KR20100023368A - Hardened material and manufacture method using stone powder sludge - Google Patents
Hardened material and manufacture method using stone powder sludge Download PDFInfo
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- KR20100023368A KR20100023368A KR20080082087A KR20080082087A KR20100023368A KR 20100023368 A KR20100023368 A KR 20100023368A KR 20080082087 A KR20080082087 A KR 20080082087A KR 20080082087 A KR20080082087 A KR 20080082087A KR 20100023368 A KR20100023368 A KR 20100023368A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B28—WORKING CEMENT, CLAY, OR STONE
- B28C—PREPARING CLAY; PRODUCING MIXTURES CONTAINING CLAY OR CEMENTITIOUS MATERIAL, e.g. PLASTER
- B28C7/00—Controlling the operation of apparatus for producing mixtures of clay or cement with other substances; Supplying or proportioning the ingredients for mixing clay or cement with other substances; Discharging the mixture
- B28C7/04—Supplying or proportioning the ingredients
- B28C7/0422—Weighing predetermined amounts of ingredients, e.g. for consecutive delivery
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B28—WORKING CEMENT, CLAY, OR STONE
- B28B—SHAPING CLAY OR OTHER CERAMIC COMPOSITIONS; SHAPING SLAG; SHAPING MIXTURES CONTAINING CEMENTITIOUS MATERIAL, e.g. PLASTER
- B28B11/00—Apparatus or processes for treating or working the shaped or preshaped articles
- B28B11/24—Apparatus or processes for treating or working the shaped or preshaped articles for curing, setting or hardening
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
- C04B28/006—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing mineral polymers, e.g. geopolymers of the Davidovits type
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
- C04B2103/30—Water reducers, plasticisers, air-entrainers, flow improvers
- C04B2103/302—Water reducers
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- 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
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/91—Use of waste materials as fillers for mortars or concrete
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Abstract
Description
본 발명은 석분슬러지를 이용한 경화체 및 그 제조방법에 관한 것으로, 더욱 상세하게는 물을 함유하고 있는 석분 슬러지를 건조하지 않고 그대로 이용하여 경화시킬 수 있도록 한 석분슬러지를 이용한 경화체 및 그 제조방법에 관한 것이다.The present invention relates to a cured product using stone powder sludge and a method for producing the same, and more particularly, to a cured product using stone powder sludge and a method for producing the same, which allows the powdered stone sludge containing water to be cured without being dried. will be.
기존의 경화체는 시멘트와 같은 분말상의 경화재를 물과 섞어 모르타르, 콘크리트 등을 제조하는 방법이 주이며, 간혹 플라이애시, 고로슬래그 미분말, 실리카흄과 같은 콘크리트용 혼화재료를 시멘트에 일부 대체하여 경화시키는 방법이 주를 이루고 있다.Conventional cured products are mainly made by mixing powdery hardener such as cement with water to make mortar and concrete.In some cases, concrete mixed materials such as fly ash, blast furnace slag powder and silica fume are replaced by cement to harden them. This week.
부순골재 생산 공정에서 발생되는 함수 상태의 석분 슬러지를 사용하는 기술에 있어서도 함유된 물을 건조 시킨 후 분쇄하여 사용하는 방법이 주를 이루고 있다. 이렇게 추가되는 건조 및 분쇄 공정은 제품을 생산하는데 경제성을 손실시켜 그 활용도가 극히 미비하다.In the technique of using water sludge in a water-containing state generated in the crushed aggregate production process, the method of drying and crushing the contained water is mainly used. This additional drying and grinding process loses the economics of producing the product, and its utilization is extremely low.
또한, 함수상태의 석분슬러지를 건조시키지 않고 그대로 경량기포 콘크리트를 제조하는 경우도 있으나, 이 역시 시멘트, 소석회, 무수석고 등 경화시키기 위한 경화재가 추가적으로 필요하며, 오토클레이브라는 고온(약 180℃), 고압(약 10기압) 양생이 추가적으로 필요하여 경제성을 손실시켜 그 활용도가 극히 미비하다. 또한, 이 경우도 경량기포콘크리트 제조에만 한정되며 석분 슬러지의 사용량도 전체중량의 8-35중량% 수준으로 대량활용에 한계가 있다.In addition, there are cases where the lightweight foamed concrete is manufactured without drying the dry powdered sludge as it is, but this also requires additional hardening materials for curing cement, slaked lime, anhydrous gypsum, and the like. Due to the additional need for high pressure (about 10 atm) curing, the economical efficiency is very low. In addition, this case is also limited to the production of lightweight foam concrete, and the amount of stone powder sludge is limited to 8 to 35% by weight of the total weight.
현재 부순 잔골재를 생산하는 과정에서 부산물로 발생한 석분 슬러지는 년간 수천만톤이 생성되지만, 지정 폐기물로 분류되어 매립 및 위탁 처리된다. 그 결과 환경오염과 부순골재 제조업체에 비용 부담을 주고 있다. 또한 일정량의 물을 함유하고 있는 석분 슬러지는 새로운 처리방안이 있더라도 건조, 분쇄 및 고온, 고압양생 공정이 경제성을 만족시키지 못해 대다수가 매립되고 있는 실정이다.At present, tens of millions of tons of sludge produced as a by-product from the production of crushed fine aggregates are produced annually, but are classified as designated wastes and landfilled and consigned. As a result, environmental pollution and crushing aggregate manufacturers are burdened. In addition, even though a new treatment method, the stone powder sludge containing a certain amount of water, the drying, pulverization, high temperature, high pressure curing process does not satisfy the economic feasibility of the majority of landfill.
본 발명은 상기한 종래 기술의 문제점을 해결하기 위하여 안출된 것으로서, 강모래의 고갈과 해사의 채취 제한으로 생산량이 증가된 부순잔골재의 제조 공정에서 부수적으로 발생하는 물을 함유한 상태의 석분 슬러지를 재활용하여 환경오염의 원인을 제거함과 동시에 시멘트를 사용하지 않고 경화시킴으로서 시멘트 생산시 발생되는 온실가스인 CO2를 발생시키지 않는 환경친화적이고 경제적인 석분슬러지를 이용한 경화체 및 그 제조방법을 제공하는데 그 목적이 있다.The present invention has been made in order to solve the above problems of the prior art, the sludge of the state containing the water generated incidentally in the manufacturing process of the crushed fine aggregates increased production due to the depletion of the river sand and the limit of the harvest of sea sand The purpose of this invention is to provide a hardened body using environmentally friendly and economical stone powder sludge that does not generate CO 2 , which is a greenhouse gas generated during cement production by removing the cause of environmental pollution by curing and curing without using cement. There is this.
상기한 과제를 해결하기 위한 본 발명에 의한 석분슬러지를 이용한 경화체는 전체 100중량%에 대하여 석분슬러지 3-60중량%와, 플라이애시(또는 고로슬래그 미분말) 15-70중량%, 알칼리 활성용액 20-45중량%를 혼합하여 제조된다.The cured product using the stone powder sludge according to the present invention for solving the above problems is 3-60% by weight of stone powder sludge, 15-70% by weight of fly ash (or blast furnace slag fine powder), alkali
여기서, 상기 알칼리 활성용액은 NaOH(또는 KOH)와 Na2SiO3(또는 K2SiO3)를 각각 단독으로 사용하거나 혼합해서 사용하며, 혼합시 NaOH(또는 KOH)와 Na2SiO3(또는 K2SiO3)의 비율은 수용액 100중량%에 대하여 NaOH(또는 KOH) 25-75중량%, Na2SiO3(또는 K2SiO3) 25-75중량%로 이루어진다.Here, the alkali active solution may be used alone or mixed with NaOH (or KOH) and Na 2 SiO 3 (or K 2 SiO 3 ), respectively, NaOH (or KOH) and Na 2 SiO 3 (or K) when mixed. The ratio of 2 SiO 3 ) is 25-75 wt% NaOH (or KOH) and 25-75 wt% Na 2 SiO 3 (or K 2 SiO 3 ) with respect to 100 wt% of the aqueous solution.
이때, 상기 NaOH(또는 KOH) 수용액은 몰농도 5-20M의 수용액이고, 상기 Na2SiO3(또는 K2SiO3) 수용액은 수용액 100중량%에 대하여 물 40-70중량%, Na2SiO3(또는 K2SiO3) 30-60중량%가 혼합되어 이루어진다.At this time, the NaOH (or KOH) aqueous solution is an aqueous solution of 5-20M molar concentration, the Na 2 SiO 3 (or K 2 SiO 3 ) aqueous solution is 40-70% by weight of water, Na 2 SiO 3 with respect to 100% by weight of the aqueous solution (Or K 2 SiO 3 ) is made by mixing 30-60% by weight.
한편, 본 발명에 의한 석분슬러지를 이용한 경화체 제조방법은 석분슬러지, 플라이애시(또는 고로슬래그 미분말)와 알칼리 활성용액을 필요 중량만큼 계량하는 계량단계(S10)와, 상기 계량단계(S10)를 통해 계량된 석분슬러지에 플라이애시(또는 고로슬래그 미분말), 알칼리 활성용액과 감수제를 혼합하여 페이스트를 제조하 는 페이스트 제조단계(S20)와, 상기 페이스트 제조단계(S20)에서 제조된 페이스트를 20-26℃의 온도에서 0-36시간동안 1차 양생하고, 50-100℃에서 5-36시간 2차 양생하는 양생단계(S30);로 구성된다.On the other hand, the method for producing a cured product using the stone powder sludge according to the present invention, the weighing step (S10) and the weighing step (S10) and the weighing step to weigh the required amount of stone actives, fly ash (or blast furnace slag fine powder) and alkali active solution as necessary. Paste manufacturing step (S20) of preparing a paste by mixing fly ash (or blast furnace slag fine powder), alkali active solution and water reducing agent to the measured stone powder sludge, and paste prepared in the paste manufacturing step (S20) of 20-26. The first curing for 0-36 hours at a temperature of ℃, the curing step of secondary curing for 5 to 36 hours at 50-100 ℃ (S30); consists of.
상기와 같이 구성되는 본 발명의 석분슬러지를 이용한 경화체 및 그 제조방법은 20-60%의 함수율을 갖는 석분 슬러지를 건조, 분쇄 및 오토클레이브 공정없이 함수 상태로 재활용하여 환경오염의 원인을 제거하면서 임의의 가공과정에서 발생하는 추가비용을 절감하여 경제성 있는 경화체를 제조할 수 있는 이점이 있다.The cured product using the powdered sludge of the present invention configured as described above and a method for manufacturing the same are used while removing the cause of environmental pollution by recycling the powdered sludge having a moisture content of 20-60% in a water-containing state without drying, pulverizing and autoclaving processes. By reducing the additional costs incurred in the processing of the advantage that can be manufactured economically hardened body.
또한 시멘트를 사용하지 않고 경화시킴으로서 시멘트 생산시 발생되는 온실가스인 CO2를 발생시키지 않는 환경친화적이고 경제적인 경화체를 제조할 수 있는 이점이 있다.In addition, by hardening without using cement, there is an advantage in that an environmentally-friendly and economical hardened body which does not generate CO 2 , which is a greenhouse gas generated in cement production, may be manufactured.
이하, 본 발명에 의한 석분슬러지를 이용한 경화체 및 그 제조방법에 대하여 상세히 설명한다.Hereinafter, the hardened | cured material using the stone powder sludge which concerns on this invention, and its manufacturing method are demonstrated in detail.
본 발명에 의한 석분슬러지를 이용한 경화체는 전체 100중량%에 대하여 석분슬러지 3-60중량%, 플라이애시(또는 고로슬래그 미분말) 15-70%, 알칼리 활성용액 20-45중량%가 혼합되어 이루어진다.The cured product using the stone powder sludge according to the present invention is composed of 3 to 60% by weight of stone powder sludge, 15 to 70% of fly ash (or fine blast furnace slag), and 20 to 45% by weight of an alkaline active solution.
상기와 같은 구성물질을 혼합할 때 혼합을 용이하게 하기 위하여 고성능감수제를 석분 슬러지와 플라이애시(또는 고로슬래그 미분말) 100 중량부에 대하여 0.1-3중량부를 혼합할 수 있다.In order to facilitate mixing, the high performance water reducing agent may be mixed with 0.1-3 parts by weight with respect to 100 parts by weight of stone flour sludge and fly ash (or blast furnace slag fine powder).
상기 알칼리 활성용액은 석분슬러지와 반응하여 경화체를 형성하는 데 중요한 영향을 미치는 것으로, NaOH(또는 KOH)와 Na2SiO3(또는 K2SiO3)를 단독 또는 혼합해서 사용한다. NaOH(또는 KOH) 수용액은 몰농도 5-20M의 수용액을 사용하고, Na2SiO3(또는 K2SiO3) 수용액은 수용액 100중량%에 대하여 물 40-70중량%, Na2SiO3(또는 K2SiO3) 30-60중량%가 혼합되어 이루어진다.The alkali active solution has an important effect in forming a cured body by reacting with stone powder sludge. NaOH (or KOH) and Na 2 SiO 3 (or K 2 SiO 3 ) may be used alone or in combination. NaOH (or KOH) aqueous solution uses an aqueous solution of 5-20M molar concentration, Na 2 SiO 3 (or K 2 SiO 3 ) aqueous solution is 40-70% by weight of water, Na 2 SiO 3 (or K 2 SiO 3 ) 30-60% by weight is mixed.
알칼리 활성용액 중 NaOH(또는 KOH)와 Na2SiO3(또는 K2SiO3)를 혼합해 사용할 경우, NaOH(또는 KOH)와 Na2SiO3(또는 K2SiO3)의 비율은 알칼리 활성용액 100중량%에 대하여 NaOH(또는 KOH) 수용액 25-75중량%, Na2SiO3(또는 K2SiO3) 수용액 25-75중량%가 혼합되어 이루어진다.When used to mix the alkali activation solution NaOH (or KOH) and Na 2 SiO 3 (or K 2 SiO 3), the proportion of NaOH (or KOH) and Na 2 SiO 3 (or K 2 SiO 3) is an alkali activation solution 25-75 weight% of NaOH (or KOH) aqueous solution and 25-75 weight% of Na 2 SiO 3 (or K 2 SiO 3 ) aqueous solution are mixed with respect to 100 weight%.
상기 고성능감수제는 콘크리트의 워커빌러티(Workability)의 개선을 주목적으로 한 혼화제로서 나프탈렌계, 멜라민계, 폴리카르본산계 등 시중에서 판매되는 감수제가 사용된다.The high performance water reducing agent is a commercially available water reducing agent such as naphthalene-based, melamine-based or polycarboxylic acid-based as a admixture mainly intended to improve the workability of concrete.
본 발명에 의한 경화체를 제조하기 위한 배합은 아래 표 1과 같다.Formulation for producing a cured product according to the invention is shown in Table 1 below.
<표 1> 사용 배합<Table 1> Use Formulation
경화체를 제조하기 위한 페이스트 1m3에 대하여,With respect to the paste 1m 3 for the preparation of a cured body,
석분슬러지 대체율이 10%일 때 Activator/Solid 비율이 50%, 석분 슬러지 6.7중량%, 플라이애시 60.0중량%, 알칼리 활성용액 33.3중량% 이고, 알칼리 활성용액 중 NaOH 수용액은 40.0중량%, Na2SiO3 수용액은 60.0중량%이다.When the percentage of stone powder sludge is 10%, the Activator / Solid ratio is 50%, stone powder sludge 6.7% by weight, fly ash 60.0% by weight, alkaline active solution 33.3% by weight, NaOH aqueous solution in alkaline active solution is 40.0% by weight, Na 2 SiO 3 aqueous solution is 60.0 weight%.
석분슬러지 대체율이 30%일 때 Activator/Solid 비율이 50%, 석분 슬러지 20.0중량%, 플라이애시 46.7중량%, 알칼리 활성용액 33.3중량% 이고, 알칼리 활성용액 중 NaOH 수용액은 40.0중량%, Na2SiO3 수용액은 60.0중량%이다.When the replacement rate of stone powder sludge is 30%, the Activator / Solid ratio is 50%, stone powder sludge 20.0% by weight, fly ash 46.7% by weight, alkaline active solution 33.3% by weight, NaOH aqueous solution in alkaline active solution is 40.0% by weight, Na 2 SiO 3 aqueous solution is 60.0 weight%.
석분슬러지 대체율이 10%일 때 Activator/Solid 비율이 50%, 석분 슬러지 6.7중량%, 고로슬래그 미분말 60.0중량%, 알칼리 활성용액 33.3중량% 이고, 알칼리 활성용액 중 NaOH 수용액은 40.0중량%, Na2SiO3 수용액은 60.0중량%이다.When the percentage of stone powder sludge is 10%, Activator / Solid ratio is 50%, stone powder sludge 6.7% by weight, blast furnace slag fine powder 60.0% by weight, alkali active solution 33.3% by weight, NaOH aqueous solution in alkaline active solution is 40.0% by weight, Na 2 The aqueous SiO 3 solution is 60.0% by weight.
석분슬러지 대체율이 30%일 때 Activator/Solid 비율이 50%, 석분 슬러지 20.0중량%, 고로슬래그 미분말 46.7중량%, 알칼리 활성용액 33.3중량% 이고, 알칼리 활성용액 중 NaOH 수용액은 40.0중량%, Na2SiO3 수용액은 60.0중량%이다.When the replacement rate of stone powder sludge is 30%, the Activator / Solid ratio is 50%, stone powder sludge 20.0% by weight, blast furnace slag fine powder 46.7% by weight, alkali active solution 33.3% by weight, NaOH aqueous solution in alkali active solution is 40.0% by weight, Na 2 The aqueous SiO 3 solution is 60.0% by weight.
여기서 석분 슬러지의 중량은 건조되지 않은 함수상태의 석분 슬러지의 중량을 말한다.Here, the weight of the powdered sludge refers to the weight of the dried powdered sludge in the dry state.
상기 표에서 석분슬러지 대체율은 석분슬러지와 플라이애시(또는 고로슬래그 미분말)의 전체 중량에서 대체된 석분슬러지의 중량비율을 나타내며, Activator/Solid 비율은 알칼리 활성용액(Activator)과 고체부분(석분 슬러지+플라이애시 또는 고로슬래그 미분말)의 중량비율을 나타낸다.In the above table, the replacement ratio of stone powder sludge represents the weight ratio of stone powder sludge replaced from the total weight of stone powder sludge and fly ash (or blast furnace slag fine powder), and the Activator / Solid ratio is an alkali activator and a solid part (stone powder sludge +). Fly ash or blast furnace slag fine powder).
경화체를 제조하기 위한 사용원료의 물리·화학적 특성은 아래 표 2-4와 도 1과 같다.Physical and chemical properties of the raw materials used to manufacture the cured product are shown in Table 2-4 and FIG. 1 below.
<표 2> 석분 슬러지의 화학적 특성Table 2 Chemical Properties of Stone Flour Sludge
<표 3> 알칼리 활성용액의 특성<Table 3> Characteristics of Alkali Active Solution
<표 4> 석분 슬러지의 입도 및 함수율Table 4 Particle Size and Water Content of Stone Sludge
본 발명에서 사용된 석분슬러지의 평균입도는 5~9μm이다.The average particle size of the lime powder sludge used in the present invention is 5 ~ 9μm.
상기와 같이 구성된 실시예 1, 2, 3 및 4의 혼합물을 Ø 2.54mm × 2.54mm 의 시편으로 제작하여 압축강도 시험을 실시하고 그 결과를 표 5에 나타내었다.The mixture of Examples 1, 2, 3, and 4 configured as described above was fabricated into specimens of Ø 2.54 mm × 2.54 mm, subjected to a compressive strength test, and the results are shown in Table 5.
<표 5> 실험 결과Table 5 Experimental Results
본 발명에 의한 석분슬러지를 이용한 경화체의 제조방법은 도 2를 참조로 하면 계량단계(S10)와, 페이스트 제조단계(S20)와, 양생단계(S30)를 포함하여 구성된다.The method for producing a cured product using stone powder sludge according to the present invention includes a measuring step S10, a paste manufacturing step S20, and a curing step S30.
상기 계량단계(S10)는 물을 함유한 상태 그대로의 석분슬러지, 플라이애시(또는 고로슬래그 미분말)와 알칼리 활성용액을 필요 중량만큼 계량하는 단계이다. The metering step (S10) is a step of measuring the amount of stone powder sludge, fly ash (or blast furnace slag fine powder) and the alkali active solution as necessary weight as it contains water.
상기 페이스트 제조단계(S20)는 상기 계량단계(S10)를 통해 계량된 석분슬러지에 플라이애시(또는 고로슬래그 미분말), 알칼리 활성용액을 혼합하여 페이스트를 제조하는 단계이다.The paste manufacturing step (S20) is a step of preparing a paste by mixing fly ash (or blast furnace slag fine powder) and an alkali active solution to the calcined sludge measured in the weighing step (S10).
여기서, 상기 페이스트 제조단계(S20)는 알카리 활성용액을 혼합할 때 필요에 따라 고성능 감수제를 더 혼합할 수도 있다.Here, the paste manufacturing step (S20) may be further mixed with a high performance water reducing agent as needed when mixing the alkaline active solution.
상기 양생단계(S30)는 상기 페이스트 제조단계(S20)에서 제조된 페이스트를 50-100℃에서 5-36시간동안 양생하는 단계이다.The curing step (S30) is a step of curing the paste prepared in the paste manufacturing step (S20) for 5 to 36 hours at 50-100 ℃.
이 양생단계(S30) 이전에는 상기 페이스트 제조단계(S20)에서 제조된 페이스 트를 20~26℃에서 10~36시간동안 먼저 양생하는 선행양생단계가 더 추가될 수도 있다.Prior to this curing step (S30) may be further added to the prior curing step of curing the paste prepared in the paste manufacturing step (S20) for 10 to 36 hours first at 20 ~ 26 ℃.
도 1은 석분 슬러지의 입도를 도시한 그래프도.1 is a graph showing the particle size of stone powder sludge.
도 2는 본 발명에 따른 석분슬러지를 이용한 경화체 제조방법을 도시한 순차도.2 is a sequential diagram showing a method for producing a cured product using stone sludge according to the present invention.
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| KR20160105642A (en) * | 2015-02-27 | 2016-09-07 | 한밭대학교 산학협력단 | Light-weigth hardened material composition using the industrial by-products and preparing method thereof |
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| KR19980033801A (en) * | 1996-11-01 | 1998-08-05 | 이현구 | Lightweight aggregate using stone flour sludge and water purification plant sludge and method of manufacturing the same |
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| KR101600747B1 (en) * | 2015-05-06 | 2016-03-08 | 한양대학교 산학협력단 | Composition for solidification of spoil or sludge, method for solidification of spoil or sludge using the same, and solid matter prepared therefrom |
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