. 산업용 탈취제(흡착제)를 직경 5mm의 Pellet으로 성형한 후, 백필터에 투입하여 도축장에 설치되어 있는 통기도가 20cc/cm2/sec인 용량의 악취방지시설에 설치한 후, 처리능력을 측정하여 표 5에 제시하였다. Adsorption experiments were performed using the industrial deodorant prepared in Examples 1-6. The industrial deodorant (adsorbent) was molded into pellets with a diameter of 5 mm, and then put into a bag filter and installed in a odor prevention facility with a capacity of 20 cc / cm 2 / sec installed in the slaughterhouse. Presented in 5.
표 5 단위 : %
산업용 탈취제 Bag Filter(PE) Bag Filter(산업용 탈취제)
실시예 3 95 94
Table 5 unit : %
Industrial deodorants Bag Filter (PE) Bag Filter (Industrial Deodorant)
Example 3 95 94
이상 표에 정리된 결과로부터 알 수 있는 바와 같이, 본 발명에 의한 흡착제는 흡착력이 우수하여, 돼지폐사저감제, 계분비료첨가제, 활성탄대체재, 산업용 탈취제로써 극히 우수한 적용을 보이고 있으므로, 페기물을 자원화하여 높은 경제성과 효율을 가지는 제품이라는 것을 알 수 있다.As can be seen from the results summarized in the above table, the adsorbent according to the present invention has excellent adsorptive power, and shows extremely excellent application as a pig lung deadener, manure fertilizer additive, activated carbon substitute, and industrial deodorant. It can be seen that the product has high economical efficiency.
본 발명의 흡착제를 산업적으로 이용하는 경우, 상수오니의 처리(매립, 소각 등)를 위해 소요되는 연간 200억 원 가량의 정부 예산, 연간 900억 원대로 추정되는 돼폐사저감제 시장, 470억 원대의 계분비료첨가제 시장, 연간 1조원대에 육박하는 활성탄의 시장, 연간 3,000억 원대에 이르고 있는 탈취제 시장 등을 감안할 때, 10%의 마켓 쉐어를 한다고 가정하여도 1,500억 대의 시장이 형성될 것으로 추정된다. When using the adsorbent of the present invention industrially, the government budget of about 20 billion won for the treatment of landfill sludge (landfill, incineration, etc.), the pig waste reduction market estimated to be 90 billion won per year, the amount of 47 billion won Considering the fertilizer additives market, the market of activated carbon nearing KRW 1 trillion annually, and the deodorant market reaching KRW 300 billion annually, the market share is estimated to be 150 billion assuming a 10% market share.
특히, 활성탄의 경우 전량 수입에 의존하는 점을 감안하면 외화 유출 차단 및 안정적인 자원 확보, 수입대체효과 등 다양한 경제적, 산업적, 환경적인 플러스 효과를 가져올 것으로 추정된다.In particular, in the case of activated carbon, it is expected to bring various economic, industrial and environmental positive effects such as blocking foreign currency outflow, securing stable resources, and import substitution effect.

Claims (10)

  1. 냉풍 건조된 상수오니를 파쇄하고, 상기 파쇄된 상수오니와 상기 상수오니에 대하여 5~15중량부의 인산 공급원을 혼합 교반하여 10~30 시간 교반 숙성하고, 100℃~300℃에서 5~15 시간 가열하여 숙성된 분말 인산 물질; 및Crush the cold-dried purified sludge, mix and stir 5-15 parts by weight of phosphoric acid source with respect to the crushed purified sludge and the purified sludge for 10 to 30 hours, and then aged at 100-300 ° C for 5-15 hours. Powdered phosphoric acid material that has been aged; And
    냉풍 건조된 상수 오니를 파쇄하고, 상기 파쇄된 상수오니와 상기 상수 오니에 대하여 5~15중량부의 황산 공급원을 혼합 교반하여 10~30 시간 교반 숙성하고, 100℃~300℃에서 5~15시간 가열하여 숙성된 분말 황산 물질을 포함하는 흡착제에 있어서, Crush the cold-dried purified sludge, mix and stir 5-15 parts by weight of sulfuric acid source with respect to the crushed purified sludge and the constant sludge for 10 to 30 hours, and stir and heat at 100 ° C to 300 ° C for 5 to 15 hours. In the adsorbent comprising a powdered sulfuric acid material aged by
    상기 인산 공급원은 인산 농도가 60~90%이며, 폐인산, 재생인산 및 인산으로 이루어지는 군에서 선택되는 하나 이상인 것이고, The phosphoric acid source is a phosphoric acid concentration of 60 to 90%, at least one selected from the group consisting of waste phosphoric acid, regenerated phosphoric acid and phosphoric acid,
    상기 황산 공급원은 황산 농도 30~70%이며, 폐황산, 재생황산 및 황산으로 이루어지는 군에서 선택 되는 하나 이상인 것이고, The sulfuric acid source is sulfuric acid concentration of 30 to 70%, at least one selected from the group consisting of spent sulfuric acid, regenerated sulfuric acid and sulfuric acid,
    상기 분말 인산 물질 및 상기 분말 황산 물질은 100~200메쉬의 분말이고,The powdered phosphate material and the powdered sulfuric acid material is a powder of 100 ~ 200 mesh,
    상기 흡착제는 분말 또는 펠렛 형상을 가지며, 경도는 92% 이상이고, The adsorbent has a powder or pellet shape, the hardness is 92% or more,
    상기 분말 및 펠렛 형상은 복층다공형원통 구조인 것을 특징으로 하는 다기능성 흡착제.The powder and pellets are multi-functional adsorbent, characterized in that the multi-layer porous cylinder structure.
  2. 제 1 항에 있어서, 상기 흡착제는 상기 분말 인산 물질과 상기 분말 황산 물질을 혼합비(A)가 55% : 45% < A < 100% : 0% 가 되도록 포함하는 것을 특징으로 하는 흡착제.The adsorbent of claim 1, wherein the adsorbent comprises the powdered phosphate material and the powdered sulfuric acid material such that a mixing ratio (A) is 55%: 45% <A <100%: 0%.
  3. 화력발전의 부산물인 애쉬와 상기 애쉬에 대하여 5~15중량부의 인산 공급원을 혼합 교반하여 10~30 시간 교반 숙성하고, 100℃~300℃에서 5~15 시간 가열하여 숙성된 분말 인산 물질; 및Powdered phosphoric acid material which is aged by stirring for 10 to 30 hours by mixing and stirring 5-15 parts by weight of phosphoric acid source with respect to the ash which is a by-product of thermal power generation, and heating at 100 ° C to 300 ° C for 5 to 15 hours; And
    화력발전의 부산물인 애쉬와 상기 애쉬에 대하여 5~15중량부의 황산 공급원을 혼합 교반하여 10~30 시간 교반 숙성하고, 100℃~300℃에서 5~15시간 가열하여 숙성된 분말 황산 물질을 포함하는 흡착제에 있어서, Ash, a byproduct of thermal power generation, and 5-15 parts by weight of sulfuric acid source are mixed and stirred with respect to the ash for 10 to 30 hours of stirring and aging, and containing powdered sulfuric acid material aged by heating at 100 ° C to 300 ° C for 5 to 15 hours. In the adsorbent,
    상기 인산 공급원은 인산 농도가 60~90%이며, 폐인산, 재생인산 및 인산으로 이루어지는 군에서 선택되는 하나 이상인 것이고, The phosphoric acid source is a phosphoric acid concentration of 60 to 90%, at least one selected from the group consisting of waste phosphoric acid, regenerated phosphoric acid and phosphoric acid,
    상기 황산 공급원은 황산 농도 30~70%이며, 폐황산, 재생황산 및 황산으로 이루어지는 군에서 선택 되는 하나 이상인 것이고, The sulfuric acid source is sulfuric acid concentration of 30 to 70%, at least one selected from the group consisting of spent sulfuric acid, regenerated sulfuric acid and sulfuric acid,
    상기 분말 인산 물질 및 상기 분말 황산 물질은 100~200메쉬의 분말이고,The powdered phosphate material and the powdered sulfuric acid material is a powder of 100 ~ 200 mesh,
    상기 흡착제는 분말 또는 펠렛 형상을 가지며, 경도는 92% 이상이고, 이때 상기 분말 및 펠렛 형상은 복층다공형원통 구조인 것을 특징으로 하는 다기능성 흡착제.The adsorbent has a powder or pellet shape, the hardness is 92% or more, wherein the powder and pellet shape is a multi-layer porous cylindrical structure, characterized in that the multifunctional adsorbent.
  4. 제 3 항에 있어서, 상기 흡착제는 상기 분말 인산 물질과 상기 분말 황산 물질이 혼합비(A)가 55% : 45% < A < 100% : 0%를 만족하도록 포함되는 것을 특징으로 하는 흡착제.The adsorbent of claim 3, wherein the powdered phosphate material and the powdered sulfuric acid material are included such that a mixing ratio (A) satisfies 55%: 45% <A <100%: 0%.
  5. 제 1 항 내지 제 4 항 중 어느 한 항에 있어서, 상기 흡착제는 암모니아가스, 황화수소, 아민류, 설파이드류, 및 알데하이드류로 이루어지는 군에서 선택되는 하나 이상을 흡착하는 것을 특징으로 하는 흡착제.The adsorbent according to any one of claims 1 to 4, wherein the adsorbent adsorbs at least one selected from the group consisting of ammonia gas, hydrogen sulfide, amines, sulfides, and aldehydes.
  6. 제 1 항 내지 제 4 항 중 어느 한 항에 있어서, 상기 흡착제는 먼지를 흡착하는 것을 특징으로 하는 흡착제.The adsorbent according to any one of claims 1 to 4, wherein the adsorbent adsorbs dust.
  7. 제 1 항 내지 제 4 항 중 어느 한 항에 있어서, 상기 흡착제를 포함하고, 돼지 폐사를 저감할 수 있는 돼지폐사저감제.The pig mortality reducing agent of any one of Claims 1-4 which contains the said adsorbent and can reduce pig mortality.
  8. 제 1 항 내지 제 4 항 중 어느 한 항에 있어서, 상기 흡착제를 포함하고, 계분을 비료로 자원화 할 수 있는 계분비료첨가제.The fertilizer additive according to any one of claims 1 to 4, which comprises the adsorbent and is capable of recycling the powder to fertilizer.
  9. 제 1 항 내지 제 4 항 중 어느 한 항에 있어서, 상기 흡착제를 포함하고, 활성탄을 대체할 수 있는 비표면적을 가지는 것을 특징으로 하는 활성탄 대체재.The activated carbon substitute according to any one of claims 1 to 4, wherein the activated carbon substitute includes the adsorbent and has a specific surface area capable of replacing activated carbon.
  10. 제 1항 내지 제 4 항 중 어느 한 항에 있어서, 상기 흡착제를 포함하는 것을 특징으로 하는 산업용 탈취제.The industrial deodorant according to any one of claims 1 to 4, comprising the adsorbent.
PCT/KR2010/000959 2009-02-17 2010-02-17 Multifunctional adsorbent using sewage sludge or ashes, and livestock environment-improving agent WO2010095842A2 (en)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3998756A (en) * 1974-06-17 1976-12-21 Hercules Incorporated Preparation of activated carbonaceous material from sewage sludge and sulfuric acid
US20020183197A1 (en) * 2001-03-29 2002-12-05 Youssef El-Shoubary Adsorption powder containing cupric chloride
JP2006061756A (en) * 2004-08-24 2006-03-09 Toshiba Corp Method of manufacturing carbonized deodorant
KR100702602B1 (en) * 2006-08-29 2007-04-02 태성건설 주식회사 The manufacturing method of deodorant for removal offensive odor and it's manufactured deodorant

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3998756A (en) * 1974-06-17 1976-12-21 Hercules Incorporated Preparation of activated carbonaceous material from sewage sludge and sulfuric acid
US20020183197A1 (en) * 2001-03-29 2002-12-05 Youssef El-Shoubary Adsorption powder containing cupric chloride
JP2006061756A (en) * 2004-08-24 2006-03-09 Toshiba Corp Method of manufacturing carbonized deodorant
KR100702602B1 (en) * 2006-08-29 2007-04-02 태성건설 주식회사 The manufacturing method of deodorant for removal offensive odor and it's manufactured deodorant

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