WO2011098091A1 - Matériau synthétique à base de pvc contenant des cendres de schistes bitumineux et produit fabriqué à partir dudit matériau - Google Patents

Matériau synthétique à base de pvc contenant des cendres de schistes bitumineux et produit fabriqué à partir dudit matériau Download PDF

Info

Publication number
WO2011098091A1
WO2011098091A1 PCT/EE2011/000002 EE2011000002W WO2011098091A1 WO 2011098091 A1 WO2011098091 A1 WO 2011098091A1 EE 2011000002 W EE2011000002 W EE 2011000002W WO 2011098091 A1 WO2011098091 A1 WO 2011098091A1
Authority
WO
WIPO (PCT)
Prior art keywords
ash
oil shale
pvc
composite material
cao
Prior art date
Application number
PCT/EE2011/000002
Other languages
English (en)
Inventor
Ivar Viira
Tiiu Kiil
Original Assignee
Ivar Viira
Tiiu Kiil
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Ivar Viira, Tiiu Kiil filed Critical Ivar Viira
Publication of WO2011098091A1 publication Critical patent/WO2011098091A1/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/346—Clay

Definitions

  • PVC composite material that contains oil shale ash
  • This invention belongs into the field of material industry.
  • the invention is related to PVC (Polyvinylchloride) based composite material, where as a filler is used certain fractions of mineral industrial waste, i.e. oil shale ash.
  • PVC Polyvinylchloride
  • Such a composite material has reduced or absent HC1 emission at increased temperatures.
  • Oil shale fly ash that is added to PVC comprises a certain amount free CaO, wherein due to its chemical reactivity it is able to neutralize/bind HC1 emitted by PVC during thermal decomposition according to the formula (I).
  • Oli shale fly ash originates from the combustion of the mixture of carbonaceous, terrigenous and organic material produced through refining of oil shale.
  • the ash from combustion is a set of particles with different dimensions, density, magnetic and electrical characteristics and chemical and mineralogical content. Thus it is a polyfractional mixture, which can be characterised and classified after several qualities [1].
  • pulverized combustion - PF and circulating fluidized bed combustion - CFBC which are essentially different for their combustion temperatures (correspondingly 1200-1400 °C and 750-800 °C) as well as fraction size of the fuel, we hereby provide data of both ash types basing on the source [2].
  • Ash will separate in several technological assemblies of boiler aggregate and has been marked as follows: BA - bottom ash, INT - intrex ash, SHA - steam heater ash, ECO - economizer ash, PHA - air preheater ash, CA - cyclonic ash, ESPA1-4 - ash from the section of electric filter with relevant number.
  • the content of general CaO in CFBC as well as PF ashes decreases along ash tract, remaining the lowest in fine-fraction electric filter ashes. At the same time, the content of insoluble residue increases along ash tract in the ashes of both types.
  • PF ashes contain essentially more free CaO (up to 25%).
  • the content of free CaO is the highest in intrex ash (up to 19%), decreasing essentially in electric filter ashes.
  • the combustion temperature is essentially higher, carbonates will decompose almost entirely in the course of fuel combustion, and C0 2 content of the ash is low.
  • CFBC ashes contain more calcite (up to 34,8% in bottom ash) and less lime.
  • Magnesium is found in ashes mainly in the form of periclase, being partially bound into carbonates (dolomite in CFBC bottom ash) and silicates (mervinite, melilite).
  • silica compounds CFBC ashes contain mainly quartz (up to 17,9%) orthoclase (up to 15,7%).
  • PF ashes contain essentially more secondary silicates, such as belite (up to 20,3%) and mervinite (up to 13,2%).
  • Relatively higher content of secondary silicates in PF ashes refers to essentially higher combustion temperature, causing reactions between lime and minerals of sand-clay part upon initiation of the molten phase.
  • Table 1 Chemical content and physical characteristics of CFBC ashes [2]
  • Fraction size of CFBC ashes is varying along ash separation tract in very broad scale (Figure la).
  • Bottom ash is the coarsest (-45% of the particles have the diameter >0,63 mm)
  • intrex ash has average coarseness (-90% of the particles have the diameter 0,4- 0,045 mm)
  • electric filter ashes are the finest (85-95% of the particles have the diameter ⁇ 0,045 mm).
  • PF ashes have more uniform fraction size, containing less particles with the diameter >0,63mm compared to CFBC ashes ( Figure lb).
  • fly ash produced through the combustion of coal has been known.
  • this ash differs from oil shlae fly ash with its composition, shape of particles as well as colour (grey to black), and therefore it is not suitable for the production of light profiles.
  • JP2009073989 discloses the use of fly ash as a filler material or reinforcing agent in a polyvinyl chloride resin, rubber resine, polyolefin resin etc, whereby the fraction of fly ash shall be ⁇ 5 ⁇ , the amount of unburned carbon shall remain below 1% and sphericity of ash particles shall be 0,9-1 ,0.
  • US2002040084 discloses a composition containing fly ash, which particles have average size not exceeding 100 ⁇ and humidity content not exceeding 0,25%.
  • the composition including filler material forms 1-80 mass fractions in 100 mass fractions of polymer.
  • the composition is especially useful for the production of tubes in polyvinyl cloride compositions.
  • JP2001043737 discloses the content of PVC cover (composite) of electric cables, including 10-100 fractions of coal fly ash per 100 fractions of PVC resin.
  • a plasticizer has been added, and if necessary, also colouring agents, additives inhibiting combustion and facilitating processing.
  • JP1 1 140331 (A) discloses a composite, which would not emit HC1 gas upon incineration.
  • a 1-10% synthetic zeolite has been added to a resin such as polyethylene or polyvinyl chlorie, which has been obtained through alkaline processing of coal ash.
  • CN1 1 10773 (A) discloses a tube made of plasticized fly ash, containing fly ash with granular mesh size exceeding 200-300, mixed together with the use of polyethylene or polyvinyl chloride at 160-180 °C.
  • CaO + 2HC1 CaCl 2 + H 2 0
  • the technical level has not introduced interactions of PVC and oil shale fly ash by the presence of oxygen at moderate temperatures (up to 300-400 °C).
  • Objective of the invention is met by a composite material, where in a preferred embodiment the amount of oil shale ash with suitable composition in PVC composite varied within the range 0,5-60 mass percent.
  • Fluidized bed ash (CFBC) and pulverized combustion ash (PF) were used.
  • FIGS. 2a and 2b SEM images of CFBC ashes: BA (ground to ⁇ 1 mm), ECO, ESPA1 and 2b: PF ashes: BA, CA, ESPA1 [2].
  • Figure 4 Composition of balance mixture in the system CaO - HC1 - C0 2 - H 2 0 depending on the temperature.
  • Figure 7 Decomposition curves of samples in PVC2 mixture with pure calcium oxide with mass ratio 1 : 1 or 1 :2.
  • Figure 8 Decomposition curves of pulverized combustion ash PF mixtures with material PVC2.
  • the most common filler material of powder PVC composite is chalk. Objective of the invention is to replace chalk with oil shale fly ash. In realisation of the invention the other components of the composite were left constant, changing only the amount of oil shale fly ash in the composite.
  • the amount of oil shale ash with suitable composition in PVC composite varied within the range 0,5-60 mass percent. Fluidized bed ash and pulverized combustion ash were used.
  • the used oil shale ashes were one pulverized combustion ash (PF ash ESPAl), with free calcium oxide content 14,9% and specific surface 1,6 m 2 /g, and one fluidized bed ash (CFBC ash ESPAl with free CaO content 8,2% and specific surface 6,7 m 2 /g) according to Table 1. Comparative tests were performed with pure calcium oxide obtained through heating of CaC0 3 at 1000 °C and not containing calcium hydroxide or non-decomposed calcium carbonate (the verified mass loss to the temperature 1000 °C was 0%).
  • Binding tests of HC1 were performed with a thermal analysis equipment MOM with the objective to determine the temperature range of decomposition of PVC and binding of HC1 and assess the extent of binding. Composition of mixtures was varied in accordance with mass ratios of PVC and the binding component (lime material) 1 : 1 and 1 :2. In case of pure CaO the mass ratio 1 : 1 also meets approximately the mole ratio CaO:HCl «l : 1.
  • Tests were performed in the conditions of dynamic increase of temperature with heating speed 10 °C min -1 to the end temperature 1000 °C. Standard platinum crucibles were used. Heating was performed in oxidizing conditios, atmospheric environment, with air feed rate 25 1 h _I . Sample mass in a crucible was 100 mg. PVC and lime material were mixed mechanically, without using any additional grinding or influencing physical qualities of the particles. In these tests the solid phase was not analysed.
  • Figure 4 shows that thermodynamically the produced balance mixture contains a stable CaCl 2 .
  • some hydrochloride will start to appear again in the balance mixture in the system, in the range 600...800 °C also the amount of CaC0 3 increases to some extent due to the presence of C0 2 and at the temperature over 900 °C the latter will decompose, increasing the amount of free CaO in the mixture.
  • the binding of HC1 with oil shale ash facilitates thermodynamically the production of calcium chloride in a broad range of temperature.
  • a smooth peak in the upper curve in the range 600-800 °C is characteristic to the reactions of C0 2 with filler material, and the fact that the difference of mass losses of the two materials remains within 5% by the end of the test confirms that in the reactions with filler material PVC1 is binding HC1 produced upon decomposition of PVC to some extent.
  • the used oil shale ashes do not have any significant mass loss until the temperature 600 °C. Only at the temperature over 650 °C the carbonate part contained in the ash will start to decompose significantly. Therefore the curve characterising binding, calculated from the difference of the curves describing decomposition of mixture and PVC, should also describe binding of HCl from gaseous phase qualitatively until this temperature.
  • the figure 8 shows that in case of the temperatures of HCl separation (250-350 °C) the peak characterising the binding has also clearly formed (curve 4). Calculated curve of a mixture with higher mass ratio matched the curve 4. Slanting peaks corresponding to the reactions of formation and decomposition of carbonates cannot be seen as clearly here as in case of pure calcium oxide, because these ashes already contain carbonates; also this graph does not enable to draw conclusions about the percentage of bound HCl, because there are more and different parallel reactions with increase and decrease of mass in this system.
  • Fluidized bed ash was much more efficient binder of HC1 compared to pulverized combustion ash, in spite of higher content of free CaO in pulverized combustion ash.
  • the difference of these two ashes is mainly in specific surface, therefore an oil shale ash with as large specific surface as possible would be preferred.
  • Fluidized bed ash contains somewhat more calcium carbonate, which can also react with hydrochloride, its surface is more porous and access of hydrochloride to non-reacted oxide or carbonate is easier due to lower diffusion resistance. This leads to a conclusion that in terms of binding of HC1 the fluidized bed ash would be the most suitable among various oil shale ashes.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Dispersion Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Processing Of Solid Wastes (AREA)

Abstract

La présente invention concerne un matériau composite à base de polychlorure de vinyle (PVC), comprenant comme charge certaines fractions de cendres de schistes bitumineux qui sont des déchets industriels minéraux, en particulier des cendres de poussières et des cendres de couches en ébullition. Un tel matériau composite émet des quantités réduites d'HCl ou n'en émet pas du tout à des températures élevées. Les cendres de schistes bitumineux ajoutées au PVC contiennent une certaine quantité de CaO libre, qui est capable, du fait de sa réactivité chimique, de neutraliser/de se lier au HCl émis pendant la désintégration thermique du PVC selon la formule CaO + 2HCl = CaCl2 + H2O. La teneur en cendres de schistes bitumineux dans le matériau composite à base de PVC va de 0,5 à 60 %. L'invention concerne également un produit fabriqué à partir dudit matériau composite.
PCT/EE2011/000002 2010-02-15 2011-02-14 Matériau synthétique à base de pvc contenant des cendres de schistes bitumineux et produit fabriqué à partir dudit matériau WO2011098091A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EEP201000022A EE05625B1 (et) 2010-02-15 2010-02-15 P?levkivituhka sisaldav PVC komposiitmaterjal ja sellest materjalist valmistatud toode
EEP201000022 2010-02-15

Publications (1)

Publication Number Publication Date
WO2011098091A1 true WO2011098091A1 (fr) 2011-08-18

Family

ID=44072719

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EE2011/000002 WO2011098091A1 (fr) 2010-02-15 2011-02-14 Matériau synthétique à base de pvc contenant des cendres de schistes bitumineux et produit fabriqué à partir dudit matériau

Country Status (2)

Country Link
EE (1) EE05625B1 (fr)
WO (1) WO2011098091A1 (fr)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2012083972A1 (fr) * 2010-12-23 2012-06-28 Tallinn University Of Technology Composite de matière polymère comportant des charges minérales
WO2014100864A1 (fr) * 2012-12-28 2014-07-03 Braskem S.A. Composition polymère et son utilisation, procédé de polymérisation et produit
US20190022554A1 (en) * 2017-07-19 2019-01-24 King Abdullah II Fund for Development Quality improvement of oily wastewater
CN109517300A (zh) * 2018-11-20 2019-03-26 内蒙古佳运通智能环保新材料有限公司 一种有机-无机固体废弃物复合材料及其制备方法和应用

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EE05806B1 (et) 2016-04-22 2018-06-15 Mineralplast Oü Põlevkivilendtuhka sisaldav polümeerkomposiitmaterjal ja meetod selle valmistamiseks

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
RU1804465C (ru) * 1990-11-29 1993-03-23 Виктор Васильевич Деревянко Полимерна композици дл линолеума
CN1110773A (zh) 1994-04-25 1995-10-25 辽宁华侨科技开发总公司 粉煤灰塑化管材
JPH11140331A (ja) 1997-11-07 1999-05-25 Fukusuke Kogyo Co Ltd 合成樹脂組成物とその製品
JP2001043737A (ja) 1999-08-02 2001-02-16 Fujikura Ltd 電気ケーブルの介在用樹脂混和物
US20020040084A1 (en) 1998-06-11 2002-04-04 Boral Material Technologies, Inc. Fly ash filler and polyvinyl chloride compositions and conduits therefrom
US20050014881A1 (en) * 2003-07-17 2005-01-20 Wacker Polymer Systems Gmbh & Co. Kg Redispersion powders comprising pozzolanic components
JP2009073989A (ja) 2007-09-21 2009-04-09 Oita Univ フライアッシュを含有する樹脂組成物

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
RU1804465C (ru) * 1990-11-29 1993-03-23 Виктор Васильевич Деревянко Полимерна композици дл линолеума
CN1110773A (zh) 1994-04-25 1995-10-25 辽宁华侨科技开发总公司 粉煤灰塑化管材
JPH11140331A (ja) 1997-11-07 1999-05-25 Fukusuke Kogyo Co Ltd 合成樹脂組成物とその製品
US20020040084A1 (en) 1998-06-11 2002-04-04 Boral Material Technologies, Inc. Fly ash filler and polyvinyl chloride compositions and conduits therefrom
JP2001043737A (ja) 1999-08-02 2001-02-16 Fujikura Ltd 電気ケーブルの介在用樹脂混和物
US20050014881A1 (en) * 2003-07-17 2005-01-20 Wacker Polymer Systems Gmbh & Co. Kg Redispersion powders comprising pozzolanic components
JP2009073989A (ja) 2007-09-21 2009-04-09 Oita Univ フライアッシュを含有する樹脂組成物

Non-Patent Citations (10)

* Cited by examiner, † Cited by third party
Title
A. OTS, POLEVKIVI POLETUSTEHNIKA, 2004
DATABASE CA [online] CHEMICAL ABSTRACTS SERVICE, COLUMBUS, OHIO, US; 14 November 1994 (1994-11-14), DEREVYANKO, VIKTOR V. ET AL: "PVC composition for linoleum", XP002641453, retrieved from STN Database accession no. 1994:632285 *
M. UIBU; M. UUS; R. KUUSIK: "C02 mineral sequestration in oil shale wastes from Estonian power production", JOURNAL OF ENVIRONMENTAL MANAGEMENT, vol. 90, 2009, pages 1253 - 1260, XP025679730, DOI: doi:10.1016/j.jenvman.2008.07.012
OH, S. C.; KWON, W.-T.; KIM, S.-R.: "Dehydrochlorination characteristics of waste PVC wires by thermal decomposition", JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY, vol. 15, 2009, pages 438 - 441, XP026172438, DOI: doi:10.1016/j.jiec.2008.11.010
OJA, V. ET AL: "Thermal processing of polyvinylchloride waste with oil shale ash to capture chloride", OIL SHALE, vol. 25, no. 2, 20 June 2008 (2008-06-20), Tallinn, Estonia, pages 203 - 208, XP002641454, ISSN: 0208-189X, DOI: 10.3176/oil.2008.2.02 *
R. KUUSIK; L. TURN; A. TRIKKEL; M. UIBU: "Carbon dioxide binding in the heterogeneous systems formed at combustion of oil shale. 2. Interactions of system components - thermodynamic analysis", OIL SHALE, vol. 19, 2002, pages 143 - 160
R. KUUSIK; M. UIBU; K. KIRSIMÄE: "Characterization of oil shale ashes formed at industrial scale boilers", OIL SHALE, vol. 22, 2005, pages 407 - 420
R. KUUSIK; M. UIBU; M. TOOM; M.-L. MUULMANN; T. KALJUVEE; A. TRIKKEL: "Sulphation and carbonization of oil shale CFBC ashes in heterogeneous systems", OIL SHALE, vol. 22, 2005, pages 421 - 434
SCIENCEDIRECT, 17 November 2009 (2009-11-17)
TIIKMA, L.; JOHANNES, I.; LUIK, H.: "Fixation of chlorine evolved in pyrolysis of PVC waste by Estonian oil shales", JOURNAL OF ANALYTICAL AND APPLIED PYROLYSIS, vol. 75, 2006, pages 205 - 210, XP024998807, DOI: doi:10.1016/j.jaap.2005.06.001

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2012083972A1 (fr) * 2010-12-23 2012-06-28 Tallinn University Of Technology Composite de matière polymère comportant des charges minérales
WO2014100864A1 (fr) * 2012-12-28 2014-07-03 Braskem S.A. Composition polymère et son utilisation, procédé de polymérisation et produit
US20190022554A1 (en) * 2017-07-19 2019-01-24 King Abdullah II Fund for Development Quality improvement of oily wastewater
US10583372B2 (en) * 2017-07-19 2020-03-10 King Abdullah II Fund for Development Quality improvement of oily wastewater
CN109517300A (zh) * 2018-11-20 2019-03-26 内蒙古佳运通智能环保新材料有限公司 一种有机-无机固体废弃物复合材料及其制备方法和应用

Also Published As

Publication number Publication date
EE201000022A (et) 2011-10-17
EE05625B1 (et) 2013-02-15

Similar Documents

Publication Publication Date Title
KR102010490B1 (ko) 응집, 침적, 부식과 같은 문제점들을 회피하고 배출들을 감소시키기 위한 미네랄 첨가제 배합 조성물들 및 연소실들의 작동 방법들
WO2011098091A1 (fr) Matériau synthétique à base de pvc contenant des cendres de schistes bitumineux et produit fabriqué à partir dudit matériau
DK2891843T3 (en) Process for incineration of waste with a mineral additive
DE2624971A1 (de) Verfahren zur verwertung industrieller abfaelle
Galhetas et al. Characterization, leachability and valorization through combustion of residual chars from gasification of coals with pine
WO2015053723A1 (fr) Utilisation en tant que combustible solide de schiste ou de cendres obtenus par des procédés de démantèlement de schiste bitumineux avec ou sans additifs
TWI483918B (zh) 水泥製造方法
Zhang et al. Combustibility of dried sewage sludge and its mineral transformation at different oxygen content in drop tube furnace
KR101104314B1 (ko) 폐 부산물을 이용한 시멘트 클링커 제조용 연료 조성물 및 이를 이용한 시멘트 클링커의 제조방법
Balgaranova et al. Utilization of wastes from the coke-chemical production and sewage sludge as additives in the brick-clay
EP2245121A2 (fr) Procédé d enrichissement de carburant
Kaljuvee et al. Behavior of sulphur compounds at combustion of oil shale semicoke
CN1015252B (zh) 石膏脱硫
WO2014181133A2 (fr) Procédé d'enrichissement d'un combustible
Mut Sulfur Release during alternative fuels combustion in cement rotary kilns
JP2006232637A (ja) 無水石膏の製造方法
Kijo-Kleczkowska et al. Research on Waste Combustion in the Aspect of Mercury Emissions. Materials 2023, 16, 3213
CN104498120A (zh) 消烟固硫环保煤及其制备方法
Claesson et al. Chemical characterization of waste fuel for fluidized bed combustion
Radojević et al. Negative impacts of petroleum coke as an energy source in the brick-making industry
JP7056793B1 (ja) 廃棄物処理装置及び廃棄物処理方法
Dudynski et al. Solid residues from gasification of biomass
Ningsih et al. Emission and heavy metal content characteristic of densified refused derived fuels of oil sludge and biomass combination as an alternative fuel for cement plant
RU2729638C1 (ru) Способ изготовления топлива из твердых коммунальных отходов
CN107285357A (zh) 一种利用电石渣捕集二氧化碳的方法

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 11709322

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 11709322

Country of ref document: EP

Kind code of ref document: A1