Classifications

• • 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
  • C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
  • C10G3/42—Catalytic treatment
  • C10G3/44—Catalytic treatment characterised by the catalyst used
  • C10G3/48—Catalytic treatment characterised by the catalyst used further characterised by the catalyst support
  • C10G3/49—Catalytic treatment characterised by the catalyst used further characterised by the catalyst support containing crystalline aluminosilicates, e.g. molecular sieves
• • 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
  • C10B53/02—Destructive distillation, specially adapted for particular solid raw materials or solid raw materials in special form of cellulose-containing material
• • 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
  • C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
  • C10B57/00—Other carbonising or coking processes; Features of destructive distillation processes in general
  • C10B57/04—Other carbonising or coking processes; Features of destructive distillation processes in general using charges of special composition
  • C10B57/06—Other carbonising or coking processes; Features of destructive distillation processes in general using charges of special composition containing additives
• • 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
  • C10G1/10—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal from rubber or rubber waste
• • 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
  • C10G75/00—Inhibiting corrosion or fouling in apparatus for treatment or conversion of hydrocarbon oils, in general
• • 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
  • C10G2300/10—Feedstock materials
  • C10G2300/1003—Waste materials
• • 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
  • C10G2300/10—Feedstock materials
  • C10G2300/1011—Biomass
  • C10G2300/1014—Biomass of vegetal origin
• • 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
• • 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
  • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
  • Y02E50/00—Technologies for the production of fuel of non-fossil origin
  • Y02E50/10—Biofuels, e.g. bio-diesel
• • 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
  • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
  • Y02P20/00—Technologies relating to chemical industry
  • Y02P20/141—Feedstock
  • Y02P20/143—Feedstock the feedstock being recycled material, e.g. plastics
• • 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
  • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
  • Y02P30/00—Technologies relating to oil refining and petrochemical industry
  • Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock

Definitions

• the invention generates, according to its configuration, the production during a chemical engineering process, of a liquid fuel that can be fractionated and from which light fractions such as gasoline, kerosene, medium fractions of the diesel type and heavier fractions similar to fuel oil c) Background of the invention
• thermochemical degradations of biomass understood as a lignocellulosic substrate or of certain plastic polymers.
• This agent is usually alumina, silicates or high pressure water vapor. It is a fluid that behaves both as a recirculating agent and as a thermal diffuser.
• chlorinated aluminas are used, since these thermodynamically favor the formation of branched products. Branched products have great interest because they raise the octane number of the resulting fuel. These chlorinated aluminas need a constant contribution of chlorine, since it is continuously released from the catalyst, when the molecular exchange takes place. These processes have several disadvantages and are very sensitive to foreign elements and contaminants present in the raw material, they greatly affect the corrosion of the equipment and pose an environmental process risk. d) Procedural news
• the originality of this invention focuses on the process itself and on the set of additives that allow the flash pyrolysis reaction to be carried out under advantageous conditions to produce combustible liquid.
• Flash pyrolysis is defined as that process of thermochemical pyrolysis in the absence of oxygen in which a heat transfer of more than 200 9 C is performed quickly in a period of time less than 1 second.
• a novelty is the combination of unit operations and the mixture of catalysts and additives with which it is possible to lower the reaction temperature between 100 and 170 2 C.
• a parameter window (temperature, heat exchange, stirring and pressure) is established which Maximizes liquid production.
• Another novelty is the thermal cracking due to heat and stirring that develops under conditions of pressure and temperature of the reactor mixture and which, thanks to the reaction conditions and the hardness of the adjuvant additives, achieves a necessary heat transfer for the development of a flash pyrolysis reaction.
• the set of reactions that take place in the chemical reactor are of the thermochemical type and require an important contribution of heat to its beginning. It is novel in this procedure to characterize the behavior of cracking reactions that are carried out in the presence of catalysts and reaction additives and that lead the thermodynamic equilibrium mostly to the production of liquid.
• Another novelty is that related to the use of a mixture of catalysts, reaction initiating additives, adjuvant additives and regulating and exchange additives, which allows producing a stable combustible liquid that can be used as a substitute for petroleum-derived fuels.
• the use of the following products as additives is noteworthy:
• Carboxylic or polycarboxylic acids as adjuvants such as oxygen scavengers. (0.5-10%)
• the purpose of the catalysts is to reduce the speed of secondary reactions to unwanted products (gases and tars) and improve the selectivity of a reaction by changing the yield towards the generation of combustible liquid.
• the catalyst does not undergo chemical transformation during the reaction, but cannot be considered as an inert substance.
• the process uses catalysts of the family of zeolite aluminosilicates that are very active, these compounds undergo transformations in the stages of the reaction mechanism. These catalysts modify the mechanism by which the reaction proceeds by facilitating the formation of intermediate complexes of lower energy level and causes a reduction in activation energies directly related to the speed of the process.
• the addition of compounds derived from carboxylic or polycarboxylic acids acts as oxygen scavengers produced in the reaction. These react with the oxygen present in the reaction medium generating CO2. The proportion of these products depends on the oxygen present in the raw materials, varying their proportion from 0.5% in the case of plastics to 10% in the case of biomass. They are dosed in the reactor.
• the inventive novelty consists in the use of compounds derived (containing) carboxylic or polycarboxylic acids as oxygen scavenging additives in the reactor bed.
• sodium bentonites are dosed which react with the water present in the reactor.
• Another inventive novelty consists in the use of sodium bentonites as additives in pyrolysis processes as water capturers present in the reactor.
• silicates of the beryl or tourmaline type are added in a proportion (between 1 and 10% by weight) necessary for the total hardness of the mixture to be greater than 4 on the Mohs scale.
• the novelty consists in the use of hard materials (static hardness) as pyrolysis reaction additives to increase the total hardness of the mixture inside the reactor under conditions of mechanical agitation (dynamic hardness), this hardness measured in conditions of agitation varies according to They break down polymeric materials.
• Another novelty related to bentonites is their use as additives in pyrolysis to regulate the viscosity of the mixture in the reaction bed.
• the process has a series of devices combined with the control of the parameters that promote various physical-chemical reactions under controlled control conditions.
• the chemical reaction process is carried out in the chemical reactor under continuous operation with stirring. In this reactor the catalytic cracking is performed.
• the stirring parameters are controlled, so that residence times of less than 2 minutes are guaranteed, an adequate heat transfer (of the order of 200 Q C per second), a pyrolysis reaction time (between 2 and 10 seconds], the quantity and dosage of the catalysts and additives initiating the reaction, CO2, pH, presence of oxygen and oxidizing elements, reducing atmosphere, N2 flow, pressure, temperature and the speed of recirculation.
• these catalysts are added by other adjuvant additives and regulators necessary for catalyst activation generating greater efficiency.
• These adjuvants fix the parameter windows (friction, lubricity, suspension and pH] in which the catalysts develop their maximum efficiency, they also establish the chemical environment of the reactions guaranteeing their effectiveness and control.
• reaction initiators are mixtures of clays compounds rich in iron oxides, especially red clays with a higher content of ferrous oxides. They are dosed at the mixer inlet in proportions of 0.5 to 2%
• the energy contribution is a necessary parameter for the decomposition of materials intermolecularly and intramolecularly, this is done by heat input in the form of heat and by contribution of kinetic energy in the form of agitation. This energy contribution is combined with the hardness of the materials that make up the mixture present in the reactor. It is necessary that the mixture of catalysts and additives have an index on the Mohs scale greater than 4. The behavior of the fluid and the cracking reaction are controlled based on the reaction parameters and the mixture of catalysts and additives.
• the energy contribution helps to generate sufficient activation energy, and therefore, to increase the activity of the chemical reaction, for the cracking of polymeric materials, it is necessary to apply an energy ratio of between 0.3 and 3 kWh per kg of raw material.
• the thermal contribution depends largely on the raw material, although a range of 0.1 to 2.5 kWh per kg of raw material can be estimated.
• Heated device that must guarantee the tightness of the entire process, as well as the fluidity and temperature of the raw material inlet. They regulate temperature and pressure.
• This dosage must guarantee the presence of oxygen in the reactor below 20 ppm.
• Condensation elements necessary for the collection of generated liquid products can be done in several complementary stages, the first two being recommended thermally.
• the condensed fluid is regulated from the condenser to the reflux (18) or to the condensate control control tank (16)
• the different products are stored in deposits with emission control (13,14 and 15)
• the process uses catalysts of the family of zeolite aluminosilicates, aluminum hydrosilicates, bauxite, highly crystalline hydrated aluminosilicates with a porous structure with minimum pore diameters between 3 and 30 Angstroms and a high specific surface area.
• the catalysts are added to the raw material prior to the start of the reaction in a proportion of 0.25 to 2% of the total matter present in the reaction bed.
• the activity of cracking catalysts is enhanced with the use of starter additives. It is clays rich in iron oxides. The use of these clays, especially the red clays with a higher content of ferrous oxides, promotes the presence of hydrogen in the reactor core. Its dosage varies depending on the raw material being its proportions of 0.5 to 2% of the total input of the raw material.
• red clay consisting of aggregates of hydrated aluminum silicates
• the clay behavior combines its cation exchange capacity with the reaction support activity by improving the lubricity of the bed.
• adjuvant additives for oxygen capture are used.
• the use of compounds derived from carboxylic or polycarboxylic acids allows to capture the oxygen produced by reacting with said compounds generating CO2.
• the proportion of these products depends on the oxygen present in the raw materials, varying between 0.5% in the case of plastics, up to 10% in the case of biomass. They are dosed in the reactor.
• Sodium bentonites are used as additives water capture adjuvants, to reduce the presence of water in the reactor thanks to the reaction of these substances with water.
• Lubrication enhancement additives are also used to improve the lubricity of the mixture and increase the viscosity.
• Calcium bentonites can be added in varying proportions of 1 to 5% of the reaction bed mixture. For the pyrolysis of mixtures with a high percentage of biomass the proportion of calcium bentonites must be greater than 3% of the reaction mixture.
• exchange and regulation additives are used which are dosed at the start of the reaction and in proportion necessary for the generation of a reaction medium between a pH range greater than 5
• the chemicals used are calcium and sodium carbonates with particle sizes less than 5 nanometers and with hardness less than 1.5, chemically stable at pH between 4 and 9.
• the raw material is introduced to the primary mixer (1) and mixed with catalysts in proportions of 0.25-2% at the inlet of the mixer.
• the process conditions are:
• the reaction temperature depends on the raw materials processed, mainly based on its elemental composition of carbon, hydrogen and oxygen, this temperature varies from 220 to 450 Q C.
• reaction temperature ranges are between 220 Q C and 320 2 C.
• reaction temperature is between 300 Q C and 450 Q C .
• the thermal energy required is of the order of 0.1 and 2.5 kWh per kg of raw material, in order to guarantee the necessary range of reaction temperatures.
• the conditions of this second stage are as follows: O2 less than 100 ppm, HzO less than 5% and hardness of the mixture greater than 4.
• the raw material After the reactors, the raw material has been transformed into a mixture of hydrocarbons that are transferred to the distillation (10) and fractionation towers 1 and 2 (11 and 12). Distillation temperatures vary at the entrance and exit in the range of 350 Q C to 200 S C and in the fractionation towers between the temperatures of 200 2 C to 10 2 C.
• Fractional products are stored in the tanks (13,14 and 15) depending on their composition resulting in heavy, medium and light products.
• Raw material biomass with a humidity below 15% from softwoods [Populus spp. Betula spp, Pinus spp]
• Oxygen capture adjuvant additives (carboxylic acids) 8%
• Raw material biomass with a humidity below 15% from hardwoods [Quercus spp, Castanea spp, Ulmus spp)
• Oxygen capture adjuvant additives (carboxylic acids) 8%
• Raw material mixture of waste from urban solid waste treatment plants to which fresh organic matter, metals and inert glass-like materials have been removed.
• Oxygen capture adjuvant additives (carboxylic acids) 0.5%

Landscapes

• Chemical & Material Sciences (AREA)
• Oil, Petroleum & Natural Gas (AREA)
• Engineering & Computer Science (AREA)
• Organic Chemistry (AREA)
• Materials Engineering (AREA)
• Chemical Kinetics & Catalysis (AREA)
• General Chemical & Material Sciences (AREA)
• Life Sciences & Earth Sciences (AREA)
• Wood Science & Technology (AREA)
• Crystallography & Structural Chemistry (AREA)
• Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)

Priority Applications (1)

Applications Claiming Priority (1)

Publications (1)

Family

ID=47116038

Family Applications (1)

Country Status (1)

Cited By (4)

Citations (3)

• 2012
  • 2012-09-12 WO PCT/ES2012/000238 patent/WO2014041212A1/fr not_active Ceased

Patent Citations (3)

Similar Documents

Legal Events