KR101010011B1 - Solidifying agent for sludge and manufacturing method of it - Google Patents

Solidifying agent for sludge and manufacturing method of it Download PDF

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KR101010011B1
KR101010011B1 KR1020100004024A KR20100004024A KR101010011B1 KR 101010011 B1 KR101010011 B1 KR 101010011B1 KR 1020100004024 A KR1020100004024 A KR 1020100004024A KR 20100004024 A KR20100004024 A KR 20100004024A KR 101010011 B1 KR101010011 B1 KR 101010011B1
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South Korea
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sludge
gypsum
solidifying agent
waste
agent
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KR1020100004024A
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Korean (ko)
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권승안
권윤회
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주식회사한국포조텍
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
    • B09B—DISPOSAL OF SOLID WASTE
    • B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
    • B09B3/20—Agglomeration, binding or encapsulation of solid waste
    • B09B3/25—Agglomeration, binding or encapsulation of solid waste using mineral binders or matrix
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
    • B09B—DISPOSAL OF SOLID WASTE
    • B09B5/00—Operations not covered by a single other subclass or by a single other group in this subclass
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F11/00—Treatment of sludge; Devices therefor
    • C02F11/008—Sludge treatment by fixation or solidification
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/20—Waste processing or separation

Abstract

PURPOSE: A sludge solidifying agent with the high water content, and a producing method thereof are provided to economically use waste resources, and to effectively process sludge with the high water content. CONSTITUTION: A sludge solidifying agent with the high water content contains the following: 30~80wt% of paper manufacturing combustion agent including an alkaline pozzolan material; 50~90wt% of first mixture containing 20~70wt% of waste phosphogypsum; and 10~50wt% of solidifying agent selected from the group consisting of cement, quicklime, calcined dolomite, anhydrous gypsum, a hardener, a coagulant, a precipitation agent, and a sedimentation agent.

Description

고함수 슬러지 고화제 및 이의 제조방법{SOLIDIFYING AGENT FOR SLUDGE AND MANUFACTURING METHOD OF IT}High-functional sludge hardener and its manufacturing method {SOLIDIFYING AGENT FOR SLUDGE AND MANUFACTURING METHOD OF IT}

본 발명은 제지공장에서 발생하는 제지연소재와 비료공장에서 인산 제조시 발생하는 폐인산석고를 이용하여, 고함수 슬러지를 저렴한 비용으로 효율적 처리하기 위한 고함수 슬러지 고화제 및 이의 제조방법에 관한 것이다.
The present invention relates to a high-functional sludge solidifying agent and a method for producing the same, which are used to efficiently treat high-functional sludges at low cost by using waste paper phosphate gypsum produced at the papermaking plant and the fertilizer plant. .

기존의 대부분의 고함수 슬러지의 고화를 위한 고화제는 양생시간이 길어 효율적인 처리기능이 떨어지고, 악취발생 등의 문제를 갖고 있었다.
The solidifying agent for the solidification of most existing high-function sludge had a long curing time, the effective treatment function is reduced, there was a problem such as odor generation.

또한, 비료공장에서 인산 제조시 발생하는 폐인산석고는 시멘트 응결조절제 및 석고보드 등 일부 건축재료로 사용이 한정되어 있어 적치장에 적치되는 양이 지속적으로 증가하여 폐기물에 의한 오염된 침출수 등의 유출에 따른 환경오염문제가 심각한 실정이다.
In addition, the waste phosphate gypsum produced during the production of phosphoric acid in the fertilizer plant is limited to some building materials such as cement coagulant and gypsum board, so the amount accumulated in the stockyard is continuously increased, and the amount of waste phosphate gypsum is discharged. The environmental pollution problem is serious situation.

따라서, 상기 폐인산석고를 재활용하는 기술 개발이 시급한 실정이며, 대한민국공개특허 10-2008-0032670(공개일자 2008.04.16)에서 매립장복토재로 사용하는 등의 기술이 개시되어 있기는 하나, 상기 공개특허는 하수슬러지에 폐인산석고를 우선적으로 투입한 후, 혼합된 하수슬러지에 표면개질 제강슬래그, 생석회를 혼합하여 매립장복토제로 활용하는 것으로, 본 발명에서 목적하고 있는 고함수 슬러지의 효율적 고화 기술로 활용하기에는 부적합하여, 상기 폐인산석고를 재활용함과 동시에 고함수 슬러지를 효율적으로 고화처리할 수 있는 고화제 기술 개발이 필요한 실정이다.
Therefore, it is urgent to develop a technology for recycling the waste phosphate gypsum, and the technique such as the use of landfill material in Korea Patent Publication No. 10-2008-0032670 (published date 2008.04.16) is disclosed, The first method is to put waste phosphate gypsum into sewage sludge, and then mix the surface modified steelmaking slag and quicklime into the mixed sewage sludge and use it as a landfill covering agent. It is not suitable for the following situation, it is necessary to develop a solidifying agent technology capable of efficiently solidifying high-functional sludge while recycling the waste phosphate gypsum.

대한민국등록특허10-0690692(등록일자2007.02.27)Republic of Korea Patent Registration 10-0690692 (Registration Date 2007.02.27) 대한민국등록특허10-0699925(등록일자2007.03.20)Republic of Korea Patent Registration 10-0699925 (Registration Date 2007.03.20) 대한민국등록특허10-0702602(등록일자2007.03.27)Republic of Korea Patent Registration 10-0702602 (Registration Date 2007.03.27) 대한민국등록특허10-0714846(등록일자2007.04.27)Republic of Korea Patent Registration 10-0714846 (Registration Date 2007.04.27) 대한민국등록특허10-0806200(등록일자2008.02.15)Republic of Korea Patent Registration 10-0806200 (Registration date 2008.02.15) 대한민국등록특허10-0838627(등록일자2008.06.10)Republic of Korea Patent Registration 10-0838627 (Registration Date 2008.06.10) 대한민국등록특허10-0509932(등록일자2008.06.10)Republic of Korea Patent Registration 10-0509932 (Registration Date 2008.06.10) 대한민국공개특허10-2004-0075498(공개일자2004.08.30)Republic of Korea Patent Publication 10-2004-0075498 (published date 2004.08.30) 대한민국공개특허10-2008-0032670(공개일자2008.04.16)Republic of Korea Patent Publication 10-2008-0032670 (Publication date 2008.04.16)

상기 문제를 해결하기 위한, 본 발명의 목적은 제지공장에서 발생하는 제지연소재와 비료공장에서 인산 제조시 발생하는 폐인산석고를 이용하여, 고함수 슬러지를 효율적으로 저렴하게 고화처리할 수 있는 고함수 슬러지 고화제 및 이의 제조방법을 제공하고자 하는 것이다.
In order to solve the above problems, an object of the present invention is to use waste paper phosphate gypsum produced during the production of phosphoric acid in the papermaking material and fertilizer plant in the paper mill, high efficiency sludge can be efficiently solidified It is an object of the present invention to provide a hydrous sludge solidifying agent and a method of preparing the same.

상기 목적을 달성하기 위하여,In order to achieve the above object,

본 발명은 알칼리성 포졸란 물질 30 ~ 80wt%와 산성물질 20 ~ 70wt%의 혼합으로 조성된 제1혼합물(A) 50 ~ 90wt%와,The present invention is the first mixture (A) 50 ~ 90wt% of a mixture of 30 ~ 80wt% alkaline pozzolanic material and 20 ~ 70wt% acidic material,

시멘트, 생석회, 경소 백운석, 무수석고, 경화제, 응집제, 침전제, 침강제 중 선택되는 어느 1종 또는 2종 이상인 고형제(B) 10 ~ 50wt%의 혼합으로 조성된 고함수 슬러지 고화제로서,
As a high-functional sludge solidifying agent, which is composed of a mixture of 10 to 50 wt% of solids (B) selected from cement, quicklime, light dolomite, anhydrous gypsum, hardener, flocculant, precipitant, and sedimentation agent,

더욱 상세하게는,More specifically,

알칼리성 포졸란 물질인 제지 회사에서 발생하는 입도 0.5 ~ 80㎛, 비중 1.8 ~ 2.2의 제지연소재 30 ~ 80wt%와 산성물질인 폐인산석고 20 ~ 70wt%의 혼합으로 조성된 제1혼합물(A) 50 ~ 90wt%와,A first mixture (A) 50 composed of a mixture of 30 to 80 wt% of paper-burning combustion materials with a particle size of 0.5 to 80 μm, specific gravity of 1.8 to 2.2 and 20 to 70 wt% of acidic waste phosphate gypsum produced by a paper maker of alkaline pozzolanic material ~ 90wt%,

시멘트, 생석회, 경소 백운석, 무수석고, 경화제, 응집제, 침전제, 침강제 중 선택되는 어느 1종 또는 2종 이상인 고형제(B) 10 ~ 50wt%의 혼합으로 조성된 고함수 슬러지 고화제와,
A high function sludge solidifying agent formed by mixing 10 to 50 wt% of solids (B) selected from cement, quicklime, light dolomite, anhydrous gypsum, hardener, flocculant, precipitant, and sedimentation agent;

상기 고함수 슬러지 고화제를 제조하기 위한 기술로서,As a technique for producing the high water sludge solidifying agent,

제지 회사에서 발생하는 입도 0.5 ~ 80㎛, 비중 1.8 ~ 2.2의 제지연소재 30 ~ 80wt%와 폐인산석고 20 ~ 70wt%를 혼합한 후 0.1 ~ 5mm 크기의 입경으로 분쇄하여 pH 3 ~ 9의 제1혼합물을 제조하는 단계와,30 ~ 80wt% of paper-burning materials with a particle size of 0.5 ~ 80㎛, specific gravity of 1.8 ~ 2.2 and 20 ~ 70wt% of waste phosphate gypsum are mixed in the paper company, and then ground to a particle size of 0.1 ~ 5mm Preparing a mixture,

상기 제1혼합물 50 ~ 90wt%와 시멘트, 생석회, 경소 백운석, 무수석고, 경화제, 응집제, 침전제, 침강제 중 선택되는 어느 1종 또는 2종 이상인 고형제 10 ~ 50wt%를 혼합하는 단계로 이루어지는 고함수 슬러지 고화제 제조방법을 주요 기술적 구성으로 한다.
50 to 90wt% of the first mixture and cement, quicklime, light dolomite, anhydrous gypsum, hardening agent, flocculant, precipitating agent, any one or two or more types of solids selected from the settling agent 10-50 wt% The method for producing hydrous sludge solidifying agent is the main technical configuration.

이상에서 살펴본 바와 같이, 본 발명에 따른 고함수 슬러지 고화제는 제지공장에서 발생하는 제지연소재와 폐인산석고를 활용함으로써 폐자원을 효율적으로 사용함으로써 매우 경제적이며, 수분함량이 높은 슬러지를 저렴한 비용과 빠른 양생시간으로 효율적인 처리가 가능하다.As described above, the high-functional sludge solidifying agent according to the present invention is very economical by using waste resources efficiently by utilizing paper burning material and waste phosphate gypsum produced in the paper mill, and low cost of sludge with high water content. And fast curing time enables efficient treatment.

그리고, 이외에 무해 및 안정성, 유해중금속 유출방지, 악취제거 및 강도개선, 고화촉진, 탁월한 수분감량 효과, 팽창성으로 인한 차수 성능 개선 효과를 갖는다.In addition, in addition to harmless and stable, preventing harmful heavy metal leakage, odor removal and strength improvement, solidification, excellent moisture loss effect, has the effect of improving the order performance due to expandability.

도 1은 본 발명에 따른 고함수 슬러지 고화제 제조과정을 보인 순서도.
도 2는 본 발명에 따른 고함수 슬러지 고화제를 이용한 슬러지 처리공정도.1 is a flow chart showing a manufacturing process of a high functional sludge solidifying agent according to the present invention.
2 is a sludge treatment process diagram using a high function sludge solidifying agent according to the present invention.

이하, 상기의 기술 구성에 대한 구체적인 내용을 살펴보고자 한다.
Hereinafter, a detailed description of the above technical configuration will be made.

고화제를 이용한 고화원리는 산, 알칼리계 원료, 경화제가 혼합되어 중화반응을 일으킴으로써, 발열로 인한 건조 및 가스발생 억제 현상이 일어나고, 칼슘, 마그네슘 결합에 의한 단립화 및 강도 증가와, 산화기능에 의한 고화물 흙색 현상이 발생하게 된다.
The solidification principle using the solidifying agent is a mixture of acid, alkali-based raw materials, and curing agent, which causes a neutralization reaction, resulting in the suppression of drying and gas generation due to heat generation, granulation and strength increase by calcium and magnesium bonding, and oxidation function. Due to the solidified soil color phenomenon occurs.

이와 같은 고화처리에 따른 효과로는 혼합과정에서 수화반응(발열)에 의한 수분량 감소로 중금속 용출억제 기능을 가지며, 양생과정에서 이온교환반응에 의한 단립화, 용출억제, 포졸란반응에 의한 강도증가, 탄산화반응에 의한 강도증가와 안정화, 토질공학적 개량, 유해병원균 사멸 및 재슬러지화의 억제 효과를 갖는다.
The effect of this solidification treatment is to reduce the amount of water by hydration reaction (exothermic) in the mixing process, has a function of inhibiting the dissolution of heavy metals, in the curing process by the separation of the ion exchange reaction, the inhibition of elution, increase in strength by the pozzolanic reaction, It has the effect of increasing strength and stabilization by carbonation reaction, improving soil engineering, killing harmful pathogens and resludge.

본 발명에 따른 고함수 슬러지 고화제는 도 1에 도시된 바와 같이,
The high functional sludge solidifying agent according to the present invention is shown in Figure 1,

알칼리성 포졸란 물질 30 ~ 80wt%와 산성물질 20 ~ 70wt%를 혼합하고, 이를 0.1 ~ 5mm 크기의 입경으로 분쇄하여 pH 3 ~ 9의 제1혼합물을 제조하는 단계와,Mixing an alkaline pozzolanic material 30 to 80wt% and an acidic material 20 to 70wt%, and pulverizing the same to a particle size of 0.1 to 5mm to prepare a first mixture having a pH of 3 to 9;

상기 제1혼합물 50 ~ 90wt%와 시멘트, 생석회, 경소 백운석, 무수석고, 경화제, 응집제, 침전제, 침강제 중 선택되는 어느 1종 또는 2종 이상인 고형제 10 ~ 50wt%를 혼합하여 제조하는 것으로,
50 to 90wt% of the first mixture and cement, quicklime, light dolomite, anhydrous gypsum, hardener, flocculant, precipitant, precipitates 10 to 50wt% of any one or two or more selected solids selected from,

더욱 구체적으로는 상기 알칼리성 포졸란 물질이 제지 회사에서 발생하는 입도 0.5 ~ 80㎛, 비중 1.8 ~ 2.2의 제지연소재이고, 상기 산성물질이 폐인산석고임을 특징으로 한다.
More specifically, the alkaline pozzolanic material is a paper burning material having a particle size of 0.5 to 80 μm, specific gravity of 1.8 to 2.2, and the acidic material is waste phosphate gypsum.

상기 알칼리성 포졸란 물질은 입도 0.5 ~ 80㎛, 비중 1.8 ~ 2.2, pH 6 ~ 12.5인 것으로, 제지 회사에서 발생하는 제지연소재, 석탄을 연소시킨 후 발생하는 플라이 애쉬(Fly ash), 쓰레기 또는 하수슬러지를 태워 발생하는 소각재, 폐석회, 제강분진 중 선택되는 어느 1종 또는 2종 이상인 것을 사용하나, 바람직하게는 상기 제지연소재를 사용한다.
The alkaline pozzolanic material has a particle size of 0.5 ~ 80㎛, specific gravity 1.8 ~ 2.2, pH 6 ~ 12.5, paper ash produced by the paper company, fly ash (fly ash) generated after burning coal, waste or sewage sludge One or two or more selected from incineration ash, waste lime, and steelmaking dust generated by burning is used, but preferably, the papermaking combustion material is used.

상기 제지연소재의 입도는 포졸란 활성도에 영향을 미치는 중요한 요소이며, 비중은 강도 및 수밀성 증대와 같은 역학적 특성을 향상시키는 요소로서, 입도 0.5 ~ 80㎛, 비중 1.8 ~ 2.2 범위의 제지연소재를 사용하는 것이 바람직하다.
Particle size of the papermaking material is an important factor affecting pozzolanic activity, specific gravity is to improve the mechanical properties such as strength and water tightness, papermaking material with a particle size of 0.5 ~ 80㎛, specific gravity 1.8 ~ 2.2 It is desirable to.

상기 알칼리성 포졸란 물질의 사용량이 30wt% 미만인 경우에는 포졸란 활성이 떨어지는 문제가 있고, 80wt%를 초과하게 되는 경우에는 pH가 높아져 최종 고화물의 암모니아 가스 발생으로 악취가 발생하거나, 고화제의 양생 기간이 길어질 수 있으므로, 상기 알칼리성 포졸란 물질의 사용량은 30 ~ 80wt%의 범위를 유지하는 것이 바람직하다.
When the amount of the alkaline pozzolanic substance is less than 30wt%, the pozzolanic activity is deteriorated, and when the amount of the alkaline pozzolanic is exceeded 80wt%, the pH is increased and odor is generated by ammonia gas generation of the final solidified product, or the curing period of the solidifying agent is increased. Since it may be longer, the amount of the alkaline pozzolanic material is preferably maintained in the range of 30 to 80wt%.

상기 산성물질은 폐인산석고, 황산, 폐산, 폐티탄석고, 황산철 중 선택되는 어느 1종 또는 2종 이상인 것을 사용하나, 바람직하게는 폐인산석고를 사용한다.
The acidic substance may be any one or two or more selected from waste gypsum, sulfuric acid, waste acid, waste titanium gypsum and iron sulfate, preferably waste gypsum is used.

상기 폐인산석고는 비료공장에서 인산 제조시 발생하게 된다.The waste phosphate gypsum is generated during the production of phosphoric acid in the fertilizer plant.

인산제조의 Raw material로서는 황산과 인광석이 반응물질로 사용되며, 인광석으로부터 인산 제조시에는 다음의 반응식에서와 같이 부산물로서 다량의 인산석고가 발생한다.
As a raw material of phosphate production, sulfuric acid and phosphate are used as reactants, and when phosphate is produced from phosphate, a large amount of phosphate gypsum is generated as a by-product, as shown in the following reaction formula.

Ca10(PO4)6(F, OH)2 + 10H2SO4 + 20H2O ---> 6H3PO4 + 10CaSO4·XH2O + 2HF
 Ca 10 (PO 4) 6 ( F, OH) 2 + 10H 2 SO 4 + 20H 2 O ---> 6H 3 PO 4 + 10CaSO 4 · XH 2 O + 2HF

인산석고는 85 ~ 93% 이상의 황산칼슘과 모래, 인산등 대부분 무기물로 이루어져 있으며, 천연석고에 비해 수분 함량이 크고, 다소의 인산기와 sodium, 불소 화합물 등의불순물을 함유하고 있으며, 천연석고보다 입자가 작다는 특징이 있다.Gypsum phosphate is composed of more than 85 ~ 93% of calcium sulfate, sand, phosphoric acid and most other minerals, it has a higher moisture content than natural gypsum, contains some phosphate, impurities such as sodium, fluorine compounds, etc. Is characterized by being small.

이와 같은 차이는 인산석고를 건조하거나 하소(calcination)할 때 상당히 큰 영향을 미치게 된다.
This difference has a significant effect on drying or calcination of phosphate gypsum.

인산석고의 화학적 구성은 다음의 표 1과 같다.
Chemical composition of the phosphate gypsum is shown in Table 1 below.

성분ingredient 함량비(wt%)Content ratio (wt%) GypsumGypsum 85.0 ~ 93.085.0 to 93.0 PhosphatePhosphate 0.2 ~ 1.70.2 to 1.7 FluorideFluoride 0.4 ~ 1.30.4 to 1.3 SandSand 1.4 ~ 8.41.4 to 8.4 Soluble saltSoluble salt 0.1 ~ 5.30.1 to 5.3

그리고, 인산석고의 물리적 성질은 다음의 표 2와 같다.
The physical properties of phosphate gypsum are shown in Table 2 below.


명칭
designation

석고량(%)
Gypsum amount (%)
비중
importance
체의 크기(% Pass)Sieve Size (% Pass) 투수성(㎠/sec)Permeability (㎠ / sec) No.40
(0.5mm)No.40
(0.5mm) No.60
(0.375mm)No.60
(0.375mm) No.200
(0.075mm)No.200
(0.075mm) 시험농도Test concentration 기준농도Reference concentration 평균Average 8989 2.402.40 9393 8888 5151 4.5×10-5 4.5 × 10 -5 5.9×10-5 5.9 × 10 -5 범위range 85 ~ 9385 to 93 2.402.40 9393 87 ~ 8887-88 49 ~ 5349-53 4.7 ~
4.3×10-5 4.7 ~
4.3 × 10 -5 7.6 ~
4.2×10-5 7.6 to
4.2 × 10 -5

상기 폐인산석고는 함수율 30 ~ 40%의 폐인산석고를 그대로 사용할 수도 있으나, 상기 폐인산석고에 포함되어 있는 중금속을 안정화처리함으로써 보다 효율적인 자원화가 가능하다.
The waste phosphate gypsum may use waste phosphate gypsum having a water content of 30 to 40% as it is, but by stabilizing heavy metals contained in the waste phosphate gypsum, more efficient resourceization is possible.

폐인산석고는 원광물을 기준으로 Cd 3.02ppm, Pb 5.24ppm, Ni 0.50ppm, As 2.94ppm, Cr 9.71ppm, V 8.06ppm, Zn 14.07ppm, Fe 163.2ppm, Mn 4.99ppm, Cu 2.62ppm, Al 1140ppm 함량을 갖는 것으로, 중금속을 안정화처리하여 사용하고자 하는 경우에는 폐인산석고에 대한 황산처리비율은 폐인산석고 100중량부에 대해 순도 80 ~ 98%의 황산 50중량부를 가하여 중금속성분을 황화물 형태의 안정한 화합물로 처리하여 중금속이 유출되지 않도록 하여 사용한다.
Waste phosphate gypsum is Cd 3.02ppm, Pb 5.24ppm, Ni 0.50ppm, As 2.94ppm, Cr 9.71ppm, V 8.06ppm, Zn 14.07ppm, Fe 163.2ppm, Mn 4.99ppm, Cu 2.62ppm, Al In the case of stabilizing heavy metals, the ratio of sulfuric acid treatment to waste phosphate gypsum is added to 50 parts by weight of sulfuric acid with a purity of 80 to 98% based on 100 parts by weight of waste phosphate. Treat it with a stable compound to prevent heavy metals from spilling.

상기 산성물질에서의 황산은 순도 20 ~ 98%인 황산을 단독으로 사용하거나, 순도 20 ~ 98%인 황산 40 ~ 50vol%와 폐산 50 ~ 60vol%를 혼합하여 조성된 것을 사용한다.
Sulfuric acid in the acidic material using a sulfuric acid of 20 to 98% purity alone, or a mixture of 40 to 50vol% sulfuric acid with a purity of 20 to 98% and waste acid 50 to 60vol%.

상기 폐산은 플루오르산 폐수 30 ~ 95vol%와 순도 95 ~ 99%의 황산 5 ~ 70vol%의 혼합으로 조성된 산혼합물을 사용한다.
The waste acid uses an acid mixture formed by mixing 30 to 95 vol% of fluoric acid wastewater and 5 to 70 vol% of sulfuric acid having a purity of 95 to 99%.

상기 폐티탄석고는 티타늄제조공정에서 발생하는 폐티탄석고를 사용한다. 상기 폐티탄석고는 최종 복토재의 토질역학적인 강도, 투수계수, 중금속 용출을 억제시키며 복토재 생성시 악취 발생을 최소화시킬 목적으로 사용된다.
The waste titanium gypsum is used waste titanium gypsum produced in the titanium manufacturing process. The waste titanium gypsum is used for the purpose of minimizing the occurrence of odors in the production of cover material, to suppress the soil mechanical strength, permeability coefficient, heavy metal leaching of the final cover material.

상기 황산철은 황산제1철 1수염 또는 황산제1철 7수염 중 어느 1종을 선택하여 사용한다. 상기 황산제1철 1수염은 분자식이 FeSO4 H2O인 결정형 고상의 무기화합물로, 그 조성은 Fe 18.4%, TiO2 5.0%, Cu 0.005%, Mn 4.0%, 수불용분 0.2%, 염산불용분 0.1%, 부착수분 5.0%이고, 상기 황산제1철 7수염은 분자식이 FeSO4 7H2O인 결정형 고상의 무기화합물로, 그 조성은 Fe 18.4%, Fe2(SO4)3 0.5%, TiO2 0.5%, Cu 0.005%, Mn 0.6%, 수불용분 0.2%, 염산불용분 0.1%, 부착수분 5.0%이다.
The said iron sulfate selects and uses any 1 type of ferrous sulfate monohydrate or ferrous sulfate monohydrate. To the ferrous sulfate 1 beard is an inorganic compound of a crystalline solid molecular formula is FeSO 4 H 2 O, the composition of Fe 18.4%, TiO 2 5.0% , Cu 0.005%, Mn 4.0%, can be insoluble content of 0.2%, HCl 0.1% insoluble content, 5.0% adhesion water, the ferrous sulfate hexahydrate is a crystalline solid inorganic compound having a molecular formula of FeSO 4 7H 2 O, the composition of Fe 18.4%, Fe 2 (SO 4 ) 3 0.5% , TiO 2 0.5%, Cu 0.005%, Mn 0.6%, water insoluble content 0.2%, hydrochloric acid insoluble content 0.1%, adhesion moisture 5.0%.

상기 산성물질의 사용량이 20wt% 미만인 경우에는 pH가 높아 산림녹화에 지장을 주게 되며, 70wt%를 초과하게 되는 경우에는 고화제의 고화능력이 떨어지고, 산성으로 인한 산림녹화에 지장을 주는 문제가 발생할 수 있으므로, 상기 산성물질의 사용량은 상기 알칼리성 포졸란 물질에 대해 20 ~ 70wt%의 범위 내를 유지하는 것이 바람직하다.
When the amount of the acidic substance is less than 20wt%, the pH is high, which hinders forest greening. When the amount of the acidic substance exceeds 70wt%, the solidification capacity of the hardener decreases, which causes problems in forestry greening due to acid. Since the amount of the acidic substance may be maintained within the range of 20 to 70wt% with respect to the alkaline pozzolanic substance.

알칼리성 포졸란 물질과 산성물질의 혼합으로 조성된 제1혼합물은 pH가 3 ~ 9인 것으로, 0.1 ~ 5mm의 크기로 분쇄된 것이다.
The first mixture formed by mixing an alkaline pozzolanic material and an acidic material has a pH of 3 to 9, and is ground to a size of 0.1 to 5 mm.

상기 제1혼합물은 시멘트, 생석회, 경소 백운석, 무수석고, 경화제, 응집제, 침전제, 침강제 중 선택되는 어느 1종 또는 2종 이상인 고형제와 혼합함으로써 고화제가 제조되는 것으로, 그 혼합비율은 제1혼합물 50 ~ 90wt%와 상기 고형제 10 ~ 50wt%로 이루어진다.The first mixture is a solidifying agent is prepared by mixing with one or two or more solids selected from cement, quicklime, light dolomite, anhydrous gypsum, hardener, flocculant, precipitant, and sedimenting agent. It is composed of 50 to 90 wt% of a mixture and 10 to 50 wt% of the solid agent.

상기 제1혼합물의 사용량이 50wt% 미만인 경우에는 상대적으로 고형제의 사용량이 증가하여 pH상승에 따른 악취발생 문제가 있고, 90wt%를 초과하게 되는 경우에는 고화제의 고화기능이 떨어질 수 있으므로, 상기 제1혼합물의 사용량은 50 ~ 90wt% 범위를 유지하는 것이 바람직하다.
When the amount of the first mixture is less than 50wt%, the amount of solidifying agent is relatively increased, resulting in a bad smell caused by a rise in pH, and when it exceeds 90wt%, the solidifying function of the solidifying agent may be deteriorated. The amount of the first mixture is preferably maintained in the range of 50 ~ 90wt%.

그리고, 상기 고형제의 사용량이 10wt% 미만인 경우에는 고화기능이 떨어질 수 있고, 50wt%를 초과하게 되는 경우에는 고화제의 pH 상승으로 인한 고함수 슬러지 고화반응시 악취가 발생할 수 있으므로, 상기 고형제의 사용량은 10 ~ 50wt% 범위를 유지하는 것이 바람직하다.
When the amount of the solidifying agent is less than 10wt%, the solidification function may be reduced, and when the amount of the solidifying agent is more than 50wt%, the odor may occur during the high functional sludge solidification reaction due to the pH increase of the solidifying agent. The amount of is preferably maintained in the range of 10 to 50wt%.

상기 시멘트는 다음의 표 3에서와 같은 화학성분을 갖는다.
The cement has the same chemical composition as in Table 3 below.

CaOCaO SiO2 SiO 2 Fe2O3 Fe 2 O 3 MgOMgO SO3 SO 3 Al2O3 Al 2 O 3 기타Etc 64.864.8 22.022.0 3.03.0 1.41.4 1.91.9 5.55.5 나머지Remainder

상기 생석회는 물에 대하여 친화도가 매우 높고 실리카겔보다 훨씬 높은 습성을 나타내는 것으로, 비중 3.25 ~ 3.38, 겉보기 밀도 1.3g/㎤, 모스 경도 2인 것을 사용한다. 상기 생석회의 성분비율은 다음의 표 4와 같다.
The quicklime has a very high affinity for water and exhibits a much higher wettability than silica gel, and has a specific gravity of 3.25 to 3.38, an apparent density of 1.3 g / cm 3, and a Mohs hardness of 2. The component ratio of the quicklime is shown in Table 4 below.

상기 경소 백운석은 제철소에서 발생하는 백운석 슬러지를 이용하여 분말 경소 백운석을 제조하는 것으로, 제철소에서 발생되는 슬러지를 괴상화처리한 다음 건조한 후 800 ~ 1,000℃에서 40 ~ 80분동안 소성하여 제조된 것을 사용한다.
The small calcined dolomite is a powder made from the dolomite sludge produced in the steel mill to produce a powdered small calcined dolomite, the sludge generated in the steel mill is agglomerated and dried and then fired for 40 to 80 minutes at 800 ~ 1,000 ℃ do.

상기 무수석고는 폐석고를 130 ~ 140℃에서 4 ~ 6시간 건식탈수하여 이루어진 것으로, 분말 형태로 사용하며, 그 분말의 분말도는 4,000 ~ 4,500㎤/g이다.
The anhydrous gypsum is made by dry dehydration of waste gypsum 4 ~ 6 hours at 130 ~ 140 ℃, used in the form of a powder, the powder of the powder is 4,000 ~ 4,500 cm 3 / g.

상기 경화제는 규산소다(Sodium Silicate), 글리옥살(Glyoxal), 염화칼슘(Calcium chloride), 골탄(Bone black), 아초산나트륨 중 선택되는 어느 1종 또는 2종 이상인 것이다.The curing agent is any one or two or more selected from sodium silicate, glyoxal, calcium chloride, bone black, and sodium acetate.

상기 응집제는 황산알루미늄(Aluminium sulfate), 폴리염화알루미늄(Poly Aluminium Chloride), 소다회(Na2CO3), 액체가성소다(NaOH) 중 선택되는 어느 1종 또는 2종 이상인 것이다.The flocculant is any one or two or more selected from aluminum sulfate, poly aluminum chloride, soda ash (Na 2 CO 3 ), and liquid caustic soda (NaOH).

상기 침전제는 수산화칼슘(Calcium hydroxide) 또는 중탄산암모늄(NH4HCO3)이다.The precipitant is calcium hydroxide or ammonium bicarbonate (NH 4 HCO 3 ).

상기 침강제는 탄산칼슘(Calcium carbonate) 또는 폴리아크릴아미드(Polyacrylamide)이다.
The settling agent is calcium carbonate or polyacrylamide.

도 1의 고함수 슬러지 고화제에 있어서, 폐인산석고는 30 ~ 40%의 함수율을 갖기 때문에, 상기 폐인산석고를 시멘트, 생석회 등의 고형제와 먼저 혼합하게 될 경우, 상기 고형제와 폐인산석고의 함수와 반응하여 굳는 현상이 발생함으로써 고형제의 성능이 떨어지기 때문에, 상기 폐인산석고의 함수율을 최소화하는 것이 중요하다. 따라서, 상기 폐인산석고를 제지연소재와 먼저 혼합하여 폐인산석고의 함수율을 최소화한 제1혼합물을 먼저 조성한 후, 상기 제1혼합물과 고형제를 혼합하여 고화제를 만드는 것이 중요하다.
In the high-function sludge solidifying agent of FIG. 1, since the waste phosphate gypsum has a water content of 30 to 40%, when the waste phosphate gypsum is first mixed with a solid agent such as cement or quicklime, the solid agent and waste phosphate It is important to minimize the water content of the waste phosphate gypsum, because the performance of the solid agent is degraded by the reaction of gypsum with the hardening occurs. Therefore, it is important to first mix the waste phosphate gypsum with the papermaking material to form a first mixture which minimizes the water content of the waste phosphate gypsum, and then mix the first mixture and a solid agent to make a solidifying agent.

도 2에 도시된 바와 같이, 본 발명에 따른 고함수 슬러지 고화제를 이용한 슬러지 처리과정은 고함수 슬러지 40 ~ 80wt%에 본 발명에 따른 고화제 20 ~ 60wt%로 첨가하여 pH 8 ~ 12.7로 조정된 것을 Mixer 혼합하여 2시간 ~ 3일간 양생한 후, 매립 및 성토한다.As shown in Figure 2, the sludge treatment process using the high-functional sludge solidifying agent according to the present invention is adjusted to pH 8 ~ 12.7 by adding 20 ~ 60wt% of the solidifying agent according to the present invention to 40 ~ 80wt% of high functional sludge Mixer was mixed and cured for 2 hours to 3 days, then landfilled and filled.

상기 고함수 슬러지로는 고함수 하수슬러지, 고함수 퇴적오니, 축산폐수, 음식물 슬러지가 있다.
The high function sludge includes high function sewage sludge, high function sedimentation sludge, livestock wastewater, and food sludge.

본 발명의 고함수 슬러지 고화제의 배합비에 따른 구체적인 예는 제지 회사에서 발생하는 입도 1.2㎛, 비중 2.0의 제지연소재 700kg과 산성물질인 폐인산석고 300kg의 혼합으로 제1혼합물을 조성한 후, 상기 제1혼합물 800kg에 시멘트 100kg, 생석회 100kg를 첨가하여 제조한다.
Specific examples according to the blending ratio of the high-functional sludge solidifying agent of the present invention is after the first mixture is formed by mixing 700 kg of papermaking material with a particle size of 1.2 μm, specific gravity of 2.0 and 300 kg of waste acid gypsum phosphate, which is produced by a paper company, It is prepared by adding 100 kg of cement and 100 kg of quicklime to 800 kg of the first mixture.

이와 같이 제조된 고화제는 다음의 표 4와 같은 성분비율을 갖는다.
Thus prepared solidifying agent has a component ratio as shown in Table 4.

구분division SiO2 SiO 2 Al2O3 Al 2 O 3 Fe2O3 Fe 2 O 3 CaOCaO MgOMgO K2OK 2 O Na2ONa 2 O SO3 SO 3 Ig.lossIg.loss 제1혼합물First mixture 30.230.2 10.310.3 8.248.24 22.2122.21 1.161.16 0.950.95 0.710.71 20.820.8 4.04.0 시멘트cement 21.421.4 5.435.43 2.922.92 63.163.1 3.43.4 0.950.95 0.040.04 2.192.19 0.760.76 생석회quicklime 7.887.88 1.881.88 0.430.43 86.1386.13 0.760.76 0.170.17 0.010.01 0.630.63 1.921.92

상기 표 4의 고화제는 고화대상물의 함수율, 성분 및 사용 용도에 따라, 고화제의 양을 차등적으로 적용하게 되며, 일례로, 함수율 70%의 하수슬러지 고화시(건식) 사용되는 평균 배합비율은 하수슬러지 100 중량부 대비 고화제 30중량부를, 함수율 80%의 하수슬러지 고화시에는 하수슬러지 100중량부 대비 고화제 50중량부를 사용한다.
According to the solidifying agent of Table 4, the amount of solidifying agent is differentially applied according to the water content, component, and use of the solidification object. For example, the average compounding ratio used during sewage sludge solidification (dry) with a water content of 70%. 30 parts by weight of solidifying agent relative to 100 parts by weight of silver sewage sludge, and 50 parts by weight of solidifying agent relative to 100 parts by weight of sewage sludge when solidifying sewage sludge having a water content of 80%.

본 발명에 따른 고함수 슬러지 고화제는 고함수 하수슬러지, 고함수 퇴적오니, 축산폐수, 음식물 슬러지와 같은 고함수 슬러지 40 ~ 80wt%에 대해 20 ~ 60wt%의 범위로 혼합하여 사용함으로써, 무해 및 안정성, 유해중금속 유출방지, 악취제거, 고화촉진, 탁월한 수분감량 효과, 팽창성으로 인한 차수 성능 개선을 갖는 저렴한 비용의 고화제를 제공할 수 있어 고함수 슬러지 처리 안정제, 차수제, 도로지반제 용도로서 산업상 이용가능성이 뛰어나다.
The high-functional sludge solidifying agent according to the present invention is used by mixing in a range of 20 to 60 wt% with respect to 40 to 80 wt% of high-functional sludges such as high-functional sewage sludge, high-water sludge sludge, livestock wastewater and food sludge, It can provide a low cost solidifying agent with stability, prevention of harmful heavy metal leakage, odor elimination, promotion of solidification, excellent water loss effect, and improvement of order performance due to expandability. Excellent industrial availability.

Claims (7)

삭제delete 알칼리성 포졸란 물질인 제지 회사에서 발생하는 입도 0.5 ~ 80㎛, 비중 1.8 ~ 2.2의 제지연소재 30 ~ 80wt%와 산성물질인 폐인산석고 20 ~ 70wt%의 혼합으로 조성된 제1혼합물(A) 50 ~ 90wt%와,
시멘트, 생석회, 경소 백운석, 무수석고, 경화제, 응집제, 침전제, 침강제 중 선택되는 어느 1종 또는 2종 이상인 고형제(B) 10 ~ 50wt%의 혼합으로 조성된 것에 있어서,
상기 산성물질인 폐인산석고는 폐인산석고 100중량부에 대하여 순도 80 ~ 98%의 황산 50중량부를 가하여 폐인산석고에 함유된 중금속성분을 황화물형태의 안정화 화합물로 처리함으로써 중금속이 유출되지 않도록 하는 것임을 특징으로 하는 고함수 슬러지 고화제.






A first mixture (A) 50 composed of a mixture of 30 to 80 wt% of paper-burning combustion materials with a particle size of 0.5 to 80 μm, specific gravity of 1.8 to 2.2 and 20 to 70 wt% of acidic waste phosphate gypsum produced by a paper maker of alkaline pozzolanic material ~ 90wt%,
In the composition composed of 10 to 50 wt% of a solid (B) which is one or two or more selected from cement, quicklime, light dolomite, anhydrous gypsum, a hardener, a flocculant, a precipitant, and a sedimentation agent,
The acidic waste phosphate gypsum is added to 50 parts by weight of sulfuric acid having a purity of 80 to 98% with respect to 100 parts by weight of waste phosphate gypsum so that heavy metals contained in the waste phosphate gypsum are treated with a sulfide-type stabilizing compound to prevent heavy metals from spilling. High water sludge solidifying agent, characterized in that.






삭제delete 삭제delete 삭제delete 삭제delete 삭제delete
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101055317B1 (en) 2011-02-15 2011-08-09 주식회사 씨엠디기술단 Sludge solidified agent and menufacturing method of artificial soil usign the same
KR101146640B1 (en) * 2011-09-29 2012-05-16 주식회사 에프원테크 Preparation of neutral solidifying agent for treatment of sewage sludge
KR101279445B1 (en) 2012-03-16 2013-06-27 (주)비썬 Chemicals to treat wastewater, method for preparing the same and use thereof
KR102060569B1 (en) * 2019-06-28 2019-12-30 한일콘(주) Sewage sludge solidification treatment method
CN113149377A (en) * 2021-02-09 2021-07-23 虞克夫 Dewatered sludge curing agent, preparation method and use method
KR102561763B1 (en) * 2023-02-20 2023-07-31 주식회사 인터퓨어 Manufacturing method of composition for removing sludge

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JP2002088362A (en) 2000-09-14 2002-03-27 Sueo Wada Setting agent for soil
JP2004323599A (en) 2003-04-22 2004-11-18 Jfe Material Co Ltd Soil-solidifying agent and method for solidifying soil
KR100539680B1 (en) 2003-11-27 2005-12-28 박상철 Scrapped material used practical use materials manufacture method
KR100838627B1 (en) * 2006-10-09 2008-06-16 (주)토고이알씨 Solidification Chemical Manufacturing Method Utilizing Waste Material

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JP2002088362A (en) 2000-09-14 2002-03-27 Sueo Wada Setting agent for soil
JP2004323599A (en) 2003-04-22 2004-11-18 Jfe Material Co Ltd Soil-solidifying agent and method for solidifying soil
KR100539680B1 (en) 2003-11-27 2005-12-28 박상철 Scrapped material used practical use materials manufacture method
KR100838627B1 (en) * 2006-10-09 2008-06-16 (주)토고이알씨 Solidification Chemical Manufacturing Method Utilizing Waste Material

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101055317B1 (en) 2011-02-15 2011-08-09 주식회사 씨엠디기술단 Sludge solidified agent and menufacturing method of artificial soil usign the same
KR101146640B1 (en) * 2011-09-29 2012-05-16 주식회사 에프원테크 Preparation of neutral solidifying agent for treatment of sewage sludge
KR101279445B1 (en) 2012-03-16 2013-06-27 (주)비썬 Chemicals to treat wastewater, method for preparing the same and use thereof
KR102060569B1 (en) * 2019-06-28 2019-12-30 한일콘(주) Sewage sludge solidification treatment method
CN113149377A (en) * 2021-02-09 2021-07-23 虞克夫 Dewatered sludge curing agent, preparation method and use method
KR102561763B1 (en) * 2023-02-20 2023-07-31 주식회사 인터퓨어 Manufacturing method of composition for removing sludge

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