Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/40—High-molecular-weight compounds
  • C08G18/64—Macromolecular compounds not provided for by groups C08G18/42 - C08G18/63
  • C08G18/6484—Polysaccharides and derivatives thereof
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/40—High-molecular-weight compounds
  • C08G18/48—Polyethers
  • C08G18/487—Polyethers containing cyclic groups
  • C08G18/4883—Polyethers containing cyclic groups containing cyclic groups having at least one oxygen atom in the ring

Definitions

• the invention relates to an environmentally friendly and cost-effective method for biopolyol production.
• the invention relates to obtaining biopolyol from biological sources with a more environmentally friendly and cost-effective method as an alternative to the acid- catalyzed solvothermal liquefaction method in the state of the art.
• biopolyol production is carried out in a step-by-step (gradual) process, and the biopolyol obtained in each step is used as a solvent in the next liquefaction process (for obtaining the next-generation biopolyol) completely or by blending with the petroleum-based solvent mixture (SM).
• SM petroleum-based solvent mixture
• Polyols are reactive raw materials containing at least two hydroxyl functional groups and forming polyurethane (PU) by reacting with isocyanate (NCO) groups through these groups.
• Polyols are very important components for polyesters as well as polyurethanes.
• Polyols which act as chain extenders in the polymer formation process, greatly control the mechanical, thermal and physical properties of the final material, and can also reduce the total cost.
• the need for polyols is increasing day by day. The reason for this is the need for polymer-based products in which polyols are used in all fields where technology and quality of life/we 11 -being are required in human life.
• polyurethanes obtained from polyols are known as a unique group of polymers that are used extensively in areas such as transportation, construction, furniture industry and mining due to their wide range of properties.
• polyols One of the most important components of polyurethane production is polyols, and it is seen that these reagents have been produced from petroleum -based sources in the historical process, however, they have started to be produced from biomass in recent years. Polyols are of great importance in determining the physico-mechanical properties of the final product. The hardness or elasticity, chemical resistance and gas and moisture permeability degrees of polyurethane foam are largely determined by the polyols used. Although polyols can be synthesized with different chemical approaches from various biomasses with easy and quick processes, there are still some aspects related to the issue which are open to improvements.
• biopolyols obtained from biomass are called “biopolyols”.
• Patent application no. KR101893878B1 mentions a biopolyol (biomass content of 90% and above) obtained using castor oil and a PU foam formulation including this biopolyol.
• the PU foam formulation comprises of a petroleum-based polyol, a biopolyol, a cell opener, an amine- based catalyst, a surfactant, a foaming agent, petroleum based diisocyanate and bioisocyanate.
• Petroleum-based polyol is obtained by mixing a diol polyol and a triol polyol with a ratio of 1: 10-1:20.
• the production method of the PU formulation obtained using a high ratio of biomass content subject to the patent application includes the following steps; i) preparing a resin premixture by mixing a petroleum-based polyol, a biopolyol, a cell opener, an amine-based catalyst, a surfactant and a foaming agent, ii) synthesizing isosorbide diol lactate (ISB di (lactate)) by reaction of isosorbide diol with lactate, and then synthesizing the NCO-pre- polymer to prepare a bioisocyanate, and iii) mixing and reacting the bioisocyanate with the resin premixture, respectively.
• biomass is used in polyol production in the state of the art
• petroleum-based polyhydric alcohols are used as solvents in biopolyol production by the acid-catalyzed solvothermal liquefaction process from biomass. It is not possible to find any studies to reduce the costs of using petroleum-based solvents in the state of the art. In other words, biopolyols in the state of the art can only be obtained as a result of costly processes.
• biopolyol Due to reasons such as the fact that costly petroleum-based polyhydric solvents are used in each liquefaction process in biopolyols production, and the lack of a cost-effective and sustainable approach in the liquefaction processes of biopolyols obtained from biomass in the known state of the art, it is necessary to develop a method in which all of these problems are eliminated, biopolyol is obtained from biological sources with a more environmentally friendly and cost-effective method, and it is possible to obtain biopolyol that maintains the sufficient quality required for the relevant fields of application/use.
• the invention describes an environmentally friendly and cost-effective method for biopolyol production.
• biopolyol production from biological sources is carried out by a more environmentally friendly and cost-effective method as an alternative to the acid-catalyzed solvothermal liquefaction method in the state of the art, which is one step (batch) process and every batch requires the use of costly petroleum-based solvents.
• biopolyol production is carried out in a step- by-step (gradual) process, and the biopolyol obtained in each step is used as a solvent in the next liquefaction process (for obtaining the next-generation biopolyol) completely or by blending with the petroleum-based solvent mixture (SM).
• SM petroleum-based solvent mixture
• SM solvent mixture
• the objective of the invention is to provide a cost-effective method for biopolyol production that requires less cost compared to the state of the art.
• the realization of biopolyol production with a more cost-effective approach is provided by the biopolyol production method of the invention. Since the biopolyol obtained in each step in the biopolyol production method of the invention is utilized as a solvent in the next liquefaction process (for obtaining the nextgeneration biopolyol) or by blending with the solvent mixture (SM), the costly and petroleumbased solvent use of the biomass in the liquefaction process is minimized or completely eliminated in the biopolyol production(s) in the next generation.
• SM solvent mixture
• Another objective of the invention is to provide a more environmentally friendly method for biopolyol production compared to biopolyol productions in the state of the art.
• the realization of biopolyol production with a more environmentally friendly approach is provided by the biopolyol production method of the invention.
• the invention relates to an environmentally friendly and cost-effective method for biopolyol production.
• the invention relates to obtaining biopolyol from biological sources with a more environmentally friendly and cost-effective method as an alternative to the acid- catalyzed solvothermal liquefaction method in the state of the art.
• biopolyol production is carried out in a step-by-step (gradual) process, and the biopolyol obtained in each step is used as a solvent in the next liquefaction process (for obtaining the next-generation biopolyol) completely or by blending with the petroleum-based solvent mixture (SM).
• SM petroleum-based solvent mixture
• OMP olive mill pomace
• Production method of a 1st generation biopolyol using petroleum-based solvent mixture (SM) only once involves the following process steps; i. subjecting the biomass to solvothermal liquefaction process in the solvent mixture (SM) consisting of 80% polyethylene glycol 400 (PEG400) and 20% glycerine by mass, accompanied by a 2-6% sulfuric acid (H2SO4) catalyst, for 20-100 minutes at 130-170°C, with a biomass: liquefaction solvent ratio of 1 :4, and thus obtaining a main biopolyol, ii.
• SM solvent mixture
• PEG400 polyethylene glycol 400
• H2SO4 2-6% sulfuric acid
• the process step no. (i) is subjecting the biomass to solvothermal liquefaction in a solvent mixture (SM) consisting of 80% polyethylene glycol 400 (PEG400) and 20% glycerine by mass, accompanied by a 3.8% sulfuric acid (H2SO4) catalyst, for 62 minutes at 170°C, with a biomass: liquefaction solvent ratio of 1:4, and thus obtaining the main biopolyol.
• SM solvent mixture
• PEG400 polyethylene glycol 400
• H2SO4 3.8% sulfuric acid
• the method of producing a 2nd generation biopolyol by the production from biomass approach involves the following process steps; i. subjecting the biomass to solvothermal liquefaction process in a solvent mixture (SM) consisting of 80% polyethylene glycol 400 (PEG400) and 20% glycerin by mass, accompanied by a 2-6% sulfuric acid (H2SO4) catalyst, for 20-100 minutes at 130-170°C, with a biomass: liquefaction solvent ratio of 1:4, and thus obtaining the main biopolyol, ii.
• SM solvent mixture
• PEG400 polyethylene glycol 400
• H2SO4 2-6% sulfuric acid
• step no. (i) is subjecting the biomass to solvothermal liquefaction in a solvent mixture (SM) consisting of 80% polyethylene glycol 400 (PEG400) and 20% glycerin by mass, accompanied by a 3.8% sulfuric acid (H2SO4) catalyst, for 62 minutes at 170°C, with a biomass: liquefaction solvent ratio of 1:4, and thus obtaining the main biopolyol.
• SM solvent mixture
• H2SO4 3.8% sulfuric acid
• the method of producing respectively 2nd, 3rd and 4th generation biopolyol by the production from biomass approach involves the following process steps; i.
• SM solvent mixture
• PEG400 polyethylene glycol 400
• H2SO4 2-6% sulfuric acid
• the process step no. (i) is subjecting the biomass to solvothermal liquefaction in a solvent mixture (SM) consisting of 80% polyethylene glycol 400 (PEG400) and 20% glycerin by mass, accompanied by a 3.8% sulfuric acid (H2SO4) catalyst, for 62 minutes at 170°C, with a biomass: liquefaction solvent ratio of 1:4, and thus obtaining the main biopolyol.
• SM solvent mixture
• PEG400 polyethylene glycol 400
• H2SO4 3.8% sulfuric acid
• the biomass used in the biomass-based biopolyol production method subject to the invention is olive mill pomace (OMP).
• OMP olive mill pomace
• sugar beet, tomatoes and red pepper, aromatic plants such as lavender and thyme, cultivated mushrooms, algae, peas, kidney beans, com, eucalyptus, various types of woody trees (poplar, cypress, birch, linden, olive, chestnut, pear, oak, white hornbeam, ash tree, walnut, elm, maple, alder, acacia, Calabrian pine, scotch pine, black pine, nut pine, Aleppo pine, maritime pine, cherry, fir, spruce, juniper, mulberry, boxwood, pavilion, paulownia, willow, eucalyptus), rice, wheat, sugar cane, rapeseed, coffee, cotton, citrus, cashew nuts, soy, hazelnut, oats, bananas, beans
• RSM is a blend of statistical and mathematical techniques to develop, improve and optimize any process, product design, system or experiment.
• the most important advantage of this method is that the effect of a large number of parameters can be evaluated at the same time and the number of experiments can be reduced.
• it also has advantages such as examining the interactions of independent variables with each other and expressing the relationship between independent variables and the response by defining the system with a mathematical model.
• RSM consists of following stages: i) determining the independent variables and the minimum and maximum values of these variables, ii) conducting experiments according to the determined parameters, iii) creating a mathematical model against the received process response and determining the optimum experimental parameters, iv) conducting validation studies according to the determined optimum values, and v) drawing three-dimensional response surface and contour graphics with computer-aided software programs.
• y is response
• /? 0 is cutting point
• ? is quadratic coefficient
• interaction coefficient is coded factor levels.
• CCD central composite design
• the CCD which is usually proposed for the design of experiments to be performed consecutively, is a full factorial design plan with five levels. These levels are discussed in three parts: two factorial (level) points, two asterisk (axial) points, and one central point.
• k is the number of factors determined for the design.
• the number of experiments to be performed is determined by the following equation.
• k refers to the number of factors determined for the design
• 2 k refers to the number of experiments corresponding to the comer points of the cube
• 2k refers to the number of experiments corresponding to the axial points of the cube
• mo refers to the number of experiments performed for the central point.
• the main effects and first-order interactions of the quadratic equation created from the CCD model are determined from the 2k experiments, while the curvature of the equation is determined with the help of central points.
• the responses obtained as a result of experimental studies are analysed using the ANOVA test.
• Figure 1 shows the 3-factor central composite design. Each circle in Figure 1 refers to an experiment.
• CCD is one of the most preferred design methods to investigate the synergistic effect of different variables on a target parameter among response surface methods.
• the 3- variable and 5-level experimental design was used to optimize the process parameters for obtaining biopolyol from olive mill pomace (OMP) by acid-catalyzed solvothermal liquefaction method using Minitab® 19 statistical software (Minitab Inc., Pennsylvania, USA).
• OMP olive mill pomace
• Minitab® 19 statistical software Minitab Inc., Pennsylvania, USA.
• the variables were selected as: amount of catalyst (A), reaction time (B) and reaction temperature (C).
• the experimental range and levels of the variables are explained in Table 2, and the experimental design and experimental order are given in Table 3. This design consists of a total of 17 experiments.
• the curvature of the model created is determined thanks to the central points, while experimental errors and noncompliance are determined by the factorial points.
• Table 2. Experimental ranges and levels of independent variables.
• R 0,9363
• the ranges where the liquefaction yield (LY) takes a maximum value are the studies where the amount of catalyst is 4-5% and the reaction time is 60-80 minutes. At the end of these ranges, the liquefaction yield (LY) tended to decrease. As can be understood from the graph (b) in Figure 3, in order for the liquefaction yield (LY) to be higher than 88%, the amount of catalyst must be more than 4.9% and the reaction time must be longer than 45 minutes.
• the optimum process parameters for obtaining biopolyol from olive mill pomace (OMP) with the highest efficiency were determined using the developed mathematical model. Accordingly, using the obtained quadratic polynomial equation, it was determined that the optimum conditions for 95% liquefaction efficiency (choosing 95% liquefaction efficiency as the response) were 3.8% for the amount of catalyst, 62 minutes for reaction time and 170°C for reaction temperature. In this study, the primary target was selected as high liquefaction efficiency when determining the optimum process parameters. In addition, low energy and catalyst consumption, short liquefaction time and physicochemical properties of the obtained biopolyol suitable being for the intended use are among the other main objectives.

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• Chemical & Material Sciences (AREA)
• Health & Medical Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Organic Chemistry (AREA)
• Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)

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• 2023
  • 2023-08-29 EP EP23861007.5A patent/EP4569050A4/de active Pending

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