WO2014068590A1 - Procédé en continu pour la dépolymérisation de lignine en produits chimiques industriellement utiles - Google Patents

Procédé en continu pour la dépolymérisation de lignine en produits chimiques industriellement utiles Download PDF

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WO2014068590A1
WO2014068590A1 PCT/IN2013/000660 IN2013000660W WO2014068590A1 WO 2014068590 A1 WO2014068590 A1 WO 2014068590A1 IN 2013000660 W IN2013000660 W IN 2013000660W WO 2014068590 A1 WO2014068590 A1 WO 2014068590A1
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lignin
reactor
lit
moles
catalyst
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PCT/IN2013/000660
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Sunil Shankar JOSHI
Bhaskar Dattatraya Kulkarni
Ajay Singh TOMER
Yogesh Dashrath SATHE
Mahesh Ramchandra JADHAV
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Council Of Scientific & Industrial Research
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07G—COMPOUNDS OF UNKNOWN CONSTITUTION
    • C07G1/00—Lignin; Lignin derivatives

Definitions

  • the invention discloses a continuous process for de-polymerization of lignin to obtain substituted aromatic compounds.
  • the invention provides a process for lignin de- polymerization to be converted into phenolic compounds having commercial importance in a tubular reactor using catalyst under hydrothermal conditions.
  • the present invention provides a process of de- polymerization of the lignin wherein the process is carried out in two stages in a continuous mode, in the first stage hydrolysis of the complex biopolymer gives oligomers, while in the second stage catalytic oxidation of the oligomers resulting into high yields of substituted aromatic compounds.
  • the reaction uses homogenous catalyst copper, H 2 0 2 as oxidant and proceeds under alkaline conditions.
  • lignin the second largest biopolymer
  • the 4-hydroxyphenyl propane, 4-hydroxy 2-methoxy phenyl propane and 4-hydroxy, 2, 5 di-methoxy phenyl propane are the main building blocks of the lignins, which can be converted into compounds of commercial interest.
  • Depolymerization of lignin using catalytic processes is known in the art.
  • US 6,214,976 B1 relates to a process for depolymerizing and / or chemically modifying lignin or lignin like compounds in which a solution of copper and peroxide acts on lignin and /or lignin-like substance at a temperature of less than 100° C, characterized in that the solution is an aqueous solution containing copper or a copper complex, a coordination compound and peroxideand Wherein the concentration of the copper or copper complex is between 0.001 % and 5%, and Wherein the concentration of the coordination compound is lower than 20% and Wherein the concentration of peroxide is between 0.01% and 20%.
  • the main object of the invention is to provide a continuous process for depolymerization of lignin to obtain substituted aromatic compounds.
  • Another object of the present invention is to provide a process of de-polymerization of the lignin wherein the process is carried out in two stages in a continuous mode, In the first stage hydrolysis of the complex biopolymer gives oligomers, while in the second stage catalytic oxidation of the oligomers resulting into high yields of substituted aromatic compounds.
  • the reaction uses homogenous catalyst copper, H 2 0 2 as oxidant and proceeds under alkaline conditions
  • Another objective of the invention is to provide a process for depolymerization of lignin that avoids the use of a capping agent.
  • Another objective of the invention is to provide a process for depolymerization of lignin in which no char formation
  • Another objective of the invention is to provide a process for depolymerization of lignin where use of Cu lowers the cost of the process making it more economical.
  • Another objective of the invention is to provide a process for depolymerization of lignin to obtain high yield of products as compared to highest (1 -8% ) of prior art.
  • Another objective of the invention is to provide a process for depolymerization of lignin which offers a great degree of selectivity to fine tune the products by altering the reaction conditions.
  • the reaction condition such as residence time, catalyst, temperature and pressure we can tune the selectivity to desired products.
  • the present invention provides a process of de-polymerization of lignin to obtain substituted aromatic compounds wherein the process is carried out in two stages in a continuous mode comprising:
  • step (b) heating reaction mixture as obtained in step (a) at temperature ranging between from 200oC to 380 oC, pressure from 150 bar to 350 bar having residence time 5 to 90 sec to obtain substituted aromatic compounds.
  • the homogeneous catalyst used is copper nitrate solution having concentration 0 to 3x10-3 moles/lit.
  • the oxidant used is hydrogen peroxide.
  • oxygen concentration from 0 to 1x10-2 moles/lit.
  • the yield of the aromatic compounds is 53 to 55%.
  • the process proceeds in a tubular reactor.
  • the aromatic products obtained comprises catechol, phenol, homovanillic acid, vanillic acid, guaicol, syringic acid, vanillin and acetovanillone.
  • the aromatic products obtained comprises preferably catechol, phenol, homovanillic acid, guaicol, vanillin and acetovanillone.
  • Figure 1 Reactor sketch for lignin de-polymerization.
  • Figure 2 Screening of lignins- de-polymerization of various lignins under subcriticai conditions of water. Reaction conditions: Lignin cone. 5x10 "3 moles/lit, Temperature 300°C, Pressure 250 bar, Residence time 65 sec.
  • Figure 3 Screening of lignins- de-polymerization of lignins under subcriticai conditions of water and oxidizing environment. Reaction conditions: Lignin cone. 5x10° moles/lit, Peroxide cone. 5x10 "3 moles/ lit, Temperature 300°C, Pressure 250bar, Residence time 65 sec.
  • Figure 4 Screening of lignins- de- polymerization of lignins under subcriticai conditions of water and oxidizing environment in presence of catalyst. Reaction conditions: Lignin cone. 5x10 "3 moles/lit, Peroxide cone. 5x10 "3 moles/lit, Catalyst cone. 1.96 x10 "3 moles/lit, Temperature 300°C , Pressure 250 bar, Residence time 65 sec, Catalyst feed from top of the reactor.
  • Figure 8 Effect of peroxide concentration on de-polymerization of sugar cane bagasse lignin under subcriticai conditions of water. Reaction conditions: Lignin cone. 5x10 '3 moles/ lit, Temperature 300 °C , Pressure 250 bar, Residence time 65 sec.
  • Figure 9 Effect of peroxide concentration on de-polymerization of sugar cane bagasse lignin under supercritical conditions of water. Reaction conditions: Lignin cone. 5x10 "3 moles/ lit, Temperature 380°C, Pressure 250 bar, Residence time 40 sec.
  • Figure 10 Effect of residence time on de-polymerization of sugar cane bagasse lignin under subcriticai conditions of water.
  • Reaction conditions Peroxide cone. 5x10 '3 moles/lit, Lignin cone. 5x10 "3 moles/lit, Temperature 300°C, Pressure 250 bar, Residence time 50-100 sec.
  • Figure 11 Effect of residence time on de-polymerization of sugar cane bagasse lignin under supercritical conditions of water.
  • Reaction conditions Peroxide cone. 5x10 '3 moles/lit, Lignin cone. 5x10 "3 moles/lit, Temperature 380°C, Pressure 250 bar, Residence time 40-70 sec.
  • Figure 12 Effect of peroxide concentration on de- polymerization of sugar cane bagasse lignin under subcritical conditions of water. Reaction conditions: Lignin cone. 5x10 "3 moles/lit, Catalyst cone. 1 .96 x10 "3 moles/lit, Temperature 300°C , Pressure 300 bar, Residence time 65 sec, Catalyst feed from top of the reactor.
  • Figure 13 Effect of peroxide concentration on de-polymerization of sugar cane bagasse lignin under supercritical conditions of water. Reaction conditions: Lignin cone. 5x10 "3 moles/lit, Catalyst cone. 1.96x10 '3 moles/lit, Temperature 380°C, Pressure 250 bar, Residence time 40 sec, Catalyst feed from top of the reactor.
  • Figure 14 Effect of residence time on de-polymerization of sugar cane bagasse lignin under subcritical conditions of water. Reaction conditions: Lignin cone. 5x10 "3 moles/lit, Peroxide cone. 5x10 '3 moles/lit, Catalyst cone. 1.96 x10 '3 moles/lit, Temperature 300 °C, Pressure 250 bar, Catalyst feed from top of the reactor.
  • Figure 1 5 Effect of residence time on de-polymerization of sugar cane bagasse lignin under supercritical conditions of water. Reaction conditions: Lignin cone. 5x10 '3 moles/lit, Peroxide cone. 5x10 '3 moles/lit, Catalyst cone. 1 .96x10 "3 moles/lit, Temperature 380 °C, Pressure 250 bar, Catalyst feed from top of the reactor.
  • Figure 16 Effect of catalyst concentration on de- polymerization of sugar cane bagasse lignin under subcritical conditions of water and oxidizing environment. Reaction conditions: Lignin cone. 5x10 '3 moles/lit, Peroxide cone. 5x10 "3 moles/lit, Temperature 300 °C, Pressure 250 bar, Residence time 65 sec, Catalyst feed from top of the reactor.
  • Figure 17 Effect of catalyst concentration on de-polymerization of sugar cane bagasse lignin under supercritical conditions of water and oxidizing environment. Reaction conditions: Lignin cone. 5x10 "3 moles/lit, Peroxide cone. 5x10 "3 moles/ lit, Temperature 380 °C, Pressure 250 bar, Residence time 40 sec, Catalyst feed from top of the reactor.
  • Figure 18 Effect of peroxide concentration on de- polymerization of sugar cane bagasse lignin under subcritical conditions of water. Reaction conditions: Lignin cone. 5x10 '3 moles/lit, Catalyst Cu cone. 1 .96x10 "3 moles/lit, Temperature 300°C , Pressure 300 bar, Residence time 65 sec, catalyst feed point middle of the reactor.
  • Figure 19 Effect of peroxide concentration on de-polymerization of sugar cane bagasse lignin under supercritical conditions of water. Reaction conditions: Lignin cone. 5x10 3 moles/lit, Catalyst Cu cone.1 .96x10 "3 moles/lit, Temperature 380°C , Pressure 250 bar, Residence time 40 sec, catalyst feed point middle of the reactor.
  • Figure 20 Effect of residence time on de- polymerization of sugar cane bagasse lignin under subcritical conditions of water.
  • Reaction conditions Peroxide cone. 5x10 "3 moles/lit, Lignin cone. 5x10 '3 moles/lit, Catalyst Cu (II) 1.96 x10 "3 moles/lit, Temperature 300°C, Pressure 300 bar, Residence time 50-100 sec, Catalyst feed point middle of the reactor.
  • Figure 21 Effect of residence time on de-polymerization of sugar cane bagasse lignin under supercritical conditions of water. Reaction conditions: Peroxide cone. 5x10 "3 moles/lit, Lignin cone.
  • Figure 22 Effect of catalyst concentration on de-polymerization of sugar cane bagasse lignin under subcritical conditions of water. Reaction conditions: Peroxide cone. 5x 10 "3 moles/lit, Lignin cone. 5 x 10 "3 moles/ lit, Temperature 300°C, Pressure 250 bar, Residence time 65 sec, Catalyst feed middle of the reactor
  • Figure 23 Effect of catalyst concentration on de-polymerization of sugar cane bagasse lignin under supercritical conditions of water. Reaction conditions: Peroxide cone. 5x 10 ' 3 moles/lit, Lignin cone. 5 x 10 '3 moles/lit, Temperature 380°C, Pressure 250 bar, Residence time 40 sec, Catalyst feed middle of the reactor
  • the various methoxy hydroxyphenyl propanes are the main building blocks of the lignins. These aromatic units are linked to each other by aliphatic carbon chains and ether links. It has been known that the lignin contains about 14 types of bonds and the majority of these bonds are ether bonds
  • the present invention provides a process of de-polymerization of the lignin wherein the process is carried out in two stages in a continuous mode, in the first stage hydrolysis of the complex biopolymer gives oligomers, while in the second stage catalytic oxidation of the oligomers resulting into high yields of substituted aromatic compounds.
  • the reaction uses homogenous catalyst copper, H202 as oxidant and proceeds under alkaline conditions.
  • the present invention provides a process wherein the reaction uses homogenous catalyst copper or substituted metal catalyst preferably Cu, hydrogen peroxide as oxidant and proceeds under alkaline conditions.
  • the source of lignin is any known source of lignin.
  • lignin is isolated from sugarcane bagasse procured for sugarcane waste procured from local sugarcane juice vendor.
  • the present invention provides a process wherein the yield of the aromatic products is >50 % and is preferably in the range of 53% to 55%.
  • the de- polymerization of lignin is carried out in a two or more stage continuous mode by mixing lignin, catalyst and oxidizing solution in appropriate ratio in the tubular reactor.
  • the experiments are conducted in sub critical and super critical conditions of water.
  • the experimental conditions for the process of the invention are temperature, from 200°C to 380 °C, pressure from 150 bar to 350 bar, oxygen concentration from 0 to 1x10 "2 moles/lit and catalyst concentration, 0 to 3x10 '3 moles/lit having residence time 0 to 90 sec.
  • the experimental set-up employed is as shown in the Figure-1 .
  • the set-up is designed and constructed by using high pressure tubes, heated by independent heaters and fitted with electronic temperature controllers.
  • the pressure in the reactor was maintained by using back pressure regulator.
  • HPLC pumps were used to feed the various components to the reactor at the desired flow rate.
  • the first section of the reactor was used to heat the water or peroxide solution, while second and third section was used to de-polymerize the lignin under different set of conditions.
  • General procedure followed was as follows.
  • the deionized water was pumped at desired flow rate (typically at 5.5 ml/min) by using pump P1 , and when the reaction was carried in the oxidizing environment a dilute solution of hydrogen peroxide in water was pumped using the pump P1 instead of water.
  • the feed water was heated to the required temperature using the pre heater- 1 and mixed with aqueous lignin solution pumped using pump P2 (typically at 0.5 ml/min) while catalyst solution was pumped using pump P3 (typically at 0.5 ml/min).
  • the reaction temperature was maintained across the reactor by using two independent heaters 2 and 3.
  • the set-up has been designed with flexibility to change the catalyst feed point to the top of the reactor (option- A), and middle of the reactor (option-B) depending upon the need of the experimentation.
  • the reaction product stream was cooled to room temperature and analyzed by the HPLC method using ODS C18 column.
  • the concentrations mentioned in the result tables are actual concentration of the reactants in the reactor during the reaction, while the procedure mentions the stock solution concentration.
  • the tubular reactor consists of three sections; the first section was used to heat the water to the desired temperature and made of 1 /16" diameter SS316 tube of 20 m length, while second and third sections were made from 1 ⁇ 4" diameter tube.
  • the reactor was made up of SS316 tubing of Swagelok make, having outer diameter 1 ⁇ 4", wall thickness 0.035", and total length 23.6", resulting into a tubular reactor of having a total volume of 9.85 ml.
  • the reactor was divided into two parts; upper section was having length 9.84" while lower section was of 13.78" length.
  • the volume of the upper section was 4.10 ml while that of lower section was 5.75 ml.
  • Each section was provided with independent heaters and controllers. Total three heaters were used, Heater-1 (2000 Watt) was used to preheat the water to desired temperature, while Heater-2 and Heater- 3 (both 500 Watt) were used to heat up reactor and to achieve the desired temperature profile in the reactor. Temperatures were controlled and monitored with Eurotherm PID controllers.
  • Thermocouples (Type ' ' Simplex Ml UG, 1 /16 "x 8"of SS316) were used as temperature sensor.
  • HPLC pumps (Gilson make 305 with monometric Module 815) were used to deliver the organic feed, solvent feed and catalyst feed to the reactor. HPLC pumps were also used to generate the desired pressure inside the reactor. Pressure in the reactor was controlled with the help of a manually operated Back Pressure Regulator (BPR) (Tescom make, controlled pressure 3.4-413 bar). This also helps to bring down the high pressure to atmospheric pressure for easy collection of samples.
  • BPR Back Pressure Regulator
  • a chilling unit thermostat (Haake K20 set to 50C) was used to cool the products stream to room temperature. For this purpose an external cooling jacket of SS316 was used.
  • a SS316 in-line filter assembly (0.7 ⁇ filter) was installed ahead of BPR in order to keep the Back Pressure Regulator free from any residual matter formed or precipitated during the cooling down of reaction mixture in cooling jacket area. All the residual matter which is collected over 0.7 ⁇ filter during the reaction time was taken out after the complete reaction run and dried in oven at 1 100C for 5hrs and analyzed by FT-IR. As the reactor is a continuous flow type, no separate assembly was used for collection of gaseous products formed during the reactions; hence gaseous fractions were not collected. All safety norms were taken into account for carrying out the reaction at high temperature and high pressure. Reactor sketch is shown in Figure- 1 below:
  • Lignins were procured from Aldrich. Lignosulfonic acid Na, salt Cat no. 471038, lignin sulfonated cat no. 471003 and alkali lignin cat no.370959 were used for the experiments. Lignin can also be derived from sugar cane bagasse by following standard procedure reported in the literature and used for de- polymerization to isolate the substituted aromatic phenols. Sugarcane bagasse taken from local
  • the reaction mixture was filtered using vacuum pump filtration assembly to separate the soluble hemi-cellulose from the mixture.
  • the residue left mainly containing cellulose and lignin was dried in an oven at 100 °C for 10 hours.
  • the dried residue was charged back to the autoclave and 100ml 10% sodium hydroxide solution was added.
  • the reaction mixture was again heated to 140°C for 5.
  • After completion of the reaction the reactor contents were cooled to room temperature ( 25°C).
  • the reaction mixture was discharged and filtered using vacuum pump filtration assembly.
  • the filtrate consist sodium salt of lignin and residue left behind in the filtration funnel is of cellulose. This filtrate as a whole was used for de- polymerization in a continuous reactor. A known quantity of this solution was acidified, filtered, and dried to estimate the concentration of the lignin in the solution.
  • the deionized water was pumped at 5.5 ml/min flow rate by using pump P1 and heated to high temperature (380°C) using heater-1 .
  • the pump P-2 was used to pump 11500 ppm concentration lignin solution having pH 13.5 at 0.5 ml/min flow rate, P3 for pumping water at 0.5 ml/min and was mixed with the hot water in the reactor.
  • the reaction mixture was allowed to pass over both the sections of the reactor, while maintaining 300°C temperature with the help of heaters 2 and 3.
  • the reaction pressure was maintained around 250 bar by using back pressure regulator throughout the reaction.
  • the reaction product stream was cooled to room temperature using the cooler.
  • the reaction samples were collected after reaching steady state and analyzed for the amount of monomers formed on de- polymerization of lignin. At least three samples were collected on reaching steady state and analyzed by the HPLC method.
  • the deionized water was pumped at 5.5 ml/min flow rate by using pump P-1.
  • the feed water was heated to the required temperature 380°C using the pre heater-1 and mixed with lignin solution in water having pH 13.5 pumped using pump P2 at 0.5 ml/min flow rate of 11500 ppm concentration, while the copper nitrate catalyst solution of desired concentration (6300 ppm) was pumped using pump P3 at 0.5 ml/min and allowed to mix in the cross section of the reactor.
  • the reaction mixture was allowed to pass over both the sections of the reactor, while maintaining 300°C temperature with the help of heaters 2 and 3.
  • the reaction pressure was maintained around 250 bar by using back pressure regulator throughout the reaction.
  • the reaction product stream was cooled to room temperature using the cooler.
  • the reaction samples were collected after reaching steady state and analyzed for the amount of monomers formed on de- polymerization of lignin. At least three samples were collected on reaching steady state and analyzed by the HPLC method.
  • the deionized water containing desired levels of hydrogen peroxide ( 200 ppm) was pumped at 5.5 ml/min flow rate by using pump P-1.
  • the feed water was heated to the required temperature 380°C using the pre heater-1 and mixed with lignin solution in water having pH 13.5 pumped using pump P2 at 0.5 ml/min flow rate of 1 1500 ppm concentration, while the copper nitrate catalyst solution of desired concentration (2000 ppm) was pumped using pump P3 at 0.5 ml/min and allowed to mix in the cross section of the reactor.
  • the reaction mixture was allowed to pass over both the sections of the reactor, while maintaining 300°C temperature with the help of heaters 2 and 3.
  • the reaction pressure was maintained around 250 bar by using back pressure regulator throughout the reaction.
  • the reaction product stream was cooled to room temperature using the cooler.
  • the reaction samples were collected after reaching steady state and analyzed for the amount of monomers formed on de- polymerization of lignin. At least three samples were collected on reaching steady state and analyzed by the HPLC method.
  • Set- 11 and Set-Ill The procedure reported in the Set- 1 was repeated except the concentration of copper catalyst solution was increased to desired level (6300 and 8000 ppm) and pumped using pump P-3. The averages of results of the samples collected are given in the Table-3.
  • the table shows the formation of catechol, phenol, and homovanillic acid as major products and guaicol and acetovanillone as minor products on de-polymerization of lignin.
  • the deionized water was pumped at 5.5 ml/min flow rate by using pump P1 and heated to high temperature 380°C using heater- 1 .
  • the pump P-2 was used to pump 11500 ppm concentration lignin solution having pH 13.5 at 0.5 ml/min flow rate and was mixed with the hot water in the reactor.
  • the reaction mixture was allowed to pass over the first section of the reactor, and in the second section the copper nitrate catalyst solution (6300 ppm) was fed at 0.5 ml/min flow rate by using the pump P-3.
  • the temperatures in the both the sections of the reactor were maintained at 300°C temperature with the help of heaters 2 and 3.
  • the reaction pressure was maintained around 250 bar by using back pressure regulator throughout the reaction.
  • the reaction product stream was cooled to room temperature using the cooler.
  • the reaction samples were collected after reaching steady state and analyzed for the amount of monomers formed on de-polymerization of lignin. At least three samples were collected on reaching steady state and analyzed by the HPLC method.
  • the deionized water containing desired levels of hydrogen peroxide (200 ppm) was pumped at 5.5 ml/min flow rate by using pump P-1 .
  • the pump P-2 was used to pump 11500 ppm concentration lignin solution having pH 13.5 at 0.5 ml/min flow rate and was mixed with the hot water in the reactor.
  • the reaction mixture was allowed to pass over the first section of the reactor, and in the second section the copper nitrate catalyst solution (2000 ppm) was fed at 0.5 ml/min flow rate by using the pump P-3.
  • the temperatures in the both the sections of the reactor were maintained at 300°C temperature with the help of heaters 2 and 3.
  • the reaction mixture was allowed to pass over both the sections of the reactor, while maintaining 300°C temperature with the help of heaters 2 and 3.
  • the reaction pressure was maintained around 250 bar by using back pressure regulator throughout the reaction.
  • the reaction product stream was cooled to room temperature using the cooler.
  • the reaction samples were collected after reaching steady state and analyzed for the amount of monomers formed on de-polymerization of lignin. At least three samples were collected on reaching steady state and analyzed by the HPLC method.
  • the deionized water was pumped at 5.5 ml/min flow rate by using pump P1 and heated to high temperature 420°C using heater-1 .
  • the pump P-2 was used to pump 11500 ppm concentration lignin solution having pH 13.5 at 0.5 ml/min flow rate, P3 for pumping water at 0.5 ml/min and was mixed with the hot water in the reactor.
  • the reaction mixture was allowed to pass over both the sections of the reactor, while maintaining 380°C temperature with the help of heaters 2 and 3.
  • the reaction pressure was maintained around 250 bar by using back pressure regulator throughout the reaction.
  • the reaction product stream was cooled to room temperature using the cooler.
  • the reaction samples were collected after reaching steady state and analyzed for the amount of monomers formed on de- polymerization of lignin. At least three samples were collected on reaching steady state and analyzed by the HPLC method.
  • the deionized water containing desired levels of hydrogen peroxide was pumped at 5.5 ml/min flow rate by using pump P-1 .
  • the feed water was heated to the required temperature using the pre heater-1 and mixed with lignin solution in water pumped having pH 13.5 using pump P2 at 0.5 ml/min flow rate of 11500 ppm concentration, while the copper nitrate catalyst solution 6300 ppm of desired concentration was pumped using pump P3 at 0.5 ml/min and allowed to mix in the cross section of the reactor.
  • the reaction mixture was allowed. to pass over both the sections of the reactor, while maintaining 380°C temperature with the help of heaters 2 and 3.
  • the reaction pressure was maintained around 250 bar by using back pressure regulator throughout the reaction.
  • the reaction product stream was cooled to room temperature using the cooler.
  • the reaction samples were collected after reaching steady state and analyzed for the amount of monomers formed on de- polymerization of lignin. At least three samples were collected on reaching steady state and analyzed by the HPLC method.
  • Set-ll and Set-Ill The procedure reported in the Set-I was repeated except the concentration of peroxide solution was increased to desired level (200 and 425 ppm) and pumped using pump P-3. The averages of results of the samples collected are given in the Table-7.
  • the table shows the formation of catechol, phenol, and homovanillic acid as major products and guaicol, syringic acid and acetovanillone as minor products on de- polymerization of lignin.
  • the deionized water containing desired levels of hydrogen peroxide ( 200 ppm) was pumped at 5.5 ml/min flow rate by using pump P-1.
  • the feed water was heated to the required temperature (380°C) using the pre heater- 1 and mixed with lignin solution having pH 1 1 , pumped using pump P2 at 0.5 ml/min flow rate of 11500 ppm concentration, while the copper nitrate catalyst solution of desired concentration (6300 ppm) was pumped using pump P3 at 0.5 ml/min and allowed to mix in the cross section of the reactor.
  • the reaction mixture was allowed to pass over both the sections of the reactor, while maintaining 300°C temperature with the help of heaters 2 and 3.
  • the reaction pressure was maintained around 250 bar by using back pressure regulator throughout the reaction.
  • the reaction product stream was cooled to room temperature using the cooler.
  • the reaction samples were collected after reaching steady state and analyzed for the amount of monomers formed on de- polymerization of lignin. At least three samples were collected on reaching steady state and analyzed by the HPLC method.
  • Set-I I The procedure reported in the Set-I was repeated except that the lignin solution having pH 13.5 was used and pumped using pump P-2.
  • the averages of results of the samples collected are given in the Table-8.
  • the table shows the formation of catechol, phenol, homovanillic acid and acetovanillone as major products at 13.5 pH compared to pH 10. It has been observed that when the de- polymerization of lignin is carried out at pH 10 the total monomer yield is around 3% which increases to 25% at higher pH of 13.5.
  • Table-1 Product distribution of sugar cane bagasse lignin under subcritical conditions of water and variable oxidizing environment
  • Table-2 Product distribution of sugar cane bagasse lignin under subcritical conditions of water, catalytic and variable oxidizing environment with catalyst feed at top of the reactor
  • Reaction conditions Lignin cone. 5x10 3 moles/lit, Catalyst cone. 1 .96x10 "3 moles/lit, Temperature 300°C, Pressure 250 bar, Residence time 65 sec, Catalyst feed from top of the reactor
  • Table-3 Product distribution of sugar cane bagasse lignin under subcritical conditions of water, oxidizing and variable catalytic environment with catalyst feed at top of the reactor
  • Reaction conditions Lignin cone. 5x10° moles/lit, Peroxide cone. 5x10 "3 moles/lit, Temperature 300°C, Pressure 250 bar, Residence time 65 sec, Catalyst feed from top of the reactor.
  • Table-4 Product distribution of sugar cane bagasse lignin under subcritical conditions of water, catalytic and variable oxidizing environment with catalyst feed at middle of the reactor
  • Reaction conditions Lignin cone. 5x10 "J moles/lit, Catalyst Cu cone. 1 .96x10° moles/lit, Temperature 300°C , Pressure 300 bar, Residence time 65 sec, catalyst feed point middle of the reactor
  • Tabie-5 Product distribution of sugar cane bagasse lignin under subcritical conditions of water, oxidizing and variable catalytic environment with catalyst feed at middle of the reactor Sr Compound % Yield
  • Reaction conditions Lignin cone. 5x10 3 moles/ lit, Temperature 380°C, Pressure 250 bar, Residence time 40 sec.
  • Table-7 Product distribution of sugar cane bagasse lignin under supercritical conditions of water, catalytic and variable oxidizing environment with catalyst feed at top of the reactor
  • Table-8 Product distribution of sugar cane bagasse lignin under subcritical conditions of water using copper catalyst, oxidizing environment and at different pH
  • reaction conditions can be tuned to manipulate the selectivity to various products e.
  • the process avoids char formation

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Abstract

La présente invention porte sur un procédé de dépolymérisation de lignine en deux étapes comprenant une hydrolyse et une oxydation catalytique des oligomères dans un réacteur tubulaire avec un rendement élevé dans des conditions hydrothermiques.
PCT/IN2013/000660 2012-10-30 2013-10-30 Procédé en continu pour la dépolymérisation de lignine en produits chimiques industriellement utiles WO2014068590A1 (fr)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
RU2671161C1 (ru) * 2017-11-27 2018-10-29 Федеральное государственное бюджетное научное учреждение "Федеральный исследовательский центр "Красноярский научный центр Сибирского отделения Российской академии наук" (ФИЦ КНЦ СО РАН, КНЦ СО РАН) Способ химической переработки древесины
WO2023092241A1 (fr) * 2021-11-29 2023-06-01 Silicycle Inc. Production de fleurs de liginine et leurs utilisations
WO2023244264A3 (fr) * 2021-12-09 2024-03-21 Wisconsin Alumni Research Foundation Dépolymérisation aérobie à base de flux de lignine

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WO2023244264A3 (fr) * 2021-12-09 2024-03-21 Wisconsin Alumni Research Foundation Dépolymérisation aérobie à base de flux de lignine

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