SK9255Y1 - Mixture for preparation of lignocellulosic specifically activated catalyst, method for preparation of lignocellulosic specifically activated catalyst and its use - Google Patents

Abstract

The mixture for the preparation of a lignocellulosic specifically activated catalyst for the thermocatalytic cracking of macromolecular organic compounds of plastics and/or municipal waste contains 10 to 15 % by weight of an alkaline mixture and the remainder up to 100 % by weight is a biomass consisting of lignocellulose and/or cellulose in the form of grain, pulp, sawdust, straw, fibers or recovered paper. The alkaline mixture consists of 0.1 to 1.5% by weight of alkalies and the remainder up to 100 % by weight is water. The lignocellulosic specifically activated catalyst is prepared by homogenizing said mixture and, after evaporating the water, drying the specifically activated catalyst at a temperature of up to 260 °C. The lignocellulosic specifically activated catalyst for the thermocatalytic cracking of macromolecular organic compounds of plastics and/or municipal waste can be used in the production of biofuels, alternative fuels, fuels or fuel components for motor vehicles, based on renewable raw materials.

Description

The technical solution relates to a mixture for the preparation of a lignocellulosic specifically activated catalyst, a process for its preparation and its use for thermal cracking of macromolecular organic compounds of plastics and / or municipal waste to obtain liquid condensates usable as ecofuel, alternative fuel or fuels for renewable vehicles. raw materials.

Prior art

Methods for the catalytic cracking of triacylglycerols to extract triacylglycerols at high temperatures up to 500 ° C are known and hydrocarbon products as fuels can be used for motor vehicles. A group of these methods according to CA patent no. 1313200 (1993) and U.S. Pat. 4992605 (1991) is added to transition metal catalysts in the presence of hydrogen.

In the petroleum industry, a pressure of 1 to 25 MPa is usually used for catalytic hydrocracking, at temperatures of 350 ° to 450 ° C. Based on Nimoy / Al ₂ O 3 and Como / Al ₂ O 3 catalysts, alkanes and alkylbenzenes having a total conversion of up to 100%, with a yield of C12 - C18 alkanes of 65 to 75%, can be continuously transformed into three independent processes: deoxygenation, decarboxylation and hydrogenation. After partial isomerization, the products are similar to fossil fuels. The disadvantage of this process is that products with excellent fuel properties are expensive. High pressure technologies using hydrogen and expensive catalysts are considered uneconomical and the activity of the catalyst in this process decreases.

Another process, known as the catalytic cracking process with natural triacylglycerols, is based on the principle of zeolites as a natural catalyst. Zeolite catalysts are crystalline aluminosilicate materials, three-dimensional on the raster surface of AIO4 and S1O4 quadrilateral structures, where the oxygen atoms are bonded. Zeolites are porous and contain pores of defined size with areas of strong electrostatic field associated with the presence of cations. These regions are highly catalytically reactive. The pore size may vary depending on the requirements of the product. Synthetic zeolite ZSM-5 or HZSM-5 is used with triacylglycerols in petroleum products. On the other hand, it can generate mesoporous forms of zeolite from MCM linearly, with a long chain of hydrocarbons similar in shape to the hydrocarbons contained in the diesel. The disadvantage of this group of processes is the high cost of zeolite catalysts and their limited recyclability, as well as the problem of dealing with the catalyst used.

In the document SK 287982 B6 the mentioned disadvantages of the process of catalytic cracking of triacylglycerols are eliminated by using a catalyst based on lignocellulose or cellulosic material in the form of granules, powders or fibers. However, in this process, the catalyst consumption is relatively high, and thus the whole process is inefficient.

The essence of the technical solution

The disadvantages of thermal cracking mentioned in the prior art documents are largely eliminated by the technical solution, the aim of which is to improve the efficiency of the cracking process with lower catalyst consumption.

For the preparation of a lignocellulosic specifically activated catalyst for the thermocatalytic cracking of macromolecular organic compounds of plastics and / or municipal waste, a mixture containing 10 to 15 wt. of alkaline mixture and the remainder up to 100 wt. is a biomass consisting of lignocellulose and / or cellulose in the form of grain, pulp, sawdust, straw, fibers or recovered paper. The alkaline mixture contains 0.1 to 1.5% by weight. alkali and the remainder up to 100 wt. is H ₂ O. The alkalis are selected from the following groups of compounds: alkali hydroxides, alkaline earth hydroxides, alkali carbonates, alkaline earth carbonates, alkaline bicarbonates, alkaline earth bicarbonates, or mixtures thereof.

The process for preparing a specifically activated catalyst consists in that a mixture containing 10 to 15 wt. of alkaline mixture and the remainder up to 100 wt. is biomass, it is homogenized. Subsequently, the H ₂ O is evaporated and the specifically activated catalyst thus prepared is dried at a temperature of up to 260 ° C. Said process achieves the desired functionality of the catalyst in question. The specifically activated catalyst thus prepared is in the form of grains or granules and its particles have at least one dimension in the range from 0.01 to 10 mm.

The lignocellulosic specifically activated catalyst prepared according to the technical solution is intended for thermocatalytic cracking of macromolecular organic compounds of plastics and / or municipal waste.

The use of biomass - lignocellulose and / or cellulose as the basic component of the catalyst is associated with its innumerable advantages. The main advantage of a specifically activated catalyst is its very low cost, since

SK 9255 Υ1 raw materials for its preparation are easily available. Specific waste can also be advantageously used as a catalyst. Preferred catalyst components include agricultural waste, processed wood waste, further ground cereal or rapeseed straw, hay, dry leaves, ground corn cobs, walnut shells, ground pressed rapeseed or sunflower seed cake, but also harvested paper.

The raw materials used are recyclable, the oil residue is usable. It can be stated that the catalytic activity of both specifically treated lignocellulose and cellulose can be used as a cracking catalyst - and not as a catalyst component.

Lignin removal and elevated temperature during cracking make lignocellulose and / or cellulose biomass a spongy but strong structure with apertures similar in size to zeolite. The porous structure then results, as does the zeolite process, in splitting the structures. The existing alkali metals in lignocellulose have the same function. In the case of natural lignocellulose, the alkali content is relatively low. By specific activation, t. j. the addition of alkalis, such as alkali hydroxides, alkaline earth hydroxides, alkali carbonates, alkaline earth carbonates, alkaline bicarbonates, alkaline earth hydrocarbons, increases the alkali content, thereby specifically activating the catalyst.

In this way, the catalyst is specifically activated and fully usable for the catalytic cracking process.

The thermocatalytic cracking process takes place in such a way that the raw material - plastics and / or municipal waste is mixed with a specifically activated catalyst in a suitable device (reactor), the proportion of specifically activated catalyst being up to 15% by weight. The raw material used for cracking can be based on plastics from plastics production, contaminated plastics with bio-components, municipal waste and the like. (Plastics may contain animal fats, tallow, lard, chicken fat, fish oils, rendering fat and similar products.) The specifically activated catalyst is in the form of grains, granules or fibers. The reaction mixture is maintained between 400 and 450 ° C. The thermal process has a limited endurance at a given temperature for a total of 60 minutes. The intensive development of vapors in the technological process during the catalytic reaction is the result of the cleavage of macromolecular structures of plastics / municipal waste carried out directly in the thermal plant, which then passes to the condenser, where its sufficient surface allows condensation of all its components. The temperature of the liquid reaction mixture and the supply of steam in the condenser are measured during the reaction and maintained at the set temperature. The device does not have to be in a protective atmosphere, as the device does not allow access to oxygen. The catalyst used is solid and brittle, has a lower density and a structure similar to charcoal. The process results in a liquid condensate in an amount of up to 75% by weight, a gaseous content of up to 15% by weight. and the remainder up to 100% is the catalyst used.

The catalyst used can be treated and used, for example, as activated carbon. The condensate liquid, as the main product of thermocatalytic cracking, contains up to 10% H ₂ O depending on the composition of the inputs. Water is insoluble with the other components in the liquid condensate, so it stabilizes spontaneously and separates as a separate phase.

It is further possible to achieve the separation of the heavy, medium and light fractions of the liquid phase by the distillation process. The light fraction includes hydrocarbons in the gasoline area, the middle fraction includes hydrocarbons in the diesel area, and the heavy fraction returns to the cracking process. No waste is generated in the process.

_{CH 4} , C2H4 and C2H6 have a dominant share in the resulting gaseous fraction.

The thermocatalytic cracking of plastics and / or municipal waste using a specifically activated catalyst can be carried out as a batch or as a continuous process.

The presented solution ensures high efficiency of the cracking process. This process makes it possible to achieve economically lower input costs which are more efficient, for example a recyclable catalyst. The lignocellulosic / cellulose-specifically activated catalyst remains in the form of a porous material of higher density, such as coal, after the first use. It can be recycled without changing parameters and used multiple times. Used or processed plastics and municipal waste have only a small effect on the liquid composition of cracked condensate. Disposal of the used catalyst is problem-free and practically at a very low cost. The natural catalyst used has a relatively high energy value. After extraction of organic residues, it can be used as coal or can be used in steel production. It can also be used as a harmless fertilizer for soil.

Examples of embodiments

Example 1

By mixing an alkali, in this case KOH, the mixing ratio being 99% by weight. H2O and 1 wt. KOH, an alkaline mixture is prepared. Subsequently, the alkaline mixture is mixed with biomass - sawdust (0.1 - 2 mm), the resulting mixture is homogenized, after evaporation of H ₂ O from said mixture, the mixture is dried at 260 ° C. The specifically activated catalyst thus prepared is activated lignocellulose in the form of grains and granules.

SK 9255 Υ1

In a two-necked glass flask with a volume of 1000 ml, 250 g of plastics and 27.5 g of specifically activated catalyst are mixed, which corresponds to its 11% by weight. fraction in the resulting mixture prepared for the catalytic cracking process. The reaction mixture is maintained at 400-450 ° C for 15 minutes. The thermal process has a limited endurance at a given temperature for a total of 20 minutes, including cooling. The intensive development of vapors in the technological process during the catalytic reaction is the result of the splitting of the plastic structure carried out directly in the thermal device, which passes into the condenser, where its sufficient surface allows condensation of all components. The temperature of the liquid reaction mixture and the supply of steam in the condenser are measured during the reaction and maintained at the set temperature. The process results in a liquid condensate in an amount of 75% by weight, a gaseous content of 7% by weight. and the balance 18 wt. consists of the catalyst used, which is solid and brittle, has a lower density and a structure similar to charcoal. The condensate liquid, as the main product of the catalytic cracking, contains 5% by weight. H2O. The water in the liquid condensate has stabilized and is subsequently separated as a separate liquid phase.

The distillation process further separates the heavy, medium and light liquid phase fractions:

heavy fraction 8%, medium fraction 83% and light fraction 9%.

No waste is generated in the process. Some parameters of the distilled residue: viscosity (40 ° C) 6.38 mm ² / s, density (15 ° C) 824 kg.m \ O2 content 3.34% by weight, H2O content 36 ppm, acid number <1 mg KOH / g, combustion heat 39.07 MJ / kg.

Example 2

An alkaline mixture is prepared by mixing an alkali, in this case NaOH, the mixing ratio being 99% by weight. H2O and 1 wt. NaOH. Subsequently, the alkaline mixture is mixed with biomass-straw (0.1-1 mm), the resulting mixture is homogenized, then the process of evaporation of H ₂ O from said mixture takes place and the mixture is dried at 260 ° C. The specifically activated catalyst thus prepared is activated lignocellulose in the form of grains and granules.

In the reactor, which is formed by a screw in the pipe and is electrically heated through the outer jacket, 5 kg of municipal waste (INPUT) and 0.55 kg of specifically activated catalyst are mixed, which corresponds to its 11% by weight. fraction in the resulting mixture prepared for the catalytic cracking process. The reactor is maintained at 450 ° C. The thermal process has a limited endurance at a given temperature for a total of 60 minutes. The intensive development of vapors in the technological process during the catalytic reaction is the result of the cleavage of macromolecular structures of municipal waste carried out directly in the thermal plant, which then passes to the condenser, where its sufficient surface allows condensation of all its components. The temperature of the liquid reaction mixture and the supply of steam in the condenser are measured during the reaction and maintained at the set temperature. The process results in a liquid condensate in an amount of 70% by weight, a gaseous fraction of 12% by weight. and the balance 18 wt. consists of the catalyst used, which is solid and brittle, has a lower density and a structure similar to charcoal. The condensate liquid, as the main product of the catalytic cracking, contains 5% by weight. H ₂ O. The water in the liquid condensate has stabilized and is subsequently separated as a separate liquid phase.

The distillation process further achieves the separation of the heavy, medium and light fractions of the liquid phase: heavy fraction 7%, medium fraction 80% and light fraction 13%.

No waste is generated in the process. Some parameters of the distilled residue: viscosity (40 ° C) 7.41 mm ² / s, density (15 ° C) 803 kg.m \ O2 content 5.47% by weight, H2O content 78 ppm, acid number 14 mg KOH / g, heat of combustion 37.97 MJ / kg.

Example 3

An alkaline mixture is prepared by mixing an alkali, in this case Na 2 CO 3, with a mixing ratio of 98.5% by weight. H ₂ O and 1.5 wt. At ₂ CO3. Subsequently, the alkaline mixture is mixed with biomass-cellulose (0-0.1 mm), the resulting mixture is homogenized, then the process of evaporation of H ₂ O from said mixture takes place and the mixture is dried at 260 ° C. The specifically activated catalyst thus prepared is activated cellulose in the form of grains and granules.

In a two-necked glass flask with a volume of 1000 ml, 250 g of plastics and 37.5 g of specifically activated catalyst are mixed, which corresponds to its 15% by weight. fraction in the resulting mixture prepared for the catalytic cracking process. The reaction mixture is maintained at 400-450 ° C for 15 minutes. The thermal process has a limited endurance at a given temperature for a total of 20 minutes, including cooling. The intensive development of vapors in the technological process during the catalytic reaction is the result of the splitting of the plastic structure carried out directly in the thermal device, which passes into the condenser, where its sufficient surface allows condensation of all components. The temperature of the liquid reaction mixture and the supply of steam in the condenser are measured during the reaction and maintained at the set temperature. The result of the process is liquid condensate in quantity

SK 9255 Υ1% by weight, gaseous content 9% by weight, and the balance 13% by weight, form the catalyst used, which is solid and brittle, has a lower density and a structure similar to charcoal. The condensate liquid, as the main product of the catalytic cracking, contains 6% by weight. H2O. The water in the liquid condensate has stabilized and is subsequently separated as a separate liquid phase.

The distillation process further separates the heavy, medium and light liquid phase fractions:

heavy fraction 7%, medium fraction 82% and light fraction 11%.

No waste is generated in the process. Some parameters of the distilled residue: viscosity (40 ° C) 4.36 mm ² / s, density (15 ° C) 798 kg.m \ O2 content 2.27% by weight, H2O content 23 ppm, acid number <1 mg KOH / g, combustion heat 39.87 MJ / kg.

Example 4

An alkaline mixture is prepared by mixing an alkali, in this case NaOH, with a mixing ratio of 99.5% by weight. H ₂ O and 0.5 wt%. NaOH. Subsequently, the alkaline mixture is mixed with biomass-straw (0.1-1 mm), the resulting mixture is homogenized, then the process of evaporation of H ₂ O from said mixture takes place and the mixture is dried at 260 ° C. The specifically activated catalyst thus prepared is activated lignocellulose in the form of grains and granules.

In the reactor, which is formed by a screw in the pipe and is electrically heated through the outer jacket, 5 kg of municipal waste (INPUT) and 0.5 kg of specifically activated catalyst, corresponding to its 10% by weight, of the mixture thus prepared for the process, are mixed. catalytic cracking. The reactor is maintained at 450 ° C. The thermal process has a limited endurance at a given temperature for a total of 60 minutes. The intensive development of vapors in the technological process during the catalytic reaction is the result of the cleavage of macromolecular structures of municipal waste carried out directly in the thermal plant, which then passes to the condenser, where its sufficient surface allows condensation of all its components. The temperature of the liquid reaction mixture and the supply of steam in the condenser are measured during the reaction and maintained at the set temperature. The process results in a liquid condensate of 73% by weight, a gaseous content of 10% by weight, and a balance of 17% by weight, constituting the catalyst used, which is solid and brittle, has a lower density and a charcoal-like structure. The condensate liquid, as the main product of the catalytic cracking, contains 7% by weight. H ₂ O. The water in the liquid condensate has stabilized and is subsequently separated as a separate liquid phase.

The distillation process further achieves the separation of the heavy, medium and light liquid phase fractions: heavy fraction 10%, medium fraction 79% and light fraction 11%.

No waste is generated in the process. Some parameters of the distilled residue: viscosity (40 ° C) 7.98 mm ² / s, density (15 ° C) 818 kg.m \ O2 content 6.07% by weight, H2O content 69 ppm, acid number 9 mg KOH / g, heat of combustion 38.56 MJ / kg.

Example 5

An alkaline mixture is prepared by mixing an alkali, in this case NaOH, in a mixing ratio of 98.5% by weight. H2O and 1.5 wt%. NaOH. Subsequently, the alkaline mixture is mixed with biomass-straw (0.1 - 1 mm), the resulting mixture is homogenized, then the process of evaporation of H ₂ O from said mixture takes place and the mixture is dried at 260 ° C. The specifically activated catalyst thus prepared is activated lignocellulose in the form of grains and granules.

In the reactor, which is formed by a screw in the pipe and is electrically heated through the outer jacket, 5 kg of municipal waste (INPUT) and 0.75 kg of specifically activated catalyst, corresponding to its 15% by weight, in the mixture thus prepared for the process, are mixed. catalytic cracking. The reactor is maintained at 450 ° C. The thermal process has a limited endurance at a given temperature for a total of 60 minutes. The intensive development of vapors in the technological process during the catalytic reaction is the result of the cleavage of macromolecular structures of municipal waste carried out directly in the thermal plant, which then passes to the condenser, where its sufficient surface allows condensation of all its components. The temperature of the liquid reaction mixture and the supply of steam in the condenser are measured during the reaction and maintained at the set temperature. The process results in a liquid condensate of 71% by weight, a gaseous content of 14% by weight, and a balance of 15% by weight, constituting the catalyst used, which is solid and brittle, has a lower density and a charcoal-like structure. The condensate liquid, as the main product of the catalytic cracking, contains 9% by weight. H ₂ O. The water in the liquid condensate has stabilized and is subsequently separated as a separate liquid phase.

The distillation process further achieves the separation of the heavy, medium and light liquid phase fractions: heavy fraction 8%, medium fraction 77% and light fraction 15%.

SK 9255 Υ1

No waste is generated in the process. Some parameters of the distilled residue: viscosity (40 ° C) 3.77 mm ² / s, density (15 ° C) 778 kg.m \ Oz content 4.47% by weight, H2O content 26 ppm, acid number 5 mg KOH / g, heat of combustion 39.17 MJ / kg.

Example 6

An alkaline mixture is prepared by mixing an alkali, in this case KHCO ₃ , the mixing ratio being 99% by weight. H2O and 1 wt. KHCO3. Subsequently, the alkaline mixture is mixed with biomass - corn husks (0.1 2 mm), the resulting mixture is homogenized, then the process of evaporation of H2O from said mixture takes place and the mixture is dried at 260 ° C. The specifically activated catalyst thus prepared is activated lignocellulose in the form of grains and granules.

In a 1000 ml two-necked glass flask, 250 g of plastics and 37.5 g of specifically activated catalyst are mixed, which corresponds to its 15% by weight. fraction in the resulting mixture prepared for the catalytic cracking process. The reaction mixture is maintained at 400-450 ° C for 15 minutes. The thermal process has a limited endurance at a given temperature for a total of 20 minutes, including cooling. The intensive development of vapors in the technological process during the catalytic reaction is the result of the splitting of the plastic structure carried out directly in the thermal device, which passes into the condenser, where its sufficient surface allows condensation of all components. The temperature of the liquid reaction mixture and the supply of steam in the condenser are measured during the reaction and maintained at the set temperature. The process results in a liquid condensate in an amount of 77% by weight, a gaseous content of 5% by weight. and the balance 18 wt. consists of a catalyst used which is solid and brittle, has a lower density and a structure similar to charcoal. The condensate liquid, as the main product of the catalytic cracking, contains 6% by weight. H ₂ O. The water in the liquid condensate has stabilized and is subsequently separated as a separate liquid phase.

The distillation process further separates the heavy, medium and light liquid phase fractions:

heavy fraction 9%, medium fraction 82% and light fraction 9%.

No waste is generated in the process. Some parameters of the distilled residue: viscosity (40 ° C) 6.95 mm ² / s, density (15 ° C) 837 kg.m \ O2 content 4.34% by weight, H ₂ O content 46 ppm, acid number 16 mg KOH / g, heat of combustion 39.96 MJ / kg.

Industrial applicability

The method of thermocatalytic cracking of macromolecular organic compounds - plastics and municipal waste using a lignocellulosic specifically activated catalyst prepared according to the technical solution can be used in the production of biofuels and alternative fuels from renewable sources. After treatment, the liquid cracking product can be used as a fuel, ecofuel, alternative fuel, fuels or fuel component for motor vehicles based on renewable raw materials.

Claims (3)

A composition for the preparation of a lignocellulosic specifically activated catalyst for the thermocatalytic cracking of macromolecular organic compounds - plastics and municipal waste, characterized in that it contains 10 to 15 wt. of alkaline mixture and the remainder up to 100 wt. is a biomass consisting of lignocellulose and / or cellulose in the form of grain, pulp, sawdust, straw, fibers or recovered paper, the alkaline mixture consisting of 0.1 to 1.5% by weight. alkali and the remainder up to 100 wt. is HjO. The composition according to claim 1, characterized in that the alkalis are selected from the following groups of compounds: alkali hydroxides, alkaline earth hydroxides, alkali carbonates, alkaline earth carbonates, alkaline bicarbonates, alkaline earth bicarbonates, or mixtures thereof. Process for the preparation of a lignocellulosic specifically activated catalyst, characterized in that the mixture according to claims 1 or 2 is homogenized and dried after evaporation of water at a temperature of up to 260 ° C, the specifically activated catalyst particles thus prepared being in the form at least one dimension in the range from 0.01 to 10 mm. Use of a lignocellulosic specifically activated catalyst prepared according to claim 3 for the thermocatalytic cracking of macromolecular organic compounds of plastics and / or municipal waste. End of document