WO2006099723A1 - Residus sulfones desasphaltes au solvant, leur procede de production et leur utilisation - Google Patents

Residus sulfones desasphaltes au solvant, leur procede de production et leur utilisation Download PDF

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WO2006099723A1
WO2006099723A1 PCT/CA2006/000412 CA2006000412W WO2006099723A1 WO 2006099723 A1 WO2006099723 A1 WO 2006099723A1 CA 2006000412 W CA2006000412 W CA 2006000412W WO 2006099723 A1 WO2006099723 A1 WO 2006099723A1
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Prior art keywords
residue
solvent deasphalting
sulfonated
solvent
sda
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PCT/CA2006/000412
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English (en)
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Henry Sawatzky
Stacey Nunes
Noel Mailvaganam
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National Research Council Of Canada
HER MAJESTY THE QUEEN IN RIGHT OF CANADA,represented by the Minister of Natural Resources Canada
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Publication of WO2006099723A1 publication Critical patent/WO2006099723A1/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
    • C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
    • C04B24/24—Macromolecular compounds
    • C04B24/36—Bituminous materials, e.g. tar, pitch
    • 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
    • C04B18/00—Use of agglomerated or waste materials or refuse as fillers for mortars, concrete or artificial stone; Treatment of agglomerated or waste materials or refuse, specially adapted to enhance their filling properties in mortars, concrete or artificial stone
    • C04B18/04—Waste materials; Refuse
    • C04B18/18—Waste materials; Refuse organic
    • 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
    • C04B28/02—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 hydraulic cements other than calcium sulfates
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G53/00—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more refining processes
    • C10G53/02—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more refining processes plural serial stages only
    • C10G53/04—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more refining processes plural serial stages only including at least one extraction step
    • C10G53/06—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more refining processes plural serial stages only including at least one extraction step including only extraction steps, e.g. deasphalting by solvent treatment followed by extraction of aromatics
    • 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 relates to sulfonated solvent deasphalting residues and their use as dispersants or superplasticizers, and more particularly, the present invention relates to a process and product for formulating a water requirement reducing admixture for cement-based mixtures formed by sulfonation of solvent deasphalted bitumen upgrading residues.
  • Non-distillable bitumen fractions such as those from conventional petroleums or from heavy oils and tar sands require pyrolytic processes to produce distillable products.
  • Common pyrolytic processes are coking and hydrocracking. There are various versions of both of these processes.
  • the products are volatile fractions and coke.
  • the volatile fractions contain heavy components and these heavy components can be recycled to the coker for further cracking to produce suitable distillable products.
  • bitumen upgrading residues are referred to as bitumen upgrading residues.
  • Hydrocracking residue and coker recycle have very low value as fuels, therefore it is desirable to be able to use them ⁇ h some way.
  • Sawatzky et al in United States Patent No. 5,584,920 issued December 17, 1996, discloses a process whereby a hydrocracking residue is sulfonated to form a water requirement reducing product for concrete mixtures. Although this process is useful, it has disadvantages. For example, hydrocracking residues still have some fuel value which is lost in this process. When sulfuric acid or oleum is used as a sulfonation agent, this process involves separation of a neutralized sulfonation product from a large amount of sulfate, which separation is not entirely successful. Efficiency of this process is limited by a methanol extraction step in which a significant amount of the sulfonation product is not recovered.
  • One way of recovering the fuel value from bitumen upgrading residue is to extract the bitumen upgrading residue with an organic solvent, for example hexanes. Such an extraction is termed solvent deasphalting. Much of the bitumen upgrading residue can be extracted in this manner leaving some insoluble material, called solvent deasphalting (SDA) residue.
  • SDA solvent deasphalting
  • solvent deasphalting (SDA) residues may be sulfonated to produce a dispersant for aqueous dispersions, especially a water requirement reducing product for cement-based mixtures.
  • a sulfonated solvent deasphalting residue of a solvent deasphalted bitumen upgrading residue there is provided a sulfonated solvent deasphalting residue of a solvent deasphalted bitumen upgrading residue.
  • a process for preparing a sulfonated solvent deasphalting residue comprising providing a solvent deasphalting residue and contacting the solvent deasphalting residue with a sulfonating agent.
  • a process for preparing sulfonated solvent deasphalting residue comprising: providing a solvent deasphalting residue; providing a sulfonating agent; contacting the solvent deasphalting residue with the sulfonating agent to produce a sulfonated solvent deasphalting residue; and neutralizing the sulfonated solvent deasphalting residue with a base.
  • the solvent deasphalting (SDA) residue may be prepared from any suitable bitumen upgrading residue, for example thermal, catalytic and conventional hydrocracking residues or coker product.
  • the bitumen upgrading residue has a weight average molecular weight of at least 200 g/mol.
  • the bitumen upgrading residue will be depleted in branched long chain aliphatics.
  • the bitumen upgrading residue is enriched in a aromatic ring containing molecules.
  • the bitumen upgrading residue has a carbon content of 80 wt% or greater.
  • One thermal hydrocracking residue generally referred to as the CANMET from PetroCanada, is a 64% conversion residue provided from cracking vacuum tower bottoms using iron based additives.
  • Another particular hydrocracking residue, referred to as HRI residue is obtained from a Husky oil catalytic cracking process.
  • One particular coker product, referred to as Syncrude coker recycle is obtained from the Syncrude flexi-coking process.
  • Bitumen upgrading residue is deasphalted (extracted) with an organic solvent to yield a solid phase comprising solvent insoluble residue, i.e. the SDA residue, and a liquid phase comprising the organic solvent and a solvent soluble fraction.
  • the solvent with the solvent soluble phase may be further treated to recover fuel values, e.g. oils.
  • the organic solvent is preferably an aliphatic solvent, more preferably a solvent comprising an alkane. In some instances a C 3 -C 2 O alkane is used. In some instances a C 3 -Ci 5 alkane is used. In some instances a C 3 -C 8 alkane is used. In some instances the alkane is linear. Paraffinic solvents, e.g.
  • propane, butanes, pentanes and hexanes are specific examples. Hexanes is particularly suitable for many purposes.
  • the use of more solvent provides cleaner separation but may lead to major utility costs in solvent recovery, greater environmental impact and might lead to sulfonation difficulties.
  • a solvent: hydrocracking residue ratio of 2:1 or greater is preferred in the deasphalting of the hydrocracking residue.
  • the SDA residue comprises asphaltenes and other solvent insoluble materials (e.g. sulfur and heavy metals (e.g. Ni and V)).
  • the SDA residue may have a weight average molecular weight of 200 g/mol or greater. In some instances, the weight average molecular weight may be 600 g/mol or greater. Higher molecular weight SDA residues may lead to better performance.
  • the SDA residue comprises 75-90 wt% of carbon.
  • the SDA residue comprises 5-10 wt% of hydrogen.
  • the SDA residue comprises 4-7 wt% of sulfur.
  • the SDA residue may comprise 75-90 wt% of carbon, 5-10 wt% of hydrogen and 4-7 wt% of sulfur.
  • the SDA residue may have lower alkyl content than the bitumen upgrading residue from which the SDA residue is produced. Lower alkyl content ultimately leads to less air entrainment in cement-based mixtures.
  • Sulfonation of the SDA residue may be achieved with any suitable sulfonating agent, for example, sulfuric acid, fuming sulfuric acid (oleum) and sulfur trioxide. Oleum and sulfur trioxide are of particular note.
  • Sulfonation is achieved by contacting the SDA residue with the sulfonating agent, or with a source of the sulfonating agent. Sulfonation may be achieved with or without the use of solvents. Without a solvent, solid or liquid SDA residue may be contacted with sulfonating agent, e.g. liquid oleum, liquid or gaseous sulfur trioxide). With a solvent, one or both of the SDA residue and the sulfonating agent may be dissolved in a solvent prior to reaction. In one embodiment, the SDA residue is dissolved in a solvent and the sulfonating agent is contacted with the SDA residue in the solvent.
  • sulfonating agent e.g. liquid oleum, liquid or gaseous sulfur trioxide
  • the sulfonating agent is dissolved in a solvent and the SDA residue is contacted with the sulfonating agent in the solvent.
  • the SDA residue and sulfonating agent are dissolved independently in solvents and the two resulting solutions contacted with each other.
  • the sulfonated product is generally insoluble in the solvent, and thus precipitates out as a solid. Removal of the supernatant liquid by centrifugation or other solid/liquid separation techniques may be used to isolate the solid sulfonated product and get rid of excess sulfonating agent after the reaction is complete.
  • Solvents are preferably inert to or only minimally reactive with one or both of the sulfonating agent and SDA residue, more preferably inert to or only minimally reactive with both.
  • Organic solvents are preferred.
  • Organic solvents having a boiling point from 3O 0 C to 13O 0 C are preferred.
  • suitable organic solvents include chlorinated organic solvents (e.g. methylene chloride, tetrachloroethylene, tetrachloroethane, etc.).
  • the weight ratio of sulfonating agent to SDA residue is preferably not lower than about 0.5:1. More preferably, the weight ratio of sulfonating agent to SDA residue is greater than or equal to about 1 :1. Diminishing returns occur at a weight ratio of sulfonating agent to SDA residue of about 3:1 and higher.
  • reaction time There are trade-offs with respect to reaction time, temperature, solvent volumes (if used), degree of acid removal, etc.
  • the temperature is preferably low enough to avoid boiling away any solvent and/or reactants. Very good mixing leads to better sulfonation of the SDA residue.
  • solvents as the ratio of sulfur trioxide (SO 3 ) to SDA residue is increased, there may be a tendency for sulfonated SDA residue to deposit on solid surfaces, which may cause some hindering of contact of SO 3 with the incompletely sulfonated product.
  • a stepwise feed i.e. adding equal amounts of SDA residue and SO 3 , then adding more SO 3 later, permits the use of less SO 3 to obtain good products.
  • a sulfonated SDA residue is produced. If the sulfonation was conducted in a solvent, it advantageous to remove the solvent, for example by evaporation, centrifugation or other techniques, before further processing. Further processing may be, for example, neutralization and/or isolation of the sulfonated SDA residue.
  • the sulfonated product is preferably separated from the sulfonating agent. Separation from liquid sulfonating agents (e.g. oleum) may be accomplished with the selection of an appropriate technique, for example, selection of an appropriate membrane for membrane separation, washing the reaction mixture with water to remove excess sulfur trioxide as sulfuric acid, etc.
  • liquid sulfonating agents e.g. oleum
  • the sulfonated SDA residue is preferably neutralized before using it as a water requirement reducing admixture.
  • Neutralization may be achieved with any suitable base.
  • suitable bases include alkali metal hydroxides (e.g. NaOH, KOH, etc.), alkali metal carbonates (e.g. Na 2 CO 3 , NaHCO 3 , etc.), alkaline earth metal hydroxides (e.g. Ca(OH) 2 , Mg(OH) 2 , etc., alkaline earth metal carbonates (e.g. CaCO 3 ), etc., and mixtures thereof.
  • the base comprises NaOH, Ca(OH) 2 , CaCO 3 , or mixtures thereof.
  • the base preferably comprises a counter-cation which forms an insoluble salt with sulfate, for example calcium (Ca 2+ ).
  • Calcium-containing bases preferably comprise Ca(OH) 2 (lime) and/or CaCO 3 (limestone). Precipitation of insoluble sulfates facilitates separation of sulfate impurities from sulfonated SDA residues.
  • the base comprises a mixture of NaOH together with Ca(OH) 2 and/or CaCO 3 .
  • Separation of sodium sulfate may also be achieved by membrane separation techniques.
  • Neutralization is preferably performed in a polar solvent, for example water, alcohol or mixtures thereof. Water is preferred.
  • a polar solvent for example water, alcohol or mixtures thereof. Water is preferred.
  • alcohol e.g. methanol
  • calcium salts of the sulfonated SDA residue may be desired, in which case complete neutralization with calcium hydroxide or calcium carbonate is preferred.
  • the neutralized sulfonated SDA residue is preferably a sodium salt, which is accomplished by the use of sodium hydroxide once the sulfonated SDA residue is separated from excess sulfate. If separation from excess sulfate was accomplished through precipitation of calcium sulfate, the calcium salts of the sulfonated SDA residue may not be readily displaced by sodium ions from the sodium hydroxide.
  • a soluble salt with a counter-anion that produces an insoluble calcium salt for example soluble bicarbonate (e.g. sodium bicarbonate), may be used to ensure removal of calcium.
  • the use of limestone rather than lime for separating excess sulfates is preferred as it minimizes Ca 2+ uptake in the final product.
  • the neutralized sulfonated SDA residue may be isolated or not depending on the intended use.
  • the neutralized sulfonated SDA is isolated before being used as a water requirement reducing admixture.
  • Isolation of the sulfonated SDA residue may be accomplished by generally known techniques, for example, centrifugation, filtration, extraction, evaporation, etc., and combinations thereof. Isolation steps may be employed before, during and/or after neutralization.
  • the sulfonated SDA residue preferably has a weight average molecular weight of 600 g/mol or greater. In some instances, the weight average molecular weight is 1000 g/mol or greater. In some instances, the sulfonated SDA residue comprises about 50 wt% aromatic components. In some instances, the sulfonated SDA residue comprises 15-40 wt% carbon. In some instances, the sulfonated SDA residue comprises 1-4 wt% hydrogen. In some instances, the sulfonated SDA residue comprises 5-20 wt% sulfur. In some instances, the sulfonated SDA residue comprises 20-35 wt% oxygen. The sulfonated SDA residue may comprise 15-40 wt% carbon, 1 -4 wt% hydrogen, 5-20 wt% sulfur and 20-35 wt% oxygen. Uses:
  • cement-based mixtures include cement, mortar, concrete, etc.
  • Cement is generally formulated by mixing water with dry powder cementitious material.
  • Mortar is generally formulated by mixing water with dry powder cementitious material and fine aggregate (e.g. sand).
  • Concrete is generally formulated by mixing water with dry powder cementitious material and both fine aggregate (e.g. sand) and coarse aggregate (e.g. stone).
  • Cementitious material includes, for example, Portland cement, high alumina cement, magnesium phosphate cement, gypsum, etc.
  • pozzolanic materials e.g. fly ash, slag, silica fume, lime, etc.
  • accelerators for reducing set time e.g. fly ash, slag, silica fume, lime, etc.
  • set retarders for delaying set time e.g., set retarders for delaying set time
  • air-entrainers for freeze-thaw resistance e.g., corrosion inhibitors
  • expansive admixtures for minimizing shrinkage, shrinkage reducing admixtures, water repelling admixtures, mixtures thereof, etc.
  • the presence of the sulfonated SDA residue in a wet cement-based mixture increases the fluidity of the mixture, thus reducing the amount of water required to make up the cement-based mixture having a given initial workability, thus increasing compressive strength of the cement-based mixture.
  • Sulfonated SDA residues of the present invention are particularly advantageous. For example, they have a significantly lower degree of surfactant properties, leading to reductions in air entrainment and retardation of set in cement-based mixtures, especially in comparison with sulfonated hydrocracking residues disclosed in US 5,584,920. Without being held to any particular mode of action, it is thought that sulfonated SDA residues have less alkyl group content in comparison to sulfonated hydrocracking residues. Alkyl groups attached to sulfonated aromatics cause surface activity leading to undesired air entrainment.
  • Fig. 1 is a graph of time (h) vs. reaction rate (mW/g) for conduction calorimetry experiments conducted on water requirement reducing admixtures.
  • Table 1 lists materials used in the Examples below.
  • Example 1 Solvent Deasphalting of Bitumen Upgrading Residues
  • Oleum (212 g containing 78.6 g SO 3 ) made from H 2 SO 4 and SO 3 was charged to a 500 ml 3-necked reaction flask fitted with an air driven stirrer and a thermometer. Powdered mortar ground CANMET SDA residue (12.6 g) was added to the vigorously stirred oleum using an addition funnel fitted with an auger feed arrangement over a 27-minute period. A cold water bath maintained temperature below 3O 0 C. The reaction mixture was stirred for a total of 60 min.
  • the reaction mixture was poured into 550 ml of water in increments so that the temperature did not exceed 4O 0 C.
  • the resulting aqueous mixture was centrifuged to obtain a lightly colored first liquid and 215.65 g of a first sludge.
  • the first sludge was separated from the lightly colored liquid and then the first sludge was dispersed in water to a total volume of about 400 ml.
  • the dispersion was treated with 550 ml of 10% NaOH resulting in a pH of 8.753.
  • the treated dispersion was centrifuged to obtain about 955 ml of a very dark second liquid and 73.82 g of a second sludge.
  • the second sludge was separated from the very dark liquid and treated with 25 ml of 10% NaOH to form 150 ml of a third liquid with pH of 12.87. In total, 70 g of NaOH was used for neutralization.
  • the first, second and third liquids were combined and centrifuged to obtain a supernatant and an insoluble solid.
  • the dried insoluble solid weighed 1.86 g, implying that a minimum of 10.74 g of the original 12.6 g of CANMET SDA residue was sulfonated (sulfonated SDA residue being generally soluble in aqueous medium). This example verifies that it is possible to sulfonate an SDA residue without the use of organic solvent.
  • Oleum (176.6 g containing 64.5 g SO 3 ) made from H 2 SO 4 and SO 3 was charged to a 500 ml 3-necked reaction flask fitted with an air driven stirrer and a thermometer.
  • Ground Husky SDA residue (16.92 g) was added to the vigorously stirred oleum using an addition funnel fitted with an auger feed arrangement over a
  • the reaction mixture was poured into 550 ml of water in increments so that the temperature did not exceed 4O 0 C.
  • the resulting 850 ml of aqueous mixture was centrifuged to obtain about 750 ml of a dark but transparent liquid and about 175 g of a sludge that was difficult to remove from the centrifuge cups.
  • the sludge was separated from the liquid and then the sludge was dispersed in water to a total volume of about 400 ml.
  • the mixture was centrifuged to obtain 555 ml of solution. Evaporation of a 50 ml aliquot of the solution yielded 3.0 g of dry solid, which indicated that a total of 33.3 g of dry solid can be obtained from the 555 ml of solution.
  • the solid is sulfonated SDA residue.
  • Table 2 provides a comparison of the composition of the Husky SDA residue feed stock and the sulfonated Husky SDA residue of Example 3.
  • Example 4A The process of Example 4A was performed except that the solution of sulfur trioxide was fed stepwise to the solution of CANMET SDA residue.
  • Example 4C The process of Example 4A was performed except that the solution of sulfur trioxide was fed stepwise to the solution of CANMET SDA residue, and the amount of SO 3 was 200 wt% more than the amount of CANMET SDA residue.
  • Table 3 provides a comparison of the composition of the CANMET SDA residue feed stock and the sulfonated CANMET SDA residue of Example 4B.
  • a 100 ml solution containing 14.96 g of Husky SDA residue in methylene chloride were fed simultaneously with a 50 ml solution containing 45 g of sulfur trioxide (SO 3 ) in methylene chloride into a reactor containing 250 ml methylene chloride.
  • the mixture was mixed with a rotor-stator mixer and the reactor was cooled with a bath at 14 0 C. Feeding was completed in 67 min and after a further 10 min the mixer was stopped. There was some solid product deposited on the reactor walls and the mixer surface.
  • the mixture was centrifuged and 210 ml of clear liquid was obtained. The solids were dispersed in water and 600 ml of aqueous acidic product was obtained.
  • the solid product (29.5 g) was treated with 300 ml of water and the resulting mixture had a pH of 8.016, perhaps due to absorbed CO 2 .
  • NaHCO 3 (4.0 g) was added and the pH was 6.567. Then, 1.8 g of Na 2 CO 3 was added to achieve a pH of 9.986. After centrifugation, the liquid was evaporated to give solid sulfonated Husky SDA residue and the solid dried to a constant weight of 26.9 g.
  • a 50 ml solution containing 12 g of Husky SDA residue in tetrachlorethylene was simultaneously fed with 10 ml of solution containing 10 g of sulfur trioxide (SO 3 ) in terachlorethylene to a reactor containing 130 ml of tetrachloroethylene and 5 g of SO 3 over a period of 38 min.
  • the reactor was cooled with a bath with initial temperature of -5°C and final temperature of -9°C.
  • the reaction mixture was mixed with a rotor-stator mixer. Then, another 20 ml of solution containing 20 g of SO 3 was fed to the reaction mixture over period of 20 min and mixing continued for another 20 min after that.
  • the reaction mixture was centrifuged to separate solvent (tetrachloroethylene) and product sludge.
  • the sludge was treated with 225 ml of water, and when centrifuged more tetrachlorethylene was separated and some sludge was obtained.
  • the sludge was dried and the dried sludge weighed 2.34 g.
  • the aqueous product mix was treated with 4.0 g of NaOH and 25.0 g of lime to produce a mixture with pH of 12.029. The mixture was centrifuged to remove precipitated gypsum.
  • the resulting supernatant solution was treated further with 5.2 g of NaHCO 3 and 0.64 g of NaOH to achieve a pH of 8.29, and then centrifuged to isolate a precipitate that was produced. The precipitate when dry weighed 3.4 g.
  • the precipitated gypsum was extracted with 200 ml of aqueous solution containing 6.0 g of Na 2 CO 3 and 8.4 g of extract was obtained.
  • the combined products were found to contain considerable amounts of poorly water soluble components and therefore were treated with another 3.2 g NaHCO 3 and 0.4 g of NaOH to a pH of 9.361. Centrifugation produced 4.4 g of precipitate when dry and 487 ml of product solution. A 50 ml aliquot when evaporated gave 3.35 g of product. Thus, total yield is calculated to be 32.63 g. This product was very water soluble.
  • Table 4 provides a comparison of the composition of the Husky SDA residue feed stock and the sulfonated Husky SDA residue of Example 5A.
  • Syncrude SDA residue was sulfonated under conditions similar to those of Example 5A to produce a sulfonated Syncrude SDA residue.
  • Table 5 provides a comparison of the composition of the Syncrude SDA residue feed stock and the sulfonated Syncrude SDA residue of Example 6.
  • Example 8 Comparative: Sulfonation of CANMET hydrocracking residue
  • a sulfonated hydrocracking residue from US 5.584,920 was prepared for comparative purposes. Sulfonation was carried out under conditions similar to those of Example 4A. 15 g of CANMET hydrocracking residue and 45 g of SO 3 were used. 27.1 g of sulfonated CANMET hydrocracking residue were obtained. Table 6 provides a comparison of the composition of CANMET hydrocracking residue feed stock and sulfonated CANMET hydrocracking residue of Example 8.
  • the densities of mixtures containing mortar were determined to assess the extent of air entrainment. Denser admixtures have less entrained air.
  • Mortar mixtures were mixed and packed into a standard steel cup using a standard procedure. Mixing was done according to an ASTM standard mix design (ASTM C305-99e1 "Standard Practice for Mechanical Mixing of Hydraulic Cement Pastes and Mortars of Plastic Consistency", ASTM International, herein incorporated by reference).
  • the standard cup had a volume of 180 ml, and was filled in three layers. A first layer was placed by tapping the cup on its bottom. Second and third layers were tamped in place by tamping each layer fifteen times.
  • Density was determined by weighing the cup and dividing by the known volume. The mixing and packing procedure were the same in all cases.
  • the mortars contained sand (ASTM 20-30 mesh, 67.9 wt%), Portland cement (22.6 wt%), water (9.4 wt%) and a water requirement reducing admixture (0.1 wt%), and differed only in the type of water requirement reducing admixture used.
  • Table 7 provides the results of the air entrainment assessment.
  • DISALTM is a commercial superplasticizer for cement-based mixtures and contains naphthalene sulphonates sodium salts.
  • Example 8 is a water requirement reducing agent made in accordance with US 5,584,920.
  • Examples 4A, 4B 1 5A, 6 and 7 are examples of the present invention. It is evident from Table 7 that sulfonated SDA residues of the present invention provide for less entrained air in a cement-based mixture than the sulfonated residues disclosed in US 5,584,920. Further, sulfonated SDA residues of the present invention can be as effective or more effective than commercially available products.
  • Mortar flow tests measure the workability of a mortar mixture. Mortar mixtures that are more workable at a given water content will require less water to be able to work.
  • a standard procedure for mortar mixing was used for each mortar composition tested. The mortar was packed using a standard procedure into a stainless steel cylindrical form having a diameter of 4.2 cm and a height of 5 cm. The form was removed to leave a cylindrical wet briquette on a platform. The platform was dropped through 33.3 cm and the average diameter of the flattened briquette was determined by measuring the longest and shortest diameters of the flattened briquette and then taking the average. The average diameter is a measure of workability, with larger average diameters indicating greater workability.
  • the mortars contained beach sand (finer than 50 mesh, 53.5 wt%), Portland cement (32.2 wt%), water (14.1 wt%) and a water requirement reducing admixture (0.2 wt%), and differed only in the type of water requirement reducing admixture used. Table 8 provides results.
  • ASTM International Standard mix design for mortar
  • ASTM C109 Standard Test Method for Compressive Strength of Hydraulic Cement Mortars (Using 2-in. or [50mm] Cube Specimens)
  • Tests in accordance with ASTM specifications were conducted on the prepared mortar samples, the samples comprising various water requirement reducing admixtures. Specifically, the following tests were performed.
  • Air entrainment was measured through wet density and air content in accordance with ASTM C185 (ASTM C185-99, "Standard Test Method for Air Content of Hydraulic Cement Mortar", ASTM International, herein incorporated by reference). Since the sand in the mortar composition was not washed, some additional air entrainment may affect the accuracy of the air content values.
  • Compressive strength was conducted in accordance with ASTM C109 using 50 mm cube specimens. (ASTM C109-99 "Standard Test Method for Compressive Strength of Hydraulic Cement Mortars (Using 2-in. or [50 mm] Cube Specimens)", ASTM International, herein incorporated by reference).
  • Table 9 provides the compositions of the mortars tested and the test results obtained therefor.
  • s/c weight ratio is the ratio of sand to cement
  • w/c ratio is the ratio of water to cement
  • admixture is the amount of water requirement reducing admixture expressed as weight percent based on weight of the cement.
  • the sand was standard ASTM 20-30 mesh sand as specified in ASTM C778 (C778-02 Standard Specification for Standard Sand) and the cement was Lafarge brand Portland cement.
  • the admixture in Ex. C2 is a commercial water requirement reducing admixture called DAXADTM 19LKN.
  • water reducing admixtures of the present invention can provide for less entrained air in a cement-based mixture than a commercially available admixture. Further, admixtures of the present invention can provide for comparable entrained air than a control without any admixture.
  • admixtures of the present invention provides for better workability of a cement- based mixture than a control without any admixture. Further, admixtures of the present invention can provide for comparable or better workability than a commercially available admixture.
  • admixtures of the present invention Based on the compressive strength, it is evident that water requirement reducing admixtures of the present invention provides for better compressive strength of a cement-based mixture than a control without any admixture. Further, admixtures of the present invention can provide for compressive strength comparable to a commercially available admixture.
  • conduction calorimetry Another indicator of water reducing requirement effectiveness is conduction calorimetry, which measures exothermicity vs. time to give an indication of cement hydration.
  • Conduction calorimetry experiments were conducted using a Thermonics Tarn Air Cement Calorimeter system. The system was maintained at 24 ⁇ 0.1 °C and configured with a ⁇ 60 mW signal range. The reference cells were loaded with a heat capacity mass equivalent weight of 5 g of cement with a water to cement ratio of 0.4. The system was set to acquire data every two minutes for the duration of the test. Glass amphiboles specifically designed for the calorimeter chamber with a crimp top were used for each specimen. The dry powder fractions for each mix design were weighed and recorded and placed into the amphibole.
  • Fig. 1 provides the results of the conduction calorimetry testing for the mortar samples listed in Table 10. Samples listed in Table 10 were prepared as per ASTM C305 as described above in Example 11.
  • w/c ratio is the ratio of water to cement and admixture is the amount of water requirement reducing admixture expressed as weight percent based on the weight of the cement.
  • the cement was Portland cement.
  • the admixture used in samples C2 and C3 was DAXADTM 19LKN.
  • the admixture used in samples 5B' and 5B" was the sulfonated solvent deasphalting residue of Example 5B.
  • the admixture used in samples 3' and 3" was the sulfonated solvent deasphalting residue of Example 3. It is evident from Fig.

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  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Organic Chemistry (AREA)
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  • Structural Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • General Chemical & Material Sciences (AREA)
  • Environmental & Geological Engineering (AREA)
  • Civil Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Curing Cements, Concrete, And Artificial Stone (AREA)

Abstract

Selon l’invention, des résidus de valorisation de bitume sont extraits avec un solvant de façon à retirer toute valeur de carburant résiduelle. Le résidu résultant insoluble désasphalté au solvant (DAS) est rendu utile en tant que dispersant (par exemple pour un ciment) par sulfonation avec l’oléum ou le trioxyde de soufre pour donner un résidu de valorisation de bitume sulfoné désasphalté au solvant.
PCT/CA2006/000412 2005-03-22 2006-03-17 Residus sulfones desasphaltes au solvant, leur procede de production et leur utilisation WO2006099723A1 (fr)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3970690A (en) * 1971-08-02 1976-07-20 Kureha Kagaku Kogyo Kabushiki Kaisha Method for preparing dispersing agent
US5322556A (en) * 1989-12-21 1994-06-21 Eniricerche S.P.A. Process for preparing a sulfonated dispersant from petroleum asphalt fractions
US5584920A (en) * 1995-04-20 1996-12-17 Natural Resources Canada Sulphonated hydrocracking residues as concrete admixtures

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3970690A (en) * 1971-08-02 1976-07-20 Kureha Kagaku Kogyo Kabushiki Kaisha Method for preparing dispersing agent
US5322556A (en) * 1989-12-21 1994-06-21 Eniricerche S.P.A. Process for preparing a sulfonated dispersant from petroleum asphalt fractions
US5584920A (en) * 1995-04-20 1996-12-17 Natural Resources Canada Sulphonated hydrocracking residues as concrete admixtures

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