WO2015014953A1 - Produits à base de ciment au soufre - Google Patents

Produits à base de ciment au soufre Download PDF

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Publication number
WO2015014953A1
WO2015014953A1 PCT/EP2014/066527 EP2014066527W WO2015014953A1 WO 2015014953 A1 WO2015014953 A1 WO 2015014953A1 EP 2014066527 W EP2014066527 W EP 2014066527W WO 2015014953 A1 WO2015014953 A1 WO 2015014953A1
Authority
WO
WIPO (PCT)
Prior art keywords
sulphur
carbon atoms
linear
inorganic material
hydrocarbyl group
Prior art date
Application number
PCT/EP2014/066527
Other languages
English (en)
Inventor
Guy Lode Magda Maria Verbist
Cornelis Pieter Hamelink
Edward Ross DIXON
Arianne Elisabeth HOMMES
Original Assignee
Shell Internationale Research Maatschappij B.V.
Shell Oil Company
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 Shell Internationale Research Maatschappij B.V., Shell Oil Company filed Critical Shell Internationale Research Maatschappij B.V.
Priority to EP14749755.6A priority Critical patent/EP3027577A1/fr
Priority to EA201690313A priority patent/EA030417B9/ru
Publication of WO2015014953A1 publication Critical patent/WO2015014953A1/fr

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Classifications

    • 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
    • C04B28/36—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 sulfur, sulfides or selenium
    • 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

Definitions

  • the present invention provides a process for the preparation of sulphur cement products.
  • the invention also provides sulphur cement products including sulphur cement, sulphur mortar and sulphur concrete.
  • invention also provides modified sulphur that can be used in the preparation of sulphur cement products.
  • the invention also provides modified particulate inorganic material that can be used in the preparation of sulphur cement products.
  • Elemental sulphur or modified sulphur can be used to bind aggregate and filler, thereby providing sulphur cement products such as sulphur mortar and sulphur concrete .
  • Sulphur concrete can be used in a variety of pre-cast concrete applications such as marine defences, paving slabs, road barriers and retaining walls.
  • WO 2008 148804 discloses that polysulphide- containing organosilanes can be used as stabilising agents to prepare sulphur cement products having improved water uptake behaviour.
  • the sulphur cement products additionally have advantageous mechanical properties.
  • Methanol and ethanol are volatile organic compounds (VOCs) and it is desirable to limit the amount of VOCs that are released during the manufacture of sulphur cement products.
  • VOCs volatile organic compounds
  • the present inventors have found that by using a different type of organosilane in a process for the preparation of sulphur cement products it is possible to have reduced VOC production but still produce sulphur cement products having satisfactory water uptake
  • the invention provides a process for the preparation of a sulphur cement product comprising the steps of:
  • R 1 is a linear or branched hydrocarbyl group having from 2-24 carbon atoms and R 2 is a linear or branched hydrocarbyl group having from 2-40 carbon atoms, and
  • the present invention provides a sulphur cement product comprising sulphur and the reaction product of particulate inorganic material and an oligomeric organosilane having one or more terminal groups of general formula (I)
  • R 1 is a linear or branched hydrocarbyl group having from 2-24 carbon atoms and R 2 is a linear or branched hydrocarbyl group having from 2-40 carbon atoms
  • the present invention provides modified sulphur comprising sulphur and an oligomeric organosilane having one or more terminal groups of general formula (I)
  • R 1 is a linear or branched hydrocarbyl group having from 2-24 carbon atoms and R 2 is a linear or branched hydrocarbyl group having from 2-40 carbon atoms.
  • the modified sulphur is suitably used in a process for the preparation of the sulphur cement products of the invention .
  • the present invention provides modified particulate inorganic material which is the reaction product of particulate inorganic material and an oligomeric organosilane having one or more terminal groups of general formula (I)
  • R 1 is a linear or branched hydrocarbyl group having from 2-24 carbon atoms and R 2 is a linear or branched hydrocarbyl group having from 2-40 carbon atoms.
  • the modified particulate inorganic material is suitably used in a process for the preparation of the sulphur cement products of the invention.
  • sulphur cement product refers to a composite comprising sulphur, filler and optionally aggregate. Fillers and aggregate are particulate
  • Fillers have an average particle size in the range of from 0.1 ⁇ to 0.1 mm. Fine
  • Sulphur cement of the invention comprises sulphur and filler, but no aggregate.
  • Sulphur mortar of the invention comprises sulphur, filler and fine aggregate, but does not comprise coarse
  • Sulphur concrete of the invention comprises sulphur, filler, coarse aggregate and optionally fine aggregate .
  • Sulphur cement preferably comprises from 25 to 80wt% sulphur and from 20 to 75wt% filler.
  • Sulphur mortar preferably comprises from 5 to 40wt% sulphur, from 45 to 90wt% fine aggregate and from 1 to 10wt% filler; more preferably from 5 to 30wt% sulphur, from 55 to 75wt% fine aggregate and from 3 to 8wt% filler.
  • Sulphur concrete preferably comprises from 5 to 40wt% sulphur, from 25 to
  • 50wt% coarse aggregate from 20 to 40wt% fine aggregate and from 1 to 10wt% filler; more preferably from 5 to 30wt% sulphur, from 30 to 40wt% coarse aggregate, from 25 to 35wt% fine aggregate and from 3 to 8wt% filler.
  • the particulate inorganic material may be any particulate inorganic material known to be suitable as sulphur cement filler or aggregate.
  • the particulate inorganic material has oxide or hydroxyl groups on its surface.
  • suitable particulate inorganic materials are silica, fly ash, limestone, quartz, iron oxide, alumina, titania, carbon black, gypsum, talc or mica, sand, gravel, rock or metal- silicates. More preferably the particulate inorganic material is a silica or a silicate. Examples of such silica or silicates are quartz, sand and metal-silicates
  • organosilane having one or more terminal groups of general formula (I) are admixed.
  • R 1 is a linear or branched hydrocarbyl group having from 2-24 carbon atoms and R 2 is a linear or branched hydrocarbyl group having from 2-40 carbon atoms.
  • the oligomeric organosilane is suitably prepared by a process wherein a silane of formula (II) is reacted with a polyhydrox -containing compound of formula (III) :
  • X is a hydrolysable leaving group, preferably Ci- 6 alkoxy and most preferably ethoxy.
  • X is a hydrolysable leaving group, preferably Ci- 6 alkoxy and most preferably ethoxy.
  • more than one silane may be used, e.g. two silanes may be used:
  • the organosilane is oligomeric in that it will have resulted from the reaction of a number of organosilane monomers .
  • the structure of the oligomeric organosilane is preferably according to formula (IV) :
  • the oligomer will have at least two terminal groups. At least one of the terminal groups, possibly more, will be of formula (I) .
  • R 1 is a linear or branched hydrocarbyl group having from 2-24 carbon atoms.
  • R 1 has from 2-16 carbon atoms, more preferably from 2-8 carbon atoms.
  • Preferred groups include 2-methylpropyl and l-methyl-3,3- dimethylpropyl .
  • the carbon chain between the linked oxygen atoms is three carbon atoms long.
  • R 1 is preferably not functionalised .
  • R 2 is a linear or branched hydrocarbyl group having from 2-40 carbon atoms.
  • R 2 has from 2-24 carbon atoms, more preferably from 2-16 carbon atoms.
  • R 2 is optionally functionalised with one or more groups chosen from thiol, thioester, alcohol, ester, carboxylic acid, carbonyl amine or amide groups .
  • R 2 is functionalised with a thiol or
  • Suitable oligomeric organosilanes and methods for making them are disclosed in WO 2006 86375 and WO 2008 21308. Oligomeric organosilanes are available from
  • the sulphur cement products of the invention are suitably prepared by a process wherein all the components are admixed at a temperature at which the sulphur is molten, i.e. typically above 120°C, preferably in the range of from 120 to 150°C, more preferably in the range of from 125 to 140°C.
  • the admixture is preferably poured into a mould.
  • the sulphur cement product is then
  • the sulphur cement product can be demoulded.
  • the amount of oligomeric organosilane that is admixed with the sulphur and the particulate inorganic material is preferably from 0.05 to lwt%, based upon the weight of the sulphur, preferably from 0.1 to 0.4wt%.
  • the modification may provide insufficient
  • a selection of the components may be supplied to the mixing step in the form of a pre-composition or masterbatch.
  • sulphur and the oligomeric organosilane may be supplied as modified sulphur. Therefore, in a further aspect, the present invention provides modified sulphur, comprising sulphur and an oligomeric organosilane having one or more terminal groups of general formula (I)
  • R 1 is a linear or branched hydrocarbyl group having from 2-24 carbon atoms and R 2 is a linear or branched hydrocarbyl group having from 2-40 carbon atoms.
  • the modified sulphur preferably comprises less than lwt% filler and less than lwt% aggregate; and most preferably comprises no filler and no aggregate.
  • the modified sulphur preferably comprises from 0.01 to 20wt% of oligomeric organosilane, more preferably from 0.01 to 10wt%, most preferably from 0.01 to lwt%, wherein weight percentages are based upon the weight of the modified sulphur.
  • the modified sulphur preferably comprises at least 80wt% sulphur.
  • the modified sulphur may comprise higher quantities of oligomeric organosilane, e.g. from 5 to 20wt%, and may also comprise higher quantities of filler, e.g. from 5 to 20wt%, wherein weight percentages are based upon the weight of the modified sulphur.
  • the modified sulphur is a "concentrated” modified sulphur and such a "concentrated” modified sulphur can be used in small quantities to provide significant amounts of oligomeric organosilane .
  • particulate inorganic material and the oligomeric organosilane may be supplied as modified particulate inorganic material. Therefore, in a further aspect, the present invention provides modified particulate inorganic material which is the reaction product of particulate inorganic material and an
  • R 1 is a linear or branched hydrocarbyl group having from 2-24 carbon atoms and R 2 is a linear or branched hydrocarbyl group having from 2-40 carbon atoms.
  • the modified particulate inorganic material is suitably prepared by combining particulate inorganic material with from 0.001 to 5wt% of oligomeric organosilane, more preferably from 0.01 to lwt%, most preferably from 0.01 to 0.1wt%, wherein weight percentages are based upon the weight of the particulate inorganic material.
  • Sulphur cement products produced according to the invention can be used in a variety of applications .
  • Sulphur concrete may be used in pre-cast concrete applications such as marine defences, paving slabs, road barriers and retaining walls .
  • NXT Z 100 is an oligomeric organosilane available from Momentive Performance Materials Inc. Three samples of the organosilane were used: sample [1] was a fresh bottle of the organosilane, sample [2] was a two-week-old bottle of the organosilane and sample [3] had been exposed to atmospheric conditions in a fume-hood
  • NXT Z 100 is prone to moisture uptake as indicated by 9.20% mass gain when exposed to atmospheric conditions overnight in a fume-hood.
  • the durability of the sulphur mortars was determined by measuring flexural strength retention and water intrusion after two months submersion in water. Results are shown in Figures 1 and 2.
  • the sulphur mortars prepared according to the process of the invention have better strength retention and water intrusion properties than a sulphur mortar that does not contain organosilane (comparative example 1) . They have similar, but slightly worse, strength retention and water intrusion properties than a sulphur mortar that comprises a TESPT organosilane (comparative example 2) .
  • NXT Z 100 modifier (0.02, 0.04, 0.06 or 0.12 wt%) was then added and mixed in for another 5 minutes.
  • Pre-heated Fly Ash (150 °C, 15% (w/w)) was then added to the mixture and stirred for another 10 minutes.
  • the mixes were poured into pre-heated (150 °C) 4 cm x 4 cm x 16 cm silicon moulds and allowed to cool to ambient temperature in a fume-hood. The mortars were allowed to cure for a minimum of 48 hours.
  • the durability of the sulphur mortars was determined by measuring water intrusion and flexural strength retention after one month submersion in water.
  • Sulphur mortar samples were made using the following method: Sulphur (25% (w/w) ) pre-heated to approximately 65 °C and pre-heated sand (150 °C, 60% (w/w)) were mixed at 140 °C until a homogenous mixture was obtained. The appropriate quantity of TESPT (0.06 wt%) or NXT Z 100 modifier (0.02, 0.04, 0.06 or 0.12 wt%) was then added and mixed in for another 5 minutes. After this pre-heated Fly Ash (150 °C, 15% (w/w)) was added to the mixture and stirred for another 10 minutes. Finally the mixes were poured into pre-heated (150 °C) 4 cm x 4 cm x 16 cm silicon moulds and allowed to cool to ambient temperature in a fume-hood. The mortars were allowed to cure for a minimum of 48 hours.
  • the durability of the sulphur mortars was determined by measuring water intrusion and flexural strength retention after submersion in water for approximately eight months .
  • Samples containing 0.02 and 0.04 wt% NXT Z 100 perform similarly in terms of water intrusion to the sample containing 0.06 wt% TESPT. Also, their strength retention after almost 8 months storage in water is rather high (83.5% and 107.2% for samples containing 0.02 and 0.04wt% NXT Z 100, respectively).

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Inorganic Fibers (AREA)

Abstract

La présente invention concerne un produit de ciment au soufre contenant du soufre et le produit de réaction d'un matériau particulaire organique et d'un organosilane oligomère.
PCT/EP2014/066527 2013-08-01 2014-07-31 Produits à base de ciment au soufre WO2015014953A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
EP14749755.6A EP3027577A1 (fr) 2013-08-01 2014-07-31 Produits à base de ciment au soufre
EA201690313A EA030417B9 (ru) 2013-08-01 2014-07-31 Способ получения продукта из серного цемента и продукт из серного цемента, полученный этим способом

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP13178940.6 2013-08-01
EP13178940 2013-08-01

Publications (1)

Publication Number Publication Date
WO2015014953A1 true WO2015014953A1 (fr) 2015-02-05

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Application Number Title Priority Date Filing Date
PCT/EP2014/066527 WO2015014953A1 (fr) 2013-08-01 2014-07-31 Produits à base de ciment au soufre

Country Status (3)

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EP (1) EP3027577A1 (fr)
EA (1) EA030417B9 (fr)
WO (1) WO2015014953A1 (fr)

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008021308A2 (fr) * 2006-08-14 2008-02-21 Momentive Performance Materials Inc. Silane à fonctions mercapto
EP1958983A1 (fr) * 2007-02-12 2008-08-20 The Goodyear Tire & Rubber Company Composition de caoutchouc renforcée au silicium et utilisation dans les pneus
WO2010086391A1 (fr) * 2009-01-29 2010-08-05 Shell Internationale Research Maatschappij B.V. Pré-composition de ciment au soufre et produit de type ciment au soufre

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008021308A2 (fr) * 2006-08-14 2008-02-21 Momentive Performance Materials Inc. Silane à fonctions mercapto
EP1958983A1 (fr) * 2007-02-12 2008-08-20 The Goodyear Tire & Rubber Company Composition de caoutchouc renforcée au silicium et utilisation dans les pneus
WO2010086391A1 (fr) * 2009-01-29 2010-08-05 Shell Internationale Research Maatschappij B.V. Pré-composition de ciment au soufre et produit de type ciment au soufre

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
GUROVICH D ET AL: "NXT Z Silane- Processing and Properties of a New Virtually Zero VOC Silane", FALL 170TH TECHNICAL MEETING OF THE RUBBER DIVISION, AMERICAN CHEMICAL SOCIETY, OCTOBER 10-12,2006),, vol. 170th, 10 October 2006 (2006-10-10), pages 978A/1 - 978A/11, XP009100756 *

Also Published As

Publication number Publication date
EA030417B9 (ru) 2018-11-30
EA201690313A1 (ru) 2016-07-29
EA030417B1 (ru) 2018-08-31
EP3027577A1 (fr) 2016-06-08

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