Classifications

• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
  • C10L8/00—Fuels not provided for in other groups of this subclass
• • 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
  • C10G19/00—Refining hydrocarbon oils in the absence of hydrogen, by alkaline treatment
• • 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
  • C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
  • C10G1/002—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal in combination with oil conversion- or refining processes
• • 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
  • C10G19/00—Refining hydrocarbon oils in the absence of hydrogen, by alkaline treatment
  • C10G19/02—Refining hydrocarbon oils in the absence of hydrogen, by alkaline treatment with aqueous alkaline solutions
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
  • C10B53/00—Destructive distillation, specially adapted for particular solid raw materials or solid raw materials in special form
  • C10B53/07—Destructive distillation, specially adapted for particular solid raw materials or solid raw materials in special form of solid raw materials consisting of synthetic polymeric materials, e.g. tyres
• • 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
  • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
  • C10G2300/40—Characteristics of the process deviating from typical ways of processing
  • C10G2300/4006—Temperature

Definitions

• the present invention relates to a process for removing siloxane-based derivatives from at least one liquid organic phase, comprising the steps of:
• Solid plastic waste is becoming more and more prevalent for many years. This plastic-based solid waste comes mainly from the recovery of metals from automobiles, household appliances and other consumer products that are contaminated by organic by-products such as plastics, rubbers, joints, coatings and sealants, textiles and expanded materials.
• thermoplastics such as, for example, to manufacture fuels from this solid waste, which allows to recover their energy value at least partially.
• This plastic-based solid waste comprises thermoplastics, thermosetting plastics, elastomers, textile, wood, such as for example polyethylene (PE), polypropylene (PP), polystyrene (PS), polyethylene terephthalate (PET) as well as often polyvinyl chloride (PVC).
• PE polyethylene
• PP polypropylene
• PS polystyrene
• PET polyethylene terephthalate
• PVC polyvinyl chloride
• This solid waste can be introduced into a catalytic cracking reactor or not at the same time as a catalyst for example based on zeolites which allows, at high temperature to promote the decomposition of plastics.
• this solid waste does not only contain carbonaceous material, but also contains impurities, such as chlorine, bromine, silicon, fluorine and sulfur.
• impurities such as chlorine, bromine, silicon, fluorine and sulfur.
• the volatile fraction from catalytic cracking of plastic waste solids from automotive waste contains up to several thousand ppm of silicon, sulfur, chlorine and several hundred ppm of bromine and fluorine.
• This volatile fraction is that used to obtain combustible materials (or fuels) and the presence of these elements in residues causes fouling, corrosion, abrasion and various breakdowns in the engines when they are used as fuel or fuel.
• the volatile fraction of catalytic cracking residues still contains silicon-based compounds, which are particularly harmful because the combustion in the engines leads to the formation of silicon oxides which are very fine residues. abrasives.
• US5166384 discloses a process for removing silicic compounds dissolved in a hydrocarbon which comprises a step of heating with stirring and a step of adding an oxygenated boron compound, for example boric acid, which causes the precipitation siloxanes in the solvent, the latter finally being separated from the solvent by filtration.
• an oxygenated boron compound for example boric acid
• sodium methoxide or potassium methoxide to increase the precipitation rate of siloxanes. This technique of removing siloxanes present in a solvent is therefore based on the addition of an oxygenated boron compound and methoxide.
• the present invention provides a process for removing siloxane-based derivatives from at least one liquid organic phase, particularly in catalytic cracking residues of plastics-based solid waste as indicated in US Pat. beginning, characterized in that said base is in the form of an alkaline hydroxide and in that the heating step is carried out at said predetermined temperature which is greater than 165 ° C.
• the siloxane-based compounds are precipitated under the effect of the base and the heating and, the liquid / solid separation such as a distillation makes it possible to recover an organic mixture which can then be used safely in a internal combustion engine.
• the concentration of halogenated compounds bromine, chlorine, fluorine, etc.
• this predetermined temperature is greater than 165 ° C which allows the use of the hydroxide in liquid or solid form since it will melt in the organic phase.
• this predetermined temperature is less than 450 ° C, even lower than 400 ° C to avoid cracking the compounds of the liquid organic phase.
• the reaction mixture is allowed to react for a predetermined period of time at said predetermined temperature, preferably with stirring.
• said predetermined temperature is between 200 and 350 ° C, preferably between 200 and 250 ° C, which represents an optimum between pressure and temperature to prevail in the reactor to maintain the base dissolved or dispersed therein with a residence time as short as possible.
• the pressure should be greater than 20 bar and require high performance materials, resistant to very high constraints that would increase the costs of these devices.
• the pressure should ideally be between 15 and 20 bar, which is already a high stress for the equipment used.
• said predetermined period of time is between 1 and 250 minutes, preferably between 1 and 45 minutes, depending on the composition of the liquid organic phase.
• the acids are neutralized and the corresponding salts are formed and then the mineralization reactions occur, allowing the silicic derivatives to be removed in the form of solid derivatives. Said period of time, although very low will depend on the content of acid derivatives (if present) and silicic derivatives.
• the added base is selected from KOH and NaOH.
• These basic compounds have indeed shown a particular efficiency for the mineralization of siloxane-based compounds at said predetermined temperature in a liquid organic phase.
• the process advantageously comprises, prior to said mineralization of the siloxane-based compounds, a separation of phenol derivatives and acids, for example carboxylic acids.
• the addition of the base allows the neutralization of phenol derivatives and acids, for example carboxylic acids possibly present in the volatile fraction of the residue from catalytic cracking, which initially consumes the base.
• carboxylic acids possibly present in the volatile fraction of the residue from catalytic cracking, which initially consumes the base.
• said liquid / solid separation is a distillation which is carried out under reduced pressure, preferably between 1 and 300 mbar until the overhead fraction reaches a temperature greater than 200 ° C., for example 250 ° C.
• the method may comprise, after said mineralization step, a filtration step for effecting the solid / liquid separation in order to recover the solid mineralized silicon derivative.
• the liquid organic phase may be a catalytic cracking residue of solid waste based on plastics comprising thermosetting plastics, thermoplastics, elastomers, textile materials and wood.
• the liquid organic phase is obtained by bubbling a gaseous phase containing siloxane-based derivatives in a diesel or an absorbing organic phase, thus making it possible to provide a solution for the abatement of the derivatives. based on siloxane transferred into the liquid absorbing organic phase or in the diesel and finally allow a treatment thereof. More particularly, according to the invention, said heating step is performed as quickly as possible to reach the predetermined temperature, to obtain optimum performance.
• the present invention therefore describes a process for removing siloxane-based derivatives from an organic phase, particularly in catalytic cracking residues of plastic-based solid wastes.
• This liquid organic phase can come from a process for the catalytic cracking of grinding residues of thermoplastics, thermosetting materials, elastomers, textiles and wood.
• waste grinding residues are of two types, light residues and heavy residues.
• grinding residues that are difficult to recycle are present on the market as a mixture in the proportions of 65% of light grinding residues and 35% of heavy grinding residues.
• Plastics including PVC, PC, PET, 29.1 52.2 PMMA, PA and ABS, ...)
• the grinding residues are then catalytically cracked in a high temperature fluidized reactor according to a conventional method and a liquid organic phase (the volatile fraction is recovered).
• said organic phase is heated as quickly as possible to the predetermined temperature of between 150 and 300 ° C., preferably between 200 and 250 ° C.
• the liquid organic phase is the result of the bubbling of a volatile gas phase containing siloxane-based derivatives in diesel or an absorbing organic phase, in order to transfer the siloxane-based derivatives therein and possibly to proceed with partial heating or preheating. of the liquid organic phase.
• the liquid organic phase may also be a mixture of a residual liquid organic phase of the catalytic cracking and of an organic phase enriched in siloxane by bubbling a gas phase.
• the bubbling can be carried out also during the heating and in the residual liquid organic phase of the catalytic cracking.
• a base selected from KOH and NaOH is then added to obtain a reaction mixture and this is allowed to react for a predetermined period of time of between 1 and 250 minutes, preferably between 1 and 45 minutes, with stirring.
• the siloxane-based compounds in said organic phase are mineralized as well as a large portion of the halogens when present by the action of the base.
• the halogens, when present, are mineralized by the reaction of the organic molecule (s) which contains them with the base.
• the present base also makes it possible, when they are present, to neutralize phenol derivatives and acids, for example carboxylic acids, and this prior to the mineralization since the neutralization will take place first.
• the acids could also be halogenated acids which would then be neutralized by the base.
• the process further comprises, in this preferred embodiment, a distillation of said reaction mixture for separating said mineralized siloxane compounds from said silicon-free organic phase and said distillation is preferably carried out under reduced pressure, preferably from 1 to 300 mbar until the overhead fraction reaches a temperature of at least 200 ° C, preferably 250 ° C.
• the mineralized silicon-based compound is an insoluble compound in the liquid organic phase and is therefore in the form of a very thin sludge, which is particularly difficult to filter. For this reason, the resulting silicon-based compound is thus removed in this particular embodiment by distillation, which furthermore advantageously makes it possible to reduce the concentration at the end of the distillation with halogenated compounds.
• a 250 ml stirred autoclave (250 ml) of a liquid cracking residue obtained from pyrolysis of waste from the recycling of motor vehicles was placed in a stirred autoclave.
• the tank of the autoclave was equipped with an agitator, pressure and temperature probes and an electric heating system.
• Table 3 shows the comparison of the composition obtained after distillation with respect to the liquid catalytic cracking residue of solid waste based on plastic.
• the autoclave was closed and heated to 205 ° C. 30 g of sodium hydroxide solution (50% by weight) were added by injecting it under pressure for 20 seconds in the autoclave. Samples (approximately 5 g) of the reaction mixture were removed from the autoclave after 5, 15 and 30 minutes at constant temperature.
• the samples were analyzed by gas chromatography / mass spectrometry in SIM (Single Ion Monitoring) mode to detect the presence of 6 arbitrarily selected dimethylsiloxane oligomers potentially present in the original cracking product resulting from the pyrolysis operation.
• SIM Single Ion Monitoring
• the calibration was performed by external standardization (values below 1 ppm are considered to be below the sensitivity / reliability threshold of the analytical method).
• Table 4 shows the amount of dimethysiloxane oligomers (in ppm) detected in the original liquid catalytic cracking product (0 minutes) and the samples after the reaction times mentioned above.
• Table 4 shows that the treatment essentially results in the disappearance of the dimethylsiloxane oligomers in the mixture after 15 minutes.
• D3 hexamethylcyclotrisiloxane
• L5 pentasiloxane of dodecamethyl.
• the autoclave was allowed to cool and after aeration, the contents of the autoclave tank were transferred to a glass distillation apparatus and the latter was distilled under reduced pressure of 15 mm Hg. the head of the column reaches 200 ° C. A sample of the distillate obtained was taken and subjected to elemental analysis for the presence of silicon (by ICP) (ion exchange chromatography after mineralization).

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• Chemical & Material Sciences (AREA)
• Oil, Petroleum & Natural Gas (AREA)
• Organic Chemistry (AREA)
• Engineering & Computer Science (AREA)
• Chemical Kinetics & Catalysis (AREA)
• General Chemical & Material Sciences (AREA)
• Life Sciences & Earth Sciences (AREA)
• Wood Science & Technology (AREA)
• Separation, Recovery Or Treatment Of Waste Materials Containing Plastics (AREA)
• Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
• Silicon Polymers (AREA)
• Extraction Or Liquid Replacement (AREA)
• Processing Of Solid Wastes (AREA)

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• 2010
  • 2010-11-22 BE BE2010/0697A patent/BE1019650A5/fr active
• 2011
  • 2011-11-22 CN CN201180063274.XA patent/CN103328614B/zh active Active
  • 2011-11-22 US US13/989,022 patent/US9441176B2/en active Active
  • 2011-11-22 DK DK11785430.7T patent/DK2643432T3/en active
  • 2011-11-22 ES ES11785430T patent/ES2531212T3/es active Active
  • 2011-11-22 CA CA2818957A patent/CA2818957C/fr active Active
  • 2011-11-22 WO PCT/EP2011/070672 patent/WO2012069467A1/fr not_active Ceased
  • 2011-11-22 EP EP11785430.7A patent/EP2643432B1/de active Active
  • 2011-11-22 PT PT11785430T patent/PT2643432E/pt unknown
  • 2011-11-22 JP JP2013539297A patent/JP5829693B2/ja active Active
  • 2011-11-22 BR BR112013012872-0A patent/BR112013012872B1/pt active IP Right Grant

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