CN111943814B - Method for preparing phenol by catalytic conversion of lignin by high-silicon molecular sieve - Google Patents

Method for preparing phenol by catalytic conversion of lignin by high-silicon molecular sieve Download PDF

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CN111943814B
CN111943814B CN202010933889.4A CN202010933889A CN111943814B CN 111943814 B CN111943814 B CN 111943814B CN 202010933889 A CN202010933889 A CN 202010933889A CN 111943814 B CN111943814 B CN 111943814B
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lignin
phenol
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CN111943814A (en
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孟庆磊
严江
韩布兴
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Institute of Chemistry CAS
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
    • C07C37/50—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions decreasing the number of carbon atoms
    • C07C37/52—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions decreasing the number of carbon atoms by splitting polyaromatic compounds, e.g. polyphenolalkanes
    • C07C37/54—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions decreasing the number of carbon atoms by splitting polyaromatic compounds, e.g. polyphenolalkanes by hydrolysis of lignin or sulfite waste liquor
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
    • B01J29/084—Y-type faujasite
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08H—DERIVATIVES OF NATURAL MACROMOLECULAR COMPOUNDS
    • C08H6/00—Macromolecular compounds derived from lignin, e.g. tannins, humic acids
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    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

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Abstract

The invention discloses a method for preparing phenol by catalytic conversion of lignin by a high-silicon molecular sieve, belonging to the field of preparation of high-added-value chemicals by catalytic conversion of biomass. The method of the invention comprises the following steps: under inert atmosphere, high-silicon molecular sieve is used as catalyst to catalyze and convert lignin into phenol. The catalyst system is simple, green and environment-friendly, the lignin is cheap and easy to obtain, and the product is mainly phenol, so that the possibility is provided for large-scale catalytic conversion and utilization of the lignin.

Description

Method for preparing phenol by catalytic conversion of lignin by high-silicon molecular sieve
Technical Field
The invention relates to the field of preparing high value-added chemicals by catalytic conversion of biomass, in particular to a method for preparing phenol by catalytic conversion of lignin by a high-silicon molecular sieve.
Background
In modern industry, phenol is an important basic chemical raw material, is used for producing important chemical raw materials such as bisphenol A, phenolic resin, caprolactam, alkylphenol, salicylic acid, cyclohexanone and the like, can also be used as a solvent and a disinfectant, and has wide application in the fields of chemical fibers, plastics, medicines, pesticides, spices, dyes, coatings, oil refining industry and the like. In 2018, the consumption of phenol in China reaches 236 ten thousand tons, and the growth trend is kept. At present, the cumyl benzene method is the mainstream process route of phenol industrial production, but the process route is complex, the intermediate product cumyl hydroperoxide is a dangerous explosive substance, almost equimolar acetone by-product is generated while the main product phenol is obtained, the development requirement of green chemistry is not met, and the raw materials of the process, namely benzene and propylene, are from non-renewable fossil energy sources.
The lignin is prepared from p-hydroxyphenylpropane (H) and guaiacyl propane (G)) The natural polymer formed by connecting the three structural units of syringyl propane (S) through ether bonds and carbon-carbon bonds contains a large number of hydroxyl and methoxyl functional groups, is widely present in nature, and is an aromatic renewable energy source with great potential. Many studies have been conducted on the cleavage of lignin ether linkages, particularly between β -O-4 linkages, but cleavage of only the β -O-4 linkage can yield alkylphenol products with a much lower range of applications than phenol. Thus, if the beta-O-4 ether bond and C can be selectively cleavedsp2-Csp3The carbon-carbon bond can obtain the non-alkylphenol product which takes phenol as the main component, thereby not only conforming to the concept of green chemistry, but also being beneficial to widening the source of aromatic compounds and optimizing the energy structure. However, the beta-O-4 ether linkage and C within and between the lignin building blockssp2-Csp3The stability of carbon-carbon bonds and the complexity of the whole structure of lignin greatly improve the difficulty of catalytic conversion of lignin. At present, the common catalytic conversion methods such as hydrogenation, oxidation, hydrolysis, thermal cracking and the like can only convert lignin into lignin oil with complex components, most of phenolic monomers are alkylphenol connected with alkyl, the application value is low, and the separation is difficult. Therefore, it would be of great practical value to obtain phenol-based non-alkylphenol compounds from lignin with high selectivity.
Disclosure of Invention
The invention provides a method for preparing phenol by catalyzing and converting lignin with a high-silicon molecular sieve.
The method for preparing phenol by catalyzing and converting lignin by using the high-silicon molecular sieve comprises the following steps: under inert atmosphere, high-silicon molecular sieve is used as catalyst to catalyze and convert lignin into phenol.
In the above method, the inert atmosphere may be specifically an argon and/or nitrogen atmosphere.
In the method, the high-silicon molecular sieve is an HY molecular sieve and/or a ZSM-5 molecular sieve;
specifically, the HY molecular sieve has an atomic ratio of Si to Al of 10-50; specifically, the concentration can be 15-40; more specifically 15, 30 or 40; the atomic ratio of Si to Al of the ZSM-5 molecular sieve is 100-500; specifically 235.
The mass of the high-silicon molecular sieve is 10-200% of that of the lignin, and specifically can be 60-150%.
In the above method, the catalytic conversion reaction is carried out in a solvent; specifically, the solvent is water; more specifically, deionized water, distilled water and/or tap water.
The mass ratio of the water to the lignin is 5-50: 1; specifically, the ratio of the total amount of the components is 10-20: 1.
In the above method, the lignin is at least one of lignin extracted from poplar, pine, willow, cedar and moso bamboo.
Extracting the lignin by using an organic solvent; specifically, the organic solvent is at least one of acetone, butanone, ethanol, isopropanol and dioxane.
Specifically, the extraction method of the lignin comprises the following steps: hydrolyzing wood powder with high-temperature water or acid to obtain organic solvent lignin; the wood powder is at least one of poplar, pine, willow, cedar and moso bamboo.
In the extraction method of the lignin, the volume ratio of the organic solvent to the water is 1-9: 1; specifically, the ratio can be 2-6: 1; more specifically, 2 to 3: 1; the mass ratio of the total volume of the organic solvent and the water to the wood powder is 5-15 ml: 1g of a compound; specifically, the volume of the solution can be 6-12 ml: 1g of a compound; more specifically, 6-10 ml: 1g of the total weight of the composition.
In the method for extracting lignin, the acid in the acid hydrolysis is hydrochloric acid; the mass ratio of the hydrochloric acid to the wood powder is 0-1: 1; specifically, the ratio of the amount of the organic compound to the amount of the organic compound is 0.01 to 0.50: 1; more specifically, the ratio of the amount of the surfactant to the amount of the surfactant is 0.01 to 0.1: 1.
In the method for extracting the lignin, the temperature of the high-temperature water hydrolysis or acid hydrolysis is 80-200 ℃; the temperature can be between 90 and 180 ℃; the time is 0.5 h-6 h, specifically 1 h-2 h.
The high-temperature water hydrolysis or acid hydrolysis is carried out under the condition of stirring; specifically, the stirring speed is 400rpm to 1600 rpm.
In the method for extracting lignin, the high-temperature water hydrolysis or acid hydrolysis is carried out in an inert atmosphere; specifically, the inert atmosphere is nitrogen and/or argon; in the inert atmosphere, the pressure of the inert gas is 0.1MPa to 2MPa, and specifically 0.5MPa to 1 MPa.
In the above method for extracting lignin, the method further comprises the following steps: (1) filtering after hydrolysis to obtain filtrate, and concentrating the filtrate; (2) adding the concentrated solution into water, and filtering to obtain precipitate; (3) freeze drying the precipitate to remove water; (4) dissolving the dried precipitate in acetone/methanol solution, and adding into anhydrous ether; (5) filtering to obtain a precipitate, and then drying in vacuum to obtain the organic solvent lignin.
In the step (4), the volumes of acetone and methanol are 5: 1-10: 1, specifically 9: 1.
in the step (5), the temperature of vacuum drying is 40-80 ℃; specifically, it may be 60 ℃.
In the above method, the conditions of the catalytic conversion reaction are as follows: the pressure of the inert gas is 0.1MPa to 10 MPa; specifically, the pressure can be 0.5MPa to 1 MPa; the temperature is 100-300 ℃, and can be 150-250 ℃; the time is 0.5 to 12 hours, specifically 3 to 8 hours, more specifically 3 to 6 hours.
In the above method, the catalytic conversion reaction is carried out under stirring conditions; specifically, the stirring speed is 400rpm to 1000 rpm.
The method provided by the invention has the advantages that the catalyst system is simple, green and environment-friendly, the lignin is cheap and easy to obtain, the product is mainly phenol, and the possibility is provided for large-scale catalytic conversion and utilization of the lignin.
Drawings
Fig. 1 shows a two-dimensional nuclear magnetic resonance spectrum and a corresponding structure of the poplar organic solvent lignin separated and extracted in example 1 of the present invention.
FIG. 2 is a gas chromatogram of the product of example 1 according to the present invention.
FIG. 3 is a mass spectrum of the product of example 1 of the present invention.
FIG. 4 is a mass spectrum of the product of example 1 of the present invention.
FIG. 5 is a mass spectrum of the product of example 1 of the present invention.
FIG. 6 is a mass spectrum of the product of example 1 of the present invention.
Fig. 7 shows the two-dimensional nmr spectrum and the corresponding structure of the pine organosolv lignin isolated and extracted in example 6 of the present invention.
Detailed Description
The present invention is described in further detail below with reference to specific embodiments, which are given for the purpose of illustration only and are not intended to limit the scope of the invention.
The experimental procedures in the following examples are conventional unless otherwise specified.
Materials, reagents and the like used in the following examples are commercially available unless otherwise specified.
The HY molecular sieves in the examples below were obtained from Afa Aesar (Alfa Aesar); beta molecular sieves and ZSM-5 molecular sieves were purchased from Tianjin Ministry of catalysis, Inc.
Example 1
(1) Preparation of poplar organic solvent lignin raw material
70g of poplar powder, 490mL of acetone and 210mL of deionized water are added into a 1000mL acid and alkali resistant high-pressure reaction kettle, and oxygen in the kettle is replaced by nitrogen. The nitrogen in the kettle was pressurized to 0.5MPa, the reaction kettle was heated to 160 ℃ with stirring at 600rpm, and the temperature was maintained for 1 h. Then cooling to room temperature, filtering, and washing filter residue by using 90% by volume of acetone aqueous solution. Mixing filtrates, concentrating, slowly adding the concentrated solution dropwise into 2000ml of deionized water, filtering the precipitate, freeze-drying to remove water, dissolving in 100ml of acetone/methanol (volume ratio of 9:1), slowly adding dropwise into 1000ml of anhydrous ether, filtering the precipitate, and finally vacuum-drying at 60 deg.C to obtain poplar organic solvent lignin. As can be seen from the two-dimensional nuclear magnetic spectrum (figure 1) of the poplar organosolv lignin extracted and separated by the method, a large amount of alpha-C hydroxyl, gamma-C hydroxyl and beta-O-4 ether bond structures (A) exist in the poplar organosolv lignin, and a structural unit B, C for polycondensation reaction also exists; H. g, S all three building blocks are present in the lignin.
(2) Reaction for preparing phenol by converting lignin
Adding 0.4g of poplar organic solvent lignin, 0.4g of HY molecular sieve (the atomic ratio of Si to Al is 30) and 5mL of deionized water into a 20mL polytetrafluoroethylene lined reaction kettle, sealing the autoclave, replacing the air in the kettle with argon, filling the argon to 0.5MPa, stirring at 800rpm, heating to 200 ℃, and maintaining for 4 hours. After the reaction is finished, the reaction mixture is rapidly cooled to room temperature, the reaction mixture is subjected to centrifugal separation after air release, liquid is extracted by ethyl acetate and then is analyzed by a gas chromatography-mass spectrometer and a gas chromatograph, and the ratio of the mass of the phenol to the mass of the lignin is the phenol yield.
(3) After the reaction, the product was mainly phenol as seen by GC-MS and GC analysis, and the yield was 10.9% by weight.
FIG. 2 is a gas chromatogram of the product; FIGS. 3-6 are mass spectra of the product.
Example 2
(1) Preparation of poplar organic solvent lignin raw material
70g of poplar powder, 490mL of acetone and 210mL of deionized water are added into a 1000mL acid and alkali resistant high-pressure reaction kettle, and oxygen in the kettle is replaced by nitrogen. The nitrogen in the kettle was pressurized to 0.5MPa, the reaction kettle was heated to 160 ℃ with stirring at 600rpm, and the temperature was maintained for 1 h. Then cooling to room temperature, filtering, and washing filter residue by using 90% by volume of acetone aqueous solution. Mixing filtrates, concentrating, slowly adding the concentrated solution dropwise into 2000ml of deionized water, filtering the precipitate, freeze-drying to remove water, dissolving in 100ml of acetone/methanol (volume ratio of 9:1), slowly adding dropwise into 1000ml of anhydrous ether, filtering the precipitate, and finally vacuum-drying at 60 deg.C to obtain poplar organic solvent lignin. Extracting multiple batches of poplar organic solvent lignin according to the same method, and mixing for later use.
(2) Reaction for preparing phenol by lignin conversion
Adding 50.0g of poplar organic solvent lignin, 50.0g of HY molecular sieve (the atomic ratio of Si to Al is 30) and 600mL of deionized water into a 1000mL Hastelloy high-pressure reaction kettle, sealing the high-pressure reaction kettle, replacing the air in the kettle with argon, filling the argon to 0.5MPa, stirring at the speed of 800rpm, and heating to 200 ℃ within 40min and maintaining for 3 h. After the reaction is finished, the reaction mixture is rapidly cooled to room temperature, the reaction mixture is subjected to centrifugal separation after air release, liquid is extracted by ethyl acetate, then ethyl acetate is removed through reduced pressure distillation, the obtained solid is separated by a silica gel column, then benzene is used for recrystallization to obtain phenol crystals, and the ratio of the mass of the obtained phenol to the mass of the lignin is the yield of the pure phenol of the amplification reaction.
(3) After the reaction, the product was phenol as shown by GC-MS and GC analysis, and the pure product yield was 8.2 wt%.
Example 3
(1) Preparation of poplar organic solvent lignin raw material
70g of poplar powder, 500mL of dioxane, 200mL of deionized water and 7g of hydrochloric acid (the mass percentage concentration is 37%) are added into a 1000mL acid-alkali-resistant high-pressure reaction kettle, and oxygen in the kettle is replaced by nitrogen. The nitrogen in the kettle is pressurized to 1MPa, the reaction kettle is heated to 100 ℃ under the stirring of 800rpm, and the temperature is kept for 1 h. Then cooling to room temperature, filtering, and washing filter residue by using 90% by volume of acetone aqueous solution. Mixing filtrates, concentrating, slowly adding the concentrated solution dropwise into 2000ml of deionized water, filtering the precipitate, freeze-drying to remove water, dissolving in 100ml of acetone/methanol (volume ratio of 9:1), slowly adding dropwise into 1000ml of anhydrous ether, filtering the precipitate, and finally vacuum-drying at 60 deg.C to obtain poplar organic solvent lignin.
(2) Reaction for preparing phenol by lignin conversion
Adding 0.4g of poplar organic solvent lignin, 0.6g of ZSM-5 molecular sieve (the atomic ratio of Si to Al is 235) and 6mL of deionized water into a 20mL polytetrafluoroethylene lined reaction kettle, sealing the reaction kettle, replacing the air in the kettle with argon, filling the argon to 0.5MPa, stirring at the speed of 600rpm, heating to 210 ℃, and maintaining for 4 hours. After the reaction is finished, the reaction mixture is rapidly cooled to room temperature, the reaction mixture is subjected to centrifugal separation after air release, liquid is extracted by ethyl acetate and then is analyzed by a gas chromatography-mass spectrometer and a gas chromatograph, and the ratio of the mass of the phenol to the mass of the lignin is the phenol yield.
(3) After the reaction, the product was mainly phenol as seen by GC-MS and GC analysis, and the yield was 4.8% by weight.
Example 4
(1) Preparation of poplar organic solvent lignin raw material
70g of poplar powder, 560mL of ethanol and 240mL of deionized water are added into a 1000mL acid and alkali resistant high-pressure reaction kettle, and the oxygen in the kettle is replaced by nitrogen. The nitrogen in the kettle was pressurized to 1MPa, the reaction kettle was heated to 150 ℃ with stirring at 600rpm, and the temperature was maintained for 1 h. Then cooling to room temperature, filtering, and washing filter residue by using ethanol water solution with the volume fraction of 90%. Mixing filtrates, concentrating, slowly adding the concentrated solution dropwise into 2000ml of deionized water, filtering the precipitate, freeze-drying to remove water, dissolving in 100ml of acetone/methanol (volume ratio of 9:1), slowly adding dropwise into 1000ml of anhydrous ether, filtering the precipitate, and finally vacuum-drying at 60 deg.C to obtain poplar organic solvent lignin.
(2) And (4) converting lignin to prepare phenol.
Adding 0.4g of poplar organic lignin, 0.6g of HY molecular sieve (the atomic ratio of Si to Al is 30) and 6mL of deionized water into a 20mL polytetrafluoroethylene-lined reaction kettle, sealing the autoclave, replacing the air in the kettle with argon, filling the argon to 0.5MPa, stirring at 800rpm, heating to 210 ℃, and maintaining for 4 hours. After the reaction is finished, the reaction mixture is rapidly cooled to room temperature, the reaction mixture is subjected to centrifugal separation after air release, liquid is extracted by ethyl acetate and then is analyzed by a gas chromatography-mass spectrometer and a gas chromatograph, and the ratio of the mass of the phenol to the mass of the lignin is the phenol yield.
(3) After the reaction, the product was mainly phenol as seen by GC-MS and GC analysis, and the yield was 7.4% by weight.
Example 5
(1) Preparation of poplar organic solvent lignin raw material
70g of poplar powder, 500mL of dioxane, 200mL of deionized water and 3.5g of hydrochloric acid (the mass percentage concentration is 37%) are added into a 1000mL acid-alkali-resistant high-pressure reaction kettle, and nitrogen is used for replacing oxygen in the kettle. The nitrogen in the kettle is pressurized to 1MPa, the reaction kettle is heated to 110 ℃ under the stirring of 800rpm, and the temperature is kept for 1 h. Then cooling to room temperature, filtering, and washing filter residue by using 90% by volume of acetone aqueous solution. Mixing filtrates, concentrating, slowly adding the concentrated solution dropwise into 2000ml of deionized water, filtering the precipitate, freeze-drying to remove water, dissolving in 100ml of acetone/methanol (volume ratio of 9:1), slowly adding dropwise into 1000ml of anhydrous ether, filtering the precipitate, and finally vacuum-drying at 60 deg.C to obtain poplar organic solvent lignin.
(2) Reaction for preparing phenol by lignin conversion
Adding 0.4g of poplar organic solvent lignin, 0.4g of HY molecular sieve (the atomic ratio of Si to Al is 15) and 8mL of deionized water into a 20mL polytetrafluoroethylene lined reaction kettle, sealing the autoclave, replacing the air in the kettle with argon, filling the argon to 0.5MPa, stirring at 1000rpm, heating to 210 ℃, and maintaining for 4 hours. After the reaction is finished, the reaction mixture is rapidly cooled to room temperature, the reaction mixture is subjected to centrifugal separation after air release, liquid is extracted by ethyl acetate and then is analyzed by a gas chromatography-mass spectrometer and a gas chromatograph, and the ratio of the mass of the phenol to the mass of the lignin is the phenol yield.
(3) After the reaction, the product was mainly phenol as seen by GC-MS and GC analysis, and the yield was 6.5% by weight.
Example 6
(1) Preparation of pine wood organic solvent lignin raw material
70g of pine wood powder, 490mL of acetone and 210mL of deionized water are added into a 1000mL acid and alkali resistant high pressure reaction kettle, and oxygen in the kettle is replaced by nitrogen. The nitrogen in the kettle was pressurized to 0.5MPa, the reaction kettle was heated to 160 ℃ with stirring at 600rpm, and the temperature was maintained for 1 h. Then cooling to room temperature, filtering, and washing filter residue by using 90% by volume of acetone aqueous solution. Mixing filtrates, concentrating, slowly adding the concentrated solution dropwise into 2000ml of deionized water, filtering the precipitate, freeze drying to remove water, dissolving in 100ml of acetone/methanol (volume ratio of 9:1), slowly adding dropwise into 1000ml of anhydrous ether, filtering the precipitate, and vacuum drying at 60 deg.C to obtain pine wood organic solvent lignin. As can be seen from the two-dimensional nuclear magnetic spectrum (figure 7) of the pine organosolv lignin extracted and separated by the method, a large amount of alpha-C hydroxyl, gamma-C hydroxyl and beta-O-4 ether bond structures (A) exist in the pine organosolv lignin, and a structural unit B, C for polycondensation reaction also exists; H. g, S all three building blocks are present in the lignin.
(2) Reaction for preparing phenol by lignin conversion
Adding 0.4g of pine organic solvent lignin, 0.4g of HY molecular sieve (the atomic ratio of Si to Al is 30) and 8mL of deionized water into a 20mL polytetrafluoroethylene lined reaction kettle, sealing the autoclave, replacing the air in the kettle with argon, filling the argon to 0.5MPa, stirring at 800rpm, heating to 200 ℃, and maintaining for 6 hours. After the reaction is finished, the reaction mixture is rapidly cooled to room temperature, the reaction mixture is subjected to centrifugal separation after air release, liquid is extracted by ethyl acetate and then is analyzed by a gas chromatography-mass spectrometer and a gas chromatograph, and the ratio of the mass of the phenol to the mass of the lignin is the phenol yield.
(3) After the reaction, the product was mainly phenol as seen by GC-MS and GC analysis, and the yield was 9.1% by weight.
Example 7
(1) Preparation of pine wood organic solvent lignin raw material
70g of pine wood powder, 600mL of acetone and 100mL of deionized water are added into a 1000mL acid and alkali resistant high-pressure reaction kettle, and oxygen in the kettle is replaced by nitrogen. The nitrogen in the kettle is pressurized to 0.5MPa, the stirring speed is 800rpm, the reaction kettle is heated to 170 ℃ under the stirring of 800rpm, and the temperature is kept constant for 2 hours. Then cooling to room temperature, filtering, and washing filter residue by using 90% by volume of acetone aqueous solution. Mixing filtrates, concentrating, slowly adding the concentrated solution dropwise into 2000ml of deionized water, filtering the precipitate, freeze drying to remove water, dissolving in 100ml of acetone/methanol (volume ratio of 9:1), slowly adding dropwise into 1000ml of anhydrous ether, filtering the precipitate, and vacuum drying at 60 deg.C to obtain pine wood organic solvent lignin.
(2) Reaction for preparing phenol by lignin conversion
Adding 0.4g of pine organic solvent lignin, 0.6g of HY molecular sieve (the atomic ratio of Si to Al is 40) and 8mL of deionized water into a 20mL polytetrafluoroethylene lined reaction kettle, sealing the reaction kettle, replacing the air in the kettle with argon, filling the argon to 0.5MPa, heating to 180 ℃, and maintaining for 8 hours. After the reaction is finished, the reaction mixture is rapidly cooled to room temperature, the reaction mixture is subjected to centrifugal separation after air release, liquid is extracted by ethyl acetate and then is analyzed by a gas chromatography-mass spectrometer and a gas chromatograph, and the ratio of the mass of the phenol to the mass of the lignin is the phenol yield.
(3) After the reaction, the product was mainly phenol as seen by GC-MS and GC analysis, and the yield was 6.4% by weight.
Example 8
(1) Preparation of pine wood organic solvent lignin raw material
70g of pine wood powder, 560mL of ethanol and 240mL of deionized water are added into a 1000mL acid and alkali resistant high-pressure reaction kettle, and oxygen in the kettle is replaced by nitrogen. The nitrogen in the kettle was pressurized to 1MPa, the reaction kettle was heated to 150 ℃ with stirring at 600rpm, and the temperature was maintained for 1 h. Then cooling to room temperature, filtering, and washing filter residue by using ethanol water solution with the volume fraction of 90%. Mixing filtrates, concentrating, slowly adding the concentrated solution dropwise into 2000ml of deionized water, filtering the precipitate, freeze drying to remove water, dissolving in 100ml of acetone/methanol (volume ratio of 9:1), slowly adding dropwise into 1000ml of anhydrous ether, filtering the precipitate, and vacuum drying at 60 deg.C to obtain pine wood organic solvent lignin.
(2) Reaction for preparing phenol by lignin conversion
Adding 0.4g of pine organic solvent lignin, 0.4g of ZSM-5 molecular sieve (the atomic ratio of Si to Al is 235) and 8mL of deionized water into a 20mL polytetrafluoroethylene lined reaction kettle, sealing the reaction kettle, replacing the air in the kettle with argon, filling the argon to 0.5MPa, stirring at the speed of 1000rpm, heating to 210 ℃, and maintaining for 6 hours. After the reaction is finished, the reaction mixture is rapidly cooled to room temperature, the reaction mixture is subjected to centrifugal separation after air release, liquid is extracted by ethyl acetate and then is analyzed by a gas chromatography-mass spectrometer and a gas chromatograph, and the ratio of the mass of the phenol to the mass of the lignin is the phenol yield.
(3) After the reaction, the product was mainly phenol as seen by GC-MS and GC analysis, and the yield was 4.8% by weight.
Example 9
(1) Preparation of pine wood organic solvent lignin raw material
70g of pine wood powder, 500mL of dioxane, 200mL of deionized water and 10g of hydrochloric acid (the mass percentage concentration is 37%) are added into a 1000mL acid-alkali-resistant high-pressure reaction kettle, and nitrogen is used for replacing oxygen in the kettle. The nitrogen in the kettle is pressurized to 1MPa, the reaction kettle is heated to 100 ℃ under the stirring of 600rpm, and the temperature is kept for 1 h. Then cooling to room temperature, filtering, and washing filter residue by using 90% by volume of acetone aqueous solution. Mixing filtrates, concentrating, slowly adding the concentrated solution dropwise into 2000ml of deionized water, filtering the precipitate, freeze drying to remove water, dissolving in 100ml of acetone/methanol (volume ratio of 9:1), slowly adding dropwise into 1000ml of anhydrous ether, filtering the precipitate, and vacuum drying at 60 deg.C to obtain pine wood organic solvent lignin.
(2) Reaction for preparing phenol by lignin conversion
Adding 0.4g of pine organic solvent lignin, 0.4g of HY molecular sieve (the atomic ratio of Si to Al is 30) and 6mL of deionized water into a 20mL polytetrafluoroethylene lined reaction kettle, sealing the autoclave, replacing the air in the kettle with argon, filling the argon to 0.5MPa, stirring at 800rpm, heating to 200 ℃, and maintaining for 4 hours. After the reaction is finished, the reaction mixture is rapidly cooled to room temperature, the reaction mixture is subjected to centrifugal separation after air release, liquid is extracted by ethyl acetate and then is analyzed by a gas chromatography-mass spectrometer and a gas chromatograph, and the ratio of the mass of the phenol to the mass of the lignin is the phenol yield.
(3) After the reaction, the product was mainly phenol as seen by GC-MS and GC analysis, and the yield was 6.2% by weight.
Example 10
(1) Preparation of willow organic solvent lignin raw material
70g of willow powder, 490mL of acetone and 210mL of deionized water are added into a 1000mL acid and alkali resistant high-pressure reaction kettle, and the oxygen in the kettle is replaced by nitrogen. The nitrogen in the kettle was pressurized to 0.5MPa, the reaction kettle was heated to 160 ℃ with stirring at 600rpm, and the temperature was maintained for 1 h. Then cooling to room temperature, filtering, and washing filter residue by using 90% by volume of acetone aqueous solution. Mixing filtrates, concentrating, slowly adding the concentrated solution dropwise into 2000ml of deionized water, filtering the precipitate, freeze drying to remove water, dissolving in 100ml of acetone/methanol (volume ratio of 9:1), slowly adding dropwise into 1000ml of anhydrous ether, filtering the precipitate, and vacuum drying at 60 deg.C to obtain willow organic solvent lignin.
(2) Reaction for preparing phenol by lignin conversion
Adding 0.4g of willow organic solvent lignin, 0.6g of HY molecular sieve (the atomic ratio of Si to Al is 40) and 6mL of deionized water into a 20mL polytetrafluoroethylene-lined reaction kettle, sealing the autoclave, replacing the air in the kettle with argon, filling the argon to 0.5MPa, stirring at 800rpm, heating to 190 ℃ and maintaining for 6 hours. After the reaction is finished, the reaction mixture is rapidly cooled to room temperature, the reaction mixture is subjected to centrifugal separation after air release, liquid is extracted by ethyl acetate and then is analyzed by a gas chromatography-mass spectrometer and a gas chromatograph, and the ratio of the mass of the phenol to the mass of the lignin is the phenol yield.
(3) After the reaction, the product was mainly phenol as seen by GC-MS and GC analysis, and the yield was 5.4% by weight.
Example 11
(1) Preparation of willow organic solvent lignin raw material
70g of willow powder, 560mL of butanone and 240mL of deionized water are added into a 1000mL of acid-alkali-resistant high-pressure reaction kettle, and the oxygen in the kettle is replaced by nitrogen. The nitrogen in the kettle was pressurized to 1MPa, the reaction kettle was heated to 150 ℃ with stirring at 600rpm, and the temperature was maintained for 1 h. Then cooling to room temperature, filtering, and washing filter residue by using ethanol water solution with the volume fraction of 90%. Mixing filtrates, concentrating, slowly adding the concentrated solution dropwise into 2000ml of deionized water, filtering the precipitate, freeze drying to remove water, dissolving in 100ml of acetone/methanol (volume ratio of 9:1), slowly adding dropwise into 1000ml of anhydrous ether, filtering the precipitate, and vacuum drying at 60 deg.C to obtain willow organic solvent lignin.
(2) Reaction for preparing phenol by lignin conversion
Adding 0.4g of willow organic solvent lignin, 0.6g of HY molecular sieve (the atomic ratio of Si to Al is 40) and 8mL of deionized water into a 20mL polytetrafluoroethylene-lined reaction kettle, sealing the reaction kettle, replacing the air in the kettle with argon, filling the argon to 0.5MPa, heating to 180 ℃, and maintaining for 8 hours. After the reaction is finished, the reaction mixture is rapidly cooled to room temperature, the reaction mixture is subjected to centrifugal separation after air release, liquid is extracted by ethyl acetate and then is analyzed by a gas chromatography-mass spectrometer and a gas chromatograph, and the ratio of the mass of the phenol to the mass of the lignin is the phenol yield.
(3) After the reaction, the product was mainly phenol as seen by GC-MS and GC analysis, and the yield was 5.9% by weight.
Example 12
(1) Preparation of willow organic solvent lignin raw material
70g of willow powder, 500mL of dioxane, 200mL of deionized water and 3.5g of hydrochloric acid (the mass percentage concentration is 37%) are added into a 1000mL acid-alkali-resistant high-pressure reaction kettle, and oxygen in the kettle is replaced by nitrogen. The nitrogen in the kettle is pressurized to 1MPa, the reaction kettle is heated to 110 ℃ under the stirring of 800rpm, and the temperature is kept for 1 h. Then cooling to room temperature, filtering, and washing filter residue by using 90% by volume of acetone aqueous solution. Mixing filtrates, concentrating, slowly adding the concentrated solution dropwise into 2000ml of deionized water, filtering the precipitate, freeze drying to remove water, dissolving in 100ml of acetone/methanol (volume ratio of 9:1), slowly adding dropwise into 1000ml of anhydrous ether, filtering the precipitate, and vacuum drying at 60 deg.C to obtain willow organic solvent lignin.
(2) Reaction for preparing phenol by lignin conversion
Adding 0.4g of willow organic solvent lignin, 0.4g of ZSM-5 molecular sieve (the atomic ratio of Si to Al is 235) and 8mL of deionized water into a 20mL polytetrafluoroethylene-lined reaction kettle, sealing the reaction kettle, replacing the air in the kettle with argon, filling the argon to 0.5MPa, stirring at the speed of 1000rpm, heating to 210 ℃, and maintaining for 6 hours. After the reaction is finished, the reaction mixture is rapidly cooled to room temperature, the reaction mixture is subjected to centrifugal separation after air release, liquid is extracted by ethyl acetate and then is analyzed by a gas chromatography-mass spectrometer and a gas chromatograph, and the ratio of the mass of the phenol to the mass of the lignin is the phenol yield.
(3) After the reaction, the product was mainly phenol as seen by GC-MS and GC analysis, and the yield was 4.8% by weight.
Example 13
(1) Preparation of cedar organic solvent lignin raw material
70g of cypress powder, 560mL of ethanol and 240mL of deionized water are added into a 1000mL acid and alkali resistant high-pressure reaction kettle, and the oxygen in the kettle is replaced by nitrogen. The nitrogen in the kettle was pressurized to 1MPa, the reaction kettle was heated to 150 ℃ with stirring at 600rpm, and the temperature was maintained for 1 h. Then cooling to room temperature, filtering, and washing filter residue by using ethanol water solution with the volume fraction of 90%. Mixing filtrates, concentrating, slowly adding the concentrated solution dropwise into 2000ml of deionized water, filtering the precipitate, freeze-drying to remove water, dissolving in 100ml of acetone/methanol (volume ratio of 9:1), slowly adding dropwise into 1000ml of anhydrous ether, filtering the precipitate, and finally vacuum-drying at 60 deg.C to obtain cedar organic solvent lignin.
(2) Reaction for preparing phenol by lignin conversion
Adding 0.4g of cedar organic solvent lignin, 0.4g of HY molecular sieve (the atomic ratio of Si to Al is 30) and 6mL of deionized water into a 20mL polytetrafluoroethylene-lined reaction kettle, sealing the reaction kettle, replacing the air in the kettle with argon, filling the argon to 0.5MPa, stirring at the speed of 800rpm, heating to 200 ℃, and maintaining for 4 hours. After the reaction is finished, the reaction mixture is rapidly cooled to room temperature, the reaction mixture is subjected to centrifugal separation after air release, liquid is extracted by ethyl acetate and then is analyzed by a gas chromatography-mass spectrometer and a gas chromatograph, and the ratio of the mass of the phenol to the mass of the lignin is the phenol yield.
(3) After the reaction, the product was mainly phenol as seen by GC-MS and GC analysis, and the yield was 6.2% by weight.
Example 14
(1) Preparation of cedar organic solvent lignin raw material
70g of cypress powder, 490mL of acetone and 210mL of deionized water are added into a 1000mL acid and alkali resistant high pressure reaction kettle, and the oxygen in the kettle is replaced by nitrogen. The nitrogen in the kettle was pressurized to 0.5MPa, the reaction kettle was heated to 160 ℃ with stirring at 600rpm, and the temperature was maintained for 1 h. Then cooling to room temperature, filtering, and washing filter residue by using 90% by volume of acetone aqueous solution. Mixing filtrates, concentrating, slowly adding the concentrated solution dropwise into 2000ml of deionized water, filtering the precipitate, freeze-drying to remove water, dissolving in 100ml of acetone/methanol (volume ratio of 9:1), slowly adding dropwise into 1000ml of anhydrous ether, filtering the precipitate, and finally vacuum-drying at 60 deg.C to obtain cedar organic solvent lignin.
(2) Reaction for preparing phenol by lignin conversion
Adding 0.4g of cedar organic solvent lignin, 0.6g of HY molecular sieve (the atomic ratio of Si to Al is 40) and 6mL of deionized water into a 20mL polytetrafluoroethylene-lined reaction kettle, sealing the reaction kettle, replacing the air in the kettle with argon, filling the argon to 0.5MPa, stirring at the speed of 800rpm, heating to 210 ℃, and maintaining for 6 hours. After the reaction is finished, the reaction mixture is rapidly cooled to room temperature, the reaction mixture is subjected to centrifugal separation after air release, liquid is extracted by ethyl acetate and then is analyzed by a gas chromatography-mass spectrometer and a gas chromatograph, and the ratio of the mass of the phenol to the mass of the lignin is the phenol yield.
(3) After the reaction, the product was mainly phenol as seen by GC-MS and GC analysis, and the yield was 5.7% by weight.
Example 15
(1) Preparation of cedar organic solvent lignin raw material
70g of cypress powder, 500mL of dioxane, 200mL of deionized water and 3.5g of hydrochloric acid (the mass percentage concentration is 37%) are added into a 1000mL acid-alkali-resistant high-pressure reaction kettle, and nitrogen is used for replacing oxygen in the kettle. The nitrogen in the kettle is pressurized to 1MPa, the reaction kettle is heated to 110 ℃ under the stirring of 800rpm, and the temperature is kept for 1 h. Then cooling to room temperature, filtering, and washing filter residue by using 90% by volume of acetone aqueous solution. Mixing filtrates, concentrating, slowly adding the concentrated solution dropwise into 2000ml of deionized water, filtering the precipitate, freeze-drying to remove water, dissolving in 100ml of acetone/methanol (volume ratio of 9:1), slowly adding dropwise into 1000ml of anhydrous ether, filtering the precipitate, and finally vacuum-drying at 60 deg.C to obtain cedar organic solvent lignin.
(2) Reaction for preparing phenol by lignin conversion
Adding 0.4g of cedar organic solvent lignin, 0.6g of HY molecular sieve (the atomic ratio of Si to Al is 40) and 8mL of deionized water into a 20mL polytetrafluoroethylene-lined reaction kettle, sealing the reaction kettle, replacing the air in the kettle with argon, filling the argon to 0.5MPa, heating to 180 ℃, and maintaining for 8 hours. After the reaction is finished, the reaction mixture is rapidly cooled to room temperature, the reaction mixture is subjected to centrifugal separation after air release, liquid is extracted by ethyl acetate and then is analyzed by a gas chromatography-mass spectrometer and a gas chromatograph, and the ratio of the mass of the phenol to the mass of the lignin is the phenol yield.
(3) After the reaction, the product was mainly phenol as seen by GC-MS and GC analysis, and the yield was 5.7% by weight.
Example 16
(1) Preparation of raw material of moso bamboo organic solvent lignin
70g of moso bamboo powder, 490mL of acetone and 210mL of deionized water are added into a 1000mL acid and alkali resistant high-pressure reaction kettle, and oxygen in the kettle is replaced by nitrogen. The nitrogen in the kettle was pressurized to 0.5MPa, the reaction kettle was heated to 160 ℃ with stirring at 600rpm, and the temperature was maintained for 1 h. Then cooling to room temperature, filtering, and washing filter residue by using 90% by volume of acetone aqueous solution. Mixing filtrates, concentrating, slowly adding the concentrated solution dropwise into 2000ml of deionized water, filtering the precipitate, freeze-drying to remove water, dissolving in 100ml of acetone/methanol (volume ratio of 9:1), slowly adding dropwise into 1000ml of anhydrous ether, filtering the precipitate, and finally vacuum-drying at 60 deg.C to obtain the final product.
(2) Reaction for preparing phenol by lignin conversion
Adding 0.4g of moso bamboo organic solvent lignin, 0.6g of HY molecular sieve (the atomic ratio of Si to Al is 40) and 6mL of deionized water into a 20mL polytetrafluoroethylene lined reaction kettle, sealing the autoclave, replacing the air in the kettle with argon, filling the argon to 0.5MPa, stirring at 800rpm, heating to 190 ℃ and maintaining for 6 hours. After the reaction is finished, the reaction mixture is rapidly cooled to room temperature, the reaction mixture is subjected to centrifugal separation after air release, liquid is extracted by ethyl acetate and then is analyzed by a gas chromatography-mass spectrometer and a gas chromatograph, and the ratio of the mass of the phenol to the mass of the lignin is the phenol yield.
(3) After the reaction, the product was mainly phenol as seen by GC-MS and GC analysis, and the yield was 10.1% by weight.
Example 17
(1) Preparation of raw material of moso bamboo organic solvent lignin
70g of moso bamboo powder, 560mL of butanone and 240mL of deionized water are added into a 1000mL acid and alkali resistant high-pressure reaction kettle, and oxygen in the kettle is replaced by nitrogen. The nitrogen in the kettle was pressurized to 1MPa, the reaction kettle was heated to 150 ℃ with stirring at 600rpm, and the temperature was maintained for 1 h. Then cooling to room temperature, filtering, and washing filter residue by using ethanol water solution with the volume fraction of 90%. Mixing filtrates, concentrating, slowly adding the concentrated solution dropwise into 2000ml of deionized water, filtering the precipitate, freeze-drying to remove water, dissolving in 100ml of acetone/methanol (volume ratio of 9:1), slowly adding dropwise into 1000ml of anhydrous ether, filtering the precipitate, and finally vacuum-drying at 60 deg.C to obtain the final product.
(2) Reaction for preparing phenol by lignin conversion
Adding 0.4g of moso bamboo organic solvent lignin, 0.6g of HY molecular sieve (the atomic ratio of Si to Al is 40) and 8mL of deionized water into a 20mL polytetrafluoroethylene lined reaction kettle, sealing the reaction kettle, replacing the air in the kettle with argon, filling the argon to 0.5MPa, heating to 180 ℃, and maintaining for 8 hours. After the reaction is finished, the reaction mixture is rapidly cooled to room temperature, the reaction mixture is subjected to centrifugal separation after air release, liquid is extracted by ethyl acetate and then is analyzed by a gas chromatography-mass spectrometer and a gas chromatograph, and the ratio of the mass of the phenol to the mass of the lignin is the phenol yield.
(3) After the reaction, the product was mainly phenol as seen by GC-MS and GC analysis, and the yield was 7.8% by weight.
Example 18
(1) Preparation of raw material of moso bamboo organic solvent lignin
70g of moso bamboo powder, 500mL of dioxane, 200mL of deionized water and 3.5g of hydrochloric acid (the mass percentage concentration is 37%) are added into a 1000mL acid-alkali-resistant high-pressure reaction kettle, and oxygen in the kettle is replaced by nitrogen. The nitrogen in the kettle is pressurized to 1MPa, the reaction kettle is heated to 110 ℃ under the stirring of 800rpm, and the temperature is kept for 1 h. Then cooling to room temperature, filtering, and washing filter residue by using 90% by volume of acetone aqueous solution. Mixing filtrates, concentrating, slowly adding the concentrated solution dropwise into 2000ml of deionized water, filtering the precipitate, freeze-drying to remove water, dissolving in 100ml of acetone/methanol (volume ratio of 9:1), slowly adding dropwise into 1000ml of anhydrous ether, filtering the precipitate, and finally vacuum-drying at 60 deg.C to obtain the final product.
(2) Reaction for preparing phenol by lignin conversion
Adding 0.4g of moso bamboo organic solvent lignin, 0.4g of ZSM-5 molecular sieve (the atomic ratio of Si to Al is 235) and 8mL of deionized water into a 20mL polytetrafluoroethylene lining reaction kettle, sealing the reaction kettle, replacing the air in the kettle with argon, filling the argon to 0.5MPa, stirring at the speed of 1000rpm, heating to 210 ℃, and maintaining for 6 hours. After the reaction is finished, the reaction mixture is rapidly cooled to room temperature, the reaction mixture is subjected to centrifugal separation after air release, liquid is extracted by ethyl acetate and then is analyzed by a gas chromatography-mass spectrometer and a gas chromatograph, and the ratio of the mass of the phenol to the mass of the lignin is the phenol yield.
(3) After the reaction, the product was mainly phenol as seen by GC-MS and GC analysis, and the yield was 5.5% by weight.
Comparative example 1
Phenol was produced by the method of example 1 except that the catalyst HY molecular sieve (Si to Al atomic ratio of 30) in example 1 was replaced with HY molecular sieve (Si to Al atomic ratio of 2.6); after the reaction, the product was free of phenol as seen by GC-MS and GC analysis.
Comparative example 2
Phenol was produced by the method of example 1 except that the catalyst HY molecular sieve (Si to Al atomic ratio of 30) in example 1 was replaced with ZSM-5 molecular sieve (Si to Al atomic ratio of 15); after the reaction, the product was free of phenol as seen by GC-MS and GC analysis.
Comparative example 3
Phenol was produced by the method of example 1 except that the catalyst HY molecular sieve (Si to Al atomic ratio of 30) in example 1 was replaced with a beta molecular sieve (Si to Al atomic ratio of 30); after the reaction, the product was free of phenol as seen by GC-MS and GC analysis.

Claims (14)

1. A method for preparing phenol by catalyzing and converting lignin with a high-silicon molecular sieve comprises the following steps: under inert atmosphere, taking a high-silicon molecular sieve as a catalyst to catalytically convert lignin into phenol;
the high-silicon molecular sieve is an HY molecular sieve and/or a ZSM-5 molecular sieve;
the HY molecular sieve has an atomic ratio of Si to Al of 15-40; the atomic ratio of Si to Al of the ZSM-5 molecular sieve is 235;
the temperature of the catalytic conversion reaction is 100-300 ℃.
2. The method of claim 1, wherein: the inert atmosphere is argon and/or nitrogen;
the catalytic conversion reaction is carried out under stirring.
3. The method of claim 2, wherein: the stirring speed is 400 rpm-1000 rpm.
4. The method according to claim 1 or 2, characterized in that: the conditions of the catalytic conversion reaction are as follows: the pressure of the inert gas is 0.1 MPa-10 MPa; the time is 0.5-12 h.
5. The method according to any one of claims 1-3, wherein: the mass of the high-silicon molecular sieve is 10-200% of the mass of the lignin.
6. The method according to any one of claims 1-3, wherein: the catalytic conversion reaction is carried out in a solvent.
7. The method of claim 6, wherein: the solvent is water; the mass ratio of the water to the lignin is 5-50: 1.
8. The method according to any one of claims 1-3, wherein: the lignin is at least one of lignin extracted from poplar, pine, willow, cedar and moso bamboo.
9. The method of claim 8, wherein: the lignin is extracted by an organic solvent.
10. The method of claim 9, wherein: the organic solvent is at least one of acetone, butanone, ethanol, isopropanol and dioxane.
11. The method according to any one of claims 1-3, wherein: the extraction method of the lignin comprises the following steps: hydrolyzing wood powder with high-temperature water or acid to obtain organic solvent lignin; the wood powder is at least one of poplar, pine, willow, cedar and moso bamboo.
12. The method of claim 11, wherein: in the extraction method of the lignin, the volume ratio of the organic solvent to the water is 1-9: 1;
the mass ratio of the total volume of the organic solvent and the water to the wood powder is 5-15 mL: 1g of a compound;
the acid in the acid hydrolysis is hydrochloric acid; the mass ratio of the hydrochloric acid to the wood powder is 0-1: 1;
the temperature of the high-temperature water hydrolysis or acid hydrolysis is 80-200 ℃; the time is 0.5-6 h.
13. The method of claim 11, wherein: the high temperature water hydrolysis or acid hydrolysis is carried out in an inert atmosphere.
14. The method of claim 13, wherein: the pressure of the inert gas is 0.5MPa-1 MPa.
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