CN113372542A - Preparation method of bio-based polyethylene glycol oxalate resin - Google Patents
Preparation method of bio-based polyethylene glycol oxalate resin Download PDFInfo
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- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 title claims abstract description 31
- 229920005989 resin Polymers 0.000 title claims abstract description 29
- 239000011347 resin Substances 0.000 title claims abstract description 29
- 229920001223 polyethylene glycol Polymers 0.000 title claims abstract description 21
- 239000002202 Polyethylene glycol Substances 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 87
- 239000002028 Biomass Substances 0.000 claims abstract description 52
- 239000002002 slurry Substances 0.000 claims abstract description 45
- 238000000034 method Methods 0.000 claims abstract description 44
- LOMVENUNSWAXEN-UHFFFAOYSA-N Methyl oxalate Chemical compound COC(=O)C(=O)OC LOMVENUNSWAXEN-UHFFFAOYSA-N 0.000 claims abstract description 38
- 238000002309 gasification Methods 0.000 claims abstract description 35
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 34
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 33
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 27
- 230000008569 process Effects 0.000 claims abstract description 25
- 238000004880 explosion Methods 0.000 claims abstract description 24
- 238000009835 boiling Methods 0.000 claims abstract description 22
- 230000007062 hydrolysis Effects 0.000 claims abstract description 22
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 22
- 238000007069 methylation reaction Methods 0.000 claims abstract description 22
- 239000002994 raw material Substances 0.000 claims abstract description 22
- 230000011987 methylation Effects 0.000 claims abstract description 17
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910002091 carbon monoxide Inorganic materials 0.000 claims abstract description 14
- 238000005691 oxidative coupling reaction Methods 0.000 claims abstract description 4
- 230000001851 biosynthetic effect Effects 0.000 claims abstract description 3
- 239000007789 gas Substances 0.000 claims description 56
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 24
- 229920005610 lignin Polymers 0.000 claims description 23
- 239000002131 composite material Substances 0.000 claims description 22
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 22
- 150000002910 rare earth metals Chemical class 0.000 claims description 22
- 239000011949 solid catalyst Substances 0.000 claims description 22
- 238000006243 chemical reaction Methods 0.000 claims description 21
- BLLFVUPNHCTMSV-UHFFFAOYSA-N methyl nitrite Chemical compound CON=O BLLFVUPNHCTMSV-UHFFFAOYSA-N 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- WMOHXRDWCVHXGS-UHFFFAOYSA-N [La].[Ce] Chemical compound [La].[Ce] WMOHXRDWCVHXGS-UHFFFAOYSA-N 0.000 claims description 14
- 239000006227 byproduct Substances 0.000 claims description 13
- 239000000463 material Substances 0.000 claims description 13
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 12
- 239000001301 oxygen Substances 0.000 claims description 12
- 229910052760 oxygen Inorganic materials 0.000 claims description 12
- ZNLAHAOCFKBYRH-UHFFFAOYSA-N 1,4-dioxane-2,3-dione Chemical compound O=C1OCCOC1=O ZNLAHAOCFKBYRH-UHFFFAOYSA-N 0.000 claims description 9
- 229920001542 oligosaccharide Polymers 0.000 claims description 9
- 239000007790 solid phase Substances 0.000 claims description 9
- 229920002488 Hemicellulose Polymers 0.000 claims description 8
- 229920002678 cellulose Polymers 0.000 claims description 8
- 239000001913 cellulose Substances 0.000 claims description 8
- HEBKCHPVOIAQTA-NGQZWQHPSA-N d-xylitol Chemical class OC[C@H](O)C(O)[C@H](O)CO HEBKCHPVOIAQTA-NGQZWQHPSA-N 0.000 claims description 8
- 238000000926 separation method Methods 0.000 claims description 8
- 229910052684 Cerium Inorganic materials 0.000 claims description 7
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 7
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 7
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 7
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- 229910052804 chromium Inorganic materials 0.000 claims description 7
- 239000011651 chromium Substances 0.000 claims description 7
- 229910052802 copper Inorganic materials 0.000 claims description 7
- 239000010949 copper Substances 0.000 claims description 7
- 229910052746 lanthanum Inorganic materials 0.000 claims description 7
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 7
- 238000001179 sorption measurement Methods 0.000 claims description 7
- 229920002522 Wood fibre Polymers 0.000 claims description 5
- FYGDTMLNYKFZSV-ZWSAEMDYSA-N cellotriose Chemical class O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@H]1O[C@@H]1[C@@H](CO)O[C@@H](O[C@@H]2[C@H](OC(O)[C@H](O)[C@H]2O)CO)[C@H](O)[C@H]1O FYGDTMLNYKFZSV-ZWSAEMDYSA-N 0.000 claims description 5
- 239000002025 wood fiber Substances 0.000 claims description 5
- 239000000835 fiber Substances 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 150000002482 oligosaccharides Chemical class 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- -1 polyethylene oxalate Polymers 0.000 claims 2
- OUNMTQFEKAIZIF-UHFFFAOYSA-N ethane-1,2-diol;oxalic acid Chemical compound OCCO.OC(=O)C(O)=O OUNMTQFEKAIZIF-UHFFFAOYSA-N 0.000 claims 1
- 150000002632 lipids Chemical class 0.000 claims 1
- 238000010298 pulverizing process Methods 0.000 claims 1
- 230000004888 barrier function Effects 0.000 abstract description 5
- 238000009776 industrial production Methods 0.000 abstract description 4
- 238000012545 processing Methods 0.000 abstract description 3
- 239000002699 waste material Substances 0.000 description 8
- 229910052763 palladium Inorganic materials 0.000 description 7
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 7
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 229920003023 plastic Polymers 0.000 description 4
- 239000004033 plastic Substances 0.000 description 4
- 208000023514 Barrett esophagus Diseases 0.000 description 3
- 244000302661 Phyllostachys pubescens Species 0.000 description 3
- 235000003570 Phyllostachys pubescens Nutrition 0.000 description 3
- 244000141353 Prunus domestica Species 0.000 description 3
- 238000006114 decarboxylation reaction Methods 0.000 description 3
- 150000002148 esters Chemical group 0.000 description 3
- 235000006408 oxalic acid Nutrition 0.000 description 3
- CTSLXHKWHWQRSH-UHFFFAOYSA-N oxalyl chloride Substances ClC(=O)C(Cl)=O CTSLXHKWHWQRSH-UHFFFAOYSA-N 0.000 description 3
- 229920000728 polyester Polymers 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 229920000704 biodegradable plastic Polymers 0.000 description 2
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 230000032050 esterification Effects 0.000 description 2
- 238000005886 esterification reaction Methods 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000004575 stone Substances 0.000 description 2
- 239000010902 straw Substances 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 239000004594 Masterbatch (MB) Substances 0.000 description 1
- 238000012356 Product development Methods 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 229920004933 Terylene® Polymers 0.000 description 1
- 229920008262 Thermoplastic starch Polymers 0.000 description 1
- 240000008042 Zea mays Species 0.000 description 1
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 1
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 1
- SNTQPBNVXYVABO-UHFFFAOYSA-N [La].[Ce].[Cr].[Cu] Chemical compound [La].[Ce].[Cr].[Cu] SNTQPBNVXYVABO-UHFFFAOYSA-N 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000007798 antifreeze agent Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 235000005822 corn Nutrition 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 239000012024 dehydrating agents Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- OJURWUUOVGOHJZ-UHFFFAOYSA-N methyl 2-[(2-acetyloxyphenyl)methyl-[2-[(2-acetyloxyphenyl)methyl-(2-methoxy-2-oxoethyl)amino]ethyl]amino]acetate Chemical compound C=1C=CC=C(OC(C)=O)C=1CN(CC(=O)OC)CCN(CC(=O)OC)CC1=CC=CC=C1OC(C)=O OJURWUUOVGOHJZ-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000747 poly(lactic acid) Polymers 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 239000004626 polylactic acid Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000004628 starch-based polymer Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/16—Dicarboxylic acids and dihydroxy compounds
-
- 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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
- C08G63/82—Preparation processes characterised by the catalyst used
- C08G63/84—Boron, aluminium, gallium, indium, thallium, rare-earth metals, or compounds 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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
- C08G63/82—Preparation processes characterised by the catalyst used
- C08G63/85—Germanium, tin, lead, arsenic, antimony, bismuth, titanium, zirconium, hafnium, vanadium, niobium, tantalum, or compounds thereof
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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)
- Processing Of Solid Wastes (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a preparation method of bio-based polyethylene glycol oxalate resin, which comprises the following steps: the biomass raw material is subjected to gas explosion crushing and methylation boiling hydrolysis process to produce methylated biomass slurry, and the methylated biomass slurry is subjected to gasification process to produce biosynthetic gas; the biological synthesis gas is transformed, separated and purified to produce biological carbon monoxide, biological dimethyl oxalate is synthesized by using a biological carbon monoxide oxidative coupling method, and biological ethylene glycol is produced by hydrogenating the biological dimethyl oxalate; the bio-based polyethylene glycol oxalate resin is produced by bio-dimethyl oxalate and bio-ethylene glycol through a polymerization process. The invention has the characteristics of cheap and easily obtained and renewable raw materials, green and environment-friendly process, low cost, good processing performance, high barrier property, good biodegradability and the like, and is suitable for industrial production.
Description
Technical Field
The invention belongs to the technical field of bio-based biodegradable plastics, and particularly relates to a preparation method of bio-based polyethylene glycol oxalate resin.
Background
The biological dimethyl oxalate, also called dimethyl oxalate, is the simplest dibasic acid dimethyl ester, has the advantages of renewable raw material resources, low price, easy obtainment, convenient storage and transportation and the like, can replace the stone-based dimethyl oxalate, and is mainly used for pharmacy, pesticides, organic synthesis and the like. The bio-glycol is the simplest dihydric alcohol, has the advantages of renewable raw material resources, low price, easy obtainment and the like, can replace fossil-based glycol, is mainly used for preparing polyester, terylene, polyester resin, moisture absorbent, plasticizer, surfactant, synthetic fiber, cosmetics and explosive, and is also used as a solvent for dye, printing ink and the like, an antifreeze agent for preparing an engine, a gas dehydrating agent and the like.
The biological poly (ethylene oxalate) is polymerized by biological dimethyl oxalate and biological ethylene glycol, has the characteristics of renewable raw material resources, low price and easy obtainment, capability of replacing stone-based poly (ethylene oxalate) and high barrier property, high melting point (higher than 100 ℃), good static thermal stability, lower glass transition temperature, wide processing temperature range and the like, can be used as general plastic, can also be used as a master batch of general plastic, or can be blended with thermoplastic starch, polylactic acid and the like to prepare biodegradable plastic. The polyoxalate material is discovered relatively early, but for various reasons, the large-scale product development is not found so far, the research is mainly performed in Japan, and no bio-based polyoxalate material is reported yet.
Polyoxalates are biodegradable, but have been studied and reported in depth since they were first synthesized in the laboratory. The oxalate Polymer (POX) can be synthesized by esterification or ester exchange polymerization method, wherein the esterification is synthesized by glycol such as ethylene glycol, propylene glycol, butanediol and the like and oxalic acid or oxalyl chloride, the method has simple process, but the molecular weight of the oxalate polymer is low, mainly the temperature at the later stage of the polycondensation reaction is high, and the oxalic acid is easy to generate decarboxylation, oxidation, degradation and other reactions, so that the molecular weight of the polyester is reduced, the color is darkened and the like. The ester exchange is synthesized by glycol such as ethylene glycol, propylene glycol, butanediol and the like and dimethyl oxalate, and the method has the advantages of convenient process, high polymerization molecular weight and avoidance of side reactions such as decarboxylation and the like.
At present, melt polymerization and solid-phase polymerization are generally adopted in the ester exchange method polyoxalate polymerization. During melt polymerization, the required high temperature can generate decarboxylation, oxidation and degradation reactions like the synthesis later stage of the glycol and the oxalic acid, so that the molecular weight of the polyester is reduced, the color is darkened, and the like. The solid phase polymerization process is one new process of obtaining high performance and high relative molecular weight polyoxalate, and is one polymerization process at temperature lower than the melting point of polyoxalate and higher than the glass transition temperature. The method has few reports on the aspect of oxalate polymerization, and industrial application is not found yet.
Disclosure of Invention
The invention aims to provide a preparation method of bio-based polyethylene glycol oxalate resin, which has the characteristics of cheap and easily available and renewable raw materials, green and environment-friendly process, low cost, good processability, high barrier property, good biodegradability and the like, and is suitable for industrial production.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
the preparation method of the bio-based polyethylene glycol oxalate resin comprises the following steps:
the biomass raw material is subjected to gas explosion crushing and methylation boiling hydrolysis process to produce methylated biomass slurry, and the methylated biomass slurry is subjected to gasification process to produce biosynthetic gas;
the biological synthesis gas is transformed, separated and purified to produce biological carbon monoxide, biological dimethyl oxalate is synthesized by using a biological carbon monoxide oxidative coupling method, and biological ethylene glycol is produced by hydrogenating the biological dimethyl oxalate;
the bio-based polyethylene glycol oxalate resin is produced by bio-dimethyl oxalate and bio-ethylene glycol through a polymerization process.
Further, the biological dimethyl oxalate and the biological ethylene glycol are placed into a polymerization reaction device, the solid-phase polymerization process is adopted to produce the biological polyethylene glycol oxalate resin, the reaction temperature is 110-150 ℃, the pressure is 0.2-0.4MPa, and the time is 5-6 hours, and the rare earth lanthanum cerium titanate composite solid catalyst is adopted.
Further, the molar ratio of the bio-dimethyl oxalate to the bio-ethylene glycol is 1: 2.
further, the gas explosion crushing comprises: placing the lignocellulose biomass raw material subjected to mechanical crushing into a tubular gas explosion reactor, introducing superheated steam with the temperature of 240-280 ℃ and the pressure of 2.4-3.1 MPa for 0.5-15 minutes, opening a valve, and exploding the material into a methylation boiling hydrolysis reactor; methylation boiling hydrolysis comprises: the temperature is 160-220 ℃, the pressure is 1.4-1.6 MPa, and the time is 5-30 minutes, so that hemicellulose in the wood fiber biomass raw material is converted into methylated xylooligosaccharide, cellulose is converted into methylated fiber oligosaccharide, lignin is converted into methylated oligomeric lignin, and the methylated biomass slurry is prepared.
Further, the proportion of the methylated biomass slurry is as follows: 5-36 wt% of methylated xylooligosaccharide, 15-65 wt% of methylated cellooligosaccharide, 10-55 wt% of methylated oligomeric lignin and 15-60 wt% of water; controlling the density range of the methylated biomass slurry to be 1.2-1.6 g/cm3The heat value range is 20.50-33.10 MJ/kg, and the water content is more than 30 wt%.
Further, the water content of the methylated biomass slurry is 30-60 wt%.
Further, the step of producing the bio-syngas by the gasification process comprises: a pressurized entrained-flow bed gasification furnace device is adopted, the solid content of the methylated biomass slurry is 60-65%, and the gasification agent is O2(ii) a Pressurized methylated biomass slurry with high pressure O2The mixture is fed into a pressurized entrained-flow bed gasification furnace device through a nozzle, the gasification temperature is 1200-1350 ℃, the pressure is 1.2-2.5 MPa, and the H-containing material is prepared2CO and CO2The biosyngas of (a); adjusting H of the biological synthesis gas by a steam shift reaction device2And CO in a ratio of 1: 7-10, preparing biological CO from the transformed biological synthesis gas through a pressure swing adsorption separation device, and preparing biological H as a byproduct2。
Further, the ratio of the biological synthesis gas is as follows: h232-36 wt% of CO, 38-41 wt% of CO210-12 wt%.
Further, biological CO and methyl nitrite are synthesized into biological dimethyl oxalate at the temperature of 100-120 ℃ by adopting a rare earth lanthanum cerium palladium composite solid catalyst, a byproduct is NO, and the NO is converted into the methyl nitrite by using oxygen and methanol for recycling; the biological ethylene glycol is synthesized by hydrogenating the biological dimethyl oxalate at the temperature of 190 ℃ and the pressure of 1.0-1.5MPa, and a rare earth lanthanum, cerium, copper and chromium composite solid catalyst is adopted.
Further, the molar ratio of biological CO to methyl nitrite is 1:2, and the molar ratio of NO, oxygen and methanol is 4:1:4, the molar ratio of the biological dimethyl oxalate to the hydrogen is 2: 3.
the invention has the technical effects that:
the invention has the characteristics of cheap and easily obtained and renewable raw materials, green and environment-friendly process, low cost, good processing performance, high barrier property, good biodegradability and the like, and is suitable for industrial production. The prepared plastic product has reliable performance and is widely used in various fields of national economy such as food, packaging materials, agriculture and forestry and the like.
(1) The lignocellulose biomass (urban landscaping residues, agricultural and forestry wastes, resource crops and the like) raw materials are cheap, easily available and renewable, are mostly waste resources, and belong to waste utilization.
(2) The hemicellulose, the cellulose and the lignin are respectively converted into the methylated xylo-oligosaccharide, the methylated cello-oligosaccharide and the methyl oligomeric lignin by adopting a gas explosion crushing-methylation boiling hydrolysis process to prepare the methylated biomass, so that the full component utilization of lignocellulose biomass resources is realized, and the process is green and efficient.
(3) The pressurized entrained-flow bed gasification process is used for producing the biological carbon monoxide from the methylated biomass slurry, the investment is low, the efficiency is high, the process has the characteristics of pure gas, no sulfur, simple and stable gasification process and the like, and the comprehensive cost-effectiveness ratio is superior to that of the fossil-based carbon monoxide.
(4) The method takes biological carbon monoxide and methyl nitrite as raw materials, adopts a rare earth lanthanum cerium palladium composite solid catalyst oxidation coupling method to produce the biological dimethyl oxalate, and adopts the rare earth lanthanum cerium copper chromium composite solid catalyst to synthesize the biological ethylene glycol by hydrogenation.
(5) The method for producing the biological poly (ethylene oxalate) resin by using the biological dimethyl oxalate and the biological ethylene glycol as raw materials and adopting the rare earth lanthanum cerium titanate composite solid catalyst has the characteristics of cheap and easily obtained raw materials, renewable property, green process, mild reaction conditions, simple and efficient process, high barrier and biodegradability of products, excellent and reliable performance and the like, is suitable for industrial production, and is a new generation of general plastic.
Detailed Description
The following description sufficiently illustrates specific embodiments of the invention to enable those skilled in the art to practice and reproduce it.
The invention takes lignocellulose biomass such as agricultural and forestry waste and the like as raw materials (urban landscaping residues, agricultural and forestry waste, resource crops and the like) to obtain methylated biomass slurry after gas explosion crushing and methylation boiling hydrolysis, the methylated biomass slurry produces biological synthesis gas through a gasification process, the biological synthesis gas produces biological carbon monoxide through conversion, separation and purification, the biological carbon monoxide is utilized to synthesize biological dimethyl oxalate through a biological carbon monoxide oxidation coupling method, the biological dimethyl oxalate is hydrogenated to synthesize biological ethylene glycol, and finally the biological dimethyl oxalate and the biological ethylene glycol are polymerized to produce the biological polyethylene glycol oxalate resin.
The preparation method of the bio-based polyethylene glycol oxalate resin comprises the following specific steps:
step 1: the wood fiber raw material is subjected to gas explosion crushing and methylation boiling hydrolysis process to produce methylated biomass slurry;
the method comprises the steps of carrying out gas explosion crushing and methylation boiling hydrolysis on wood fiber raw materials such as agricultural and forestry wastes to obtain methylated biomass slurry, wherein the two steps of gas explosion crushing and methylation boiling hydrolysis are included.
Gas explosion and crushing: placing the lignocellulose biomass raw material subjected to mechanical crushing into a tubular gas explosion reactor, introducing superheated steam with the temperature of 240-280 ℃ and the pressure of 2.4-3.1 MPa for 0.5-15 minutes, opening a valve, and exploding the material into a methylation boiling hydrolysis reactor;
methylation boiling hydrolysis: converting hemicellulose in the wood fiber biomass raw material into methylated xylo-oligosaccharide, converting cellulose into methylated fiber oligosaccharide, converting lignin into methylated oligo-lignin and preparing methylated biomass at the temperature of 160-220 ℃ and the pressure of 1.4-1.6 MPa for 5-30 minutes; the proportion of the methylated biomass slurry is as follows: 5-36 wt% of methylated xylooligosaccharide, 15-65 wt% of methylated cellooligosaccharide, 10-55 wt% of methylated oligomeric lignin and 15-60 wt% of water; controlThe density range of the prepared methylated biomass slurry is 1.2-1.6 g/cm3The heat value range is 20.50-33.10 MJ/kg, and the water content is more than 30 wt% (preferably 30-60 wt%).
Step 2: producing the biological synthesis gas by the methylated biomass slurry through a gasification process;
a pressurized entrained-flow bed gasification furnace device is adopted, the solid content of the methylated biomass slurry is 60-65 wt%, and the gasification agent is O2(purity > 99%); pressurized methylated biomass slurry with high pressure O2The mixture is fed into a pressurized entrained-flow bed gasification furnace device through a nozzle, the gasification temperature is 1200-1350 ℃, the pressure is 1.2-2.5 MPa, and the product mainly containing H is prepared2CO and CO2The ratio of the biological synthesis gas is as follows: h232-36 wt% of CO, 38-41 wt% of CO210-12 wt%.
Adjusting H by adopting steam conversion process for biological synthesis gas2The ratio of the CO to the biological synthesis gas is 1: 7-10, the transformed biological synthesis gas is subjected to a Pressure Swing Adsorption (PSA) separation device to prepare biological CO, and the byproduct is biological H2。
And step 3: the biological synthesis gas is transformed, separated and purified to produce biological carbon monoxide, biological dimethyl oxalate is synthesized by using a biological carbon monoxide oxidative coupling method, and biological ethylene glycol is produced by hydrogenating the biological dimethyl oxalate;
biological CO and methyl nitrite (the molar ratio is 1: 2) are synthesized into biological dimethyl oxalate at the temperature of 100-120 ℃ by adopting a rare earth lanthanum cerium palladium composite solid catalyst, and the byproduct is NO. NO is converted to methyl nitrite with oxygen and methanol (molar ratio 4:1: 4) for recycle.
Biological ethylene glycol is synthesized by hydrogenating biological dimethyl oxalate (the molar ratio is 2: 3) at the temperature of 190 ℃ and the pressure of 1.0-1.5MPa, and a rare earth lanthanum, cerium, copper and chromium composite solid catalyst is adopted.
And 4, step 4: the bio-based polyethylene glycol oxalate resin is produced by bio-dimethyl oxalate and bio-ethylene glycol through a polymerization process.
The biological dimethyl oxalate and the biological ethylene glycol (the molar ratio is 1: 2) are placed into a polymerization reaction device, the solid-phase polymerization process is adopted to produce the biological polyethylene glycol oxalate resin, the reaction temperature is 110-.
Example 1
(1) 200kg of corn straws (with the water content of about 25 wt%) are crushed to be less than 1cm, the crushed materials are sent into a gas explosion crushing-methylation boiling hydrolysis reactor, superheated steam is introduced for gas explosion crushing at the temperature of 245 ℃ and 250 ℃ and under the pressure of 2.4-2.5MPa for 0.5 minute, the materials are sent into a methylation boiling hydrolysis device after being crushed into nano-micron particles by explosion, the temperature is 180 ℃ and 190 ℃ and the pressure is 1.4-1.5MPa for 10-15 minutes, the reaction is carried out to convert hemicellulose in the straws into methylated xylo-oligosaccharides, convert cellulose into methylated cello-oligosaccharides, convert lignin into methylated lignin, and generate methylated biomass slurry containing 35-40% of water.
(2) 130.2kg of methylated biomass slurry is fed by adopting a pressurized entrained flow gasifier device, the content of lignin semicoke in the methylated biomass is 61-63 wt%, and the gasifying agent is O2The pressurized methylated biomass and high-pressure oxygen are sent into a gasification furnace device through a nozzle, the gasification temperature is 1250-1280 ℃, the pressure is 1.2-1.3MPa, and the material mainly containing H is prepared2CO and CO2The biological synthesis gas of (1) is 32-36 wt% of H238-41 wt% of CO, 10-12 wt% of CO2. Adjusting H of the biological synthesis gas by a steam shift reaction device2The ratio of the CO and the biological synthesis gas is 1:7, the transformed biological synthesis gas is separated by a Pressure Swing Adsorption (PSA) separation device to prepare biological CO and byproduct biological H2。
(3) Biological CO and methyl nitrite are synthesized into biological dimethyl oxalate at the temperature of 100-120 ℃ by adopting a rare earth lanthanum cerium palladium composite solid catalyst, and NO is a byproduct. The NO is converted to methyl nitrite with oxygen and methanol for recycle. The dimethyl oxalate is hydrogenated to synthesize the biological ethylene glycol at the temperature of 190 ℃ and the temperature of 200 ℃ and the pressure of 1.0-1.1MPa, and a rare earth lanthanum, cerium, copper and chromium composite solid catalyst is adopted.
(4) The dimethyl oxalate and the ethylene glycol are put into a polymerization reaction device, the biological polyethylene glycol oxalate resin is produced by adopting a solid phase polymerization process, the reaction temperature is 110-120 ℃, the pressure is 0.2-0.3MPa, and the time is 5 hours, and the rare earth lanthanum cerium titanate composite solid catalyst is adopted.
Example 2
(1) 200kg of tree prunes (with the water content of about 20 wt%) are crushed to be less than 1cm, the tree prunes are sent into a gas explosion crushing-methylation boiling hydrolysis reactor, superheated steam is introduced for gas explosion crushing, the temperature is 240-245 ℃, the pressure is 2.5-2.6MPa, the time is 1 minute, the materials are exploded and crushed into nano-micron particles, the nano-micron particles are sent into a methylation boiling hydrolysis device, the temperature is 160-170 ℃, the pressure is 1.4-1.5MPa, and the time is 10-15 minutes, the reaction converts hemicellulose in the tree prunes into methylated xylo-oligosaccharides, the cellulose into methylated cello-oligosaccharides, and the lignin is converted into methylated lignin to generate methylated biomass slurry containing 37-40 wt% of water.
(2) 131.3kg of methylated biomass slurry is fed by adopting a pressurized entrained-flow bed gasification furnace device, the content of lignin semicoke in the slurry is 60-62 wt%, and the gasification agent is O2The pressurized slurry and high-pressure oxygen are sent into a gasification furnace device through a nozzle, the gasification temperature is 1270-1290 ℃, the pressure is 1.5-1.6 MPa, and the slurry mainly containing H is prepared2CO and CO2The biological synthesis gas of (1) is 32-36 wt% of H238-41 wt% of CO, 10-12 wt% of CO2. Adjusting H of the biological synthesis gas by a steam shift reaction device2The ratio of the CO and the biological synthesis gas is 1:8, the transformed biological synthesis gas is separated by a Pressure Swing Adsorption (PSA) separation device to prepare biological CO and byproduct biological H2。
(3) Biological CO and methyl nitrite are synthesized into biological dimethyl oxalate at the temperature of 110 ℃ below 100 ℃ by adopting a rare earth lanthanum cerium palladium composite solid catalyst, and NO is a byproduct. The NO is converted to methyl nitrite with oxygen and methanol for recycle. The dimethyl oxalate is hydrogenated to synthesize the biological ethylene glycol at the temperature of 190 ℃ and the temperature of 200 ℃ and the pressure of 1.0-1.1MPa, and a rare earth lanthanum, cerium, copper and chromium composite solid catalyst is adopted.
(4) The dimethyl oxalate and the ethylene glycol are placed into a polymerization reaction device, the biological polyethylene glycol oxalate resin is produced by adopting a solid phase polymerization process, the reaction temperature is 115-125 ℃, the pressure is 0.2-0.3MPa, and the time is 5.5 hours, and the rare earth lanthanum cerium titanate composite solid catalyst is adopted.
Example 3
(1) 200kg of landscaping waste branches (the water content is about 25 wt%) are crushed to be less than 1cm, the crushed branches are sent to a gas explosion crushing-methylation boiling hydrolysis reactor, superheated steam is introduced for gas explosion crushing, the temperature is 250-260 ℃, the pressure is 3.0-3.1MPa, and the time is 1.5 minutes, the materials are sent to a methylation boiling hydrolysis device after being crushed into nano-micron particles by explosion, the temperature is 180-190 ℃, the pressure is 1.4-1.5MPa, and the time is 15-20 minutes, the reaction is carried out to convert hemicellulose in the landscaping waste branches into methylated xylo-oligosaccharides, convert cellulose into methylated cello-oligosaccharides, convert lignin into methylated lignin, and generate methylated biomass slurry containing 35-37 wt% of water.
(2) 132.2kg of methylated biomass slurry is fed by adopting a pressurized entrained-flow bed gasification furnace device, the content of lignin semicoke in the slurry is 63-65 wt%, and the gasification agent is O2The pressurized slurry and high-pressure oxygen are sent into a gasification furnace device through a nozzle, the gasification temperature is 1280-1300 ℃, the pressure is 1.7-1.8 MPa, and the slurry mainly containing H is prepared2CO and CO2The biological synthesis gas of (1) is 32-36 wt% of H238-41 wt% of CO, 10-12 wt% of CO2. Adjusting H of the biological synthesis gas by a steam shift reaction device2The ratio of the CO and the biological synthesis gas is 1:9, the transformed biological synthesis gas is separated by a Pressure Swing Adsorption (PSA) separation device to prepare biological CO and byproduct biological H2。
(3) Biological CO and methyl nitrite are synthesized into biological dimethyl oxalate at the temperature of 105-115 ℃ by adopting a rare earth lanthanum cerium palladium composite solid catalyst, and NO is a byproduct. The NO is converted to methyl nitrite with oxygen and methanol for recycle. The dimethyl oxalate is hydrogenated to synthesize the biological ethylene glycol at the temperature of 200 ℃ and the pressure of 1.2-1.3MPa by adopting a rare earth lanthanum, cerium, copper and chromium composite solid catalyst.
(4) The dimethyl oxalate and the ethylene glycol are placed into a polymerization reaction device, the biological polyethylene glycol oxalate resin is produced by adopting a solid phase polymerization process, the reaction temperature is 115-125 ℃, the pressure is 0.3-0.4MPa, and the time is 5.2 hours, and the rare earth lanthanum cerium titanate composite solid catalyst is adopted.
Example 4
(1) 200kg of moso bamboo (with the water content of 23 wt%) is crushed to be less than 1cm, the moso bamboo is sent into a gas explosion crushing-methylation boiling hydrolysis reactor, superheated steam is introduced for gas explosion crushing, the temperature is 270 ℃ and 280 ℃, the pressure is 2.5-2.6MPa, and the time is 3 minutes, the materials are exploded and crushed into nano-micron particles, the nano-micron particles are sent into a methylation boiling hydrolysis device, the temperature is 200 ℃ and 210 ℃, the pressure is 1.4-1.5MPa, and the time is 20-25 minutes, the reaction is carried out to convert hemicellulose in the moso bamboo into methylated xylo-oligosaccharide, convert cellulose into methylated cello-oligosaccharide, convert lignin into methylated lignin, and generate methylated biomass slurry containing 35-37 wt% of water.
(2) 132.2kg of methylated biomass slurry is fed by adopting a pressurized entrained-flow bed gasification furnace device, the content of lignin semicoke in the slurry is 62-64 wt%, and the gasification agent is O2The pressurized slurry and high-pressure oxygen are sent into a gasification furnace device through a nozzle, the gasification temperature is 1300-1320 ℃, the pressure is 1.2-1.3MPa, and the slurry mainly containing H is prepared2CO and CO2The biological synthesis gas of (1) is 32-36 wt% of H238-41 wt% of CO, 10-12 wt% of CO2. Adjusting H of the biological synthesis gas by a steam shift reaction device2And CO in a ratio of 1: 10, preparing biological CO and byproduct biological H from the transformed biological synthesis gas by a Pressure Swing Adsorption (PSA) separation device2。
(3) Biological CO and methyl nitrite are synthesized into biological dimethyl oxalate at the temperature of 110-120 ℃ by adopting a rare earth lanthanum cerium palladium composite solid catalyst, and NO is a byproduct. The NO is converted to methyl nitrite with oxygen and methanol for recycle. The dimethyl oxalate is hydrogenated to synthesize the biological ethylene glycol at the temperature of 210 ℃ and 220 ℃ and under the pressure of 1.2-1.3MPa, and a rare earth lanthanum, cerium, copper and chromium composite solid catalyst is adopted.
(4) The dimethyl oxalate and the ethylene glycol are put into a polymerization reaction device, the biological polyethylene glycol oxalate resin is produced by adopting a solid phase polymerization process, the reaction temperature is 130-140 ℃, the pressure is 0.3-0.4MPa, and the time is 6 hours, and the rare earth lanthanum cerium titanate composite solid catalyst is adopted.
The terminology used herein is for the purpose of description and illustration, rather than of limitation. As the present invention may be embodied in several forms without departing from the spirit or essential characteristics thereof, it should also be understood that the above-described embodiments are not limited by any of the details of the foregoing description, but rather should be construed broadly within its spirit and scope as defined in the appended claims, and therefore all changes and modifications that fall within the meets and bounds of the claims, or equivalences of such meets and bounds are therefore intended to be embraced by the appended claims.
Claims (10)
1. A preparation method of bio-based polyethylene glycol oxalate resin comprises the following steps:
the biomass raw material is subjected to gas explosion crushing and methylation boiling hydrolysis process to produce methylated biomass slurry, and the methylated biomass slurry is subjected to gasification process to produce biosynthetic gas;
the biological synthesis gas is transformed, separated and purified to produce biological carbon monoxide, biological dimethyl oxalate is synthesized by using a biological carbon monoxide oxidative coupling method, and biological ethylene glycol is produced by hydrogenating the biological dimethyl oxalate;
the bio-based polyethylene glycol oxalate resin is produced by bio-dimethyl oxalate and bio-ethylene glycol through a polymerization process.
2. The method for preparing bio-based poly (ethylene oxalate) resin as defined in claim 1, wherein the bio-dimethyl oxalate and the bio-ethylene glycol are placed in a polymerization reaction device, and the bio-based poly (ethylene oxalate) resin is produced by a solid phase polymerization process at a reaction temperature of 110-150 ℃ and a pressure of 0.2-0.4MPa for 5-6 hours, and a rare earth lanthanum cerium titanate composite solid catalyst is used.
3. The method of preparing bio-based polyethylene oxalate resin according to claim 2, wherein the molar ratio of bio-dimethyl oxalate to bio-ethylene glycol is 1: 2.
4. the method of preparing bio-based polyethylene oxalate resin of claim 1, wherein the gas explosion pulverization comprises: placing the lignocellulose biomass raw material subjected to mechanical crushing into a tubular gas explosion reactor, introducing superheated steam with the temperature of 240-280 ℃ and the pressure of 2.4-3.1 MPa for 0.5-15 minutes, opening a valve, and exploding the material into a methylation boiling hydrolysis reactor; methylation boiling hydrolysis comprises: the temperature is 160-220 ℃, the pressure is 1.4-1.6 MPa, and the time is 5-30 minutes, so that hemicellulose in the wood fiber biomass raw material is converted into methylated xylooligosaccharide, cellulose is converted into methylated fiber oligosaccharide, lignin is converted into methylated oligomeric lignin, and the methylated biomass slurry is prepared.
5. The method of preparing bio-based poly (ethylene oxalate) resin of claim 4, wherein the methylated biomass slurry is prepared in the following proportions: 5-36 wt% of methylated xylooligosaccharide, 15-65 wt% of methylated cellooligosaccharide, 10-55 wt% of methylated oligomeric lignin and 15-60 wt% of water; controlling the density range of the methylated biomass slurry to be 1.2-1.6 g/cm3The heat value range is 20.50-33.10 MJ/kg, and the water content is more than 30 wt%.
6. The method for preparing bio-based poly (ethylene oxalate) resin according to claim 5, wherein the methylated biomass slurry has a water content of 30 to 60 wt%.
7. The method of preparing bio-based poly (ethylene oxalate) resin according to claim 1, wherein the step of producing the bio-syngas by a gasification process comprises: a pressurized entrained-flow bed gasification furnace device is adopted, the solid content of the methylated biomass slurry is 60-65%, and the gasification agent is O2(ii) a Pressurized methylated biomass slurry with high pressure O2The mixture is fed into a pressurized entrained-flow bed gasification furnace device through a nozzle, the gasification temperature is 1200-1350 ℃, the pressure is 1.2-2.5 MPa, and the H-containing material is prepared2CO and CO2The biosyngas of (a); adjusting H of the biological synthesis gas by a steam shift reaction device2The ratio of the CO to the CO is 1: 7-10, the transformed biological synthesis gas is subjected to a pressure swing adsorption separation device to prepare biological CO, and the byproduct is biological H2。
8. The bio-based polyethylene glycol oxalate tree of claim 7The preparation method of the lipid is characterized in that the ratio of the biological synthesis gas is as follows: h232-36 wt% of CO, 38-41 wt% of CO210-12 wt%.
9. The method for preparing bio-based poly (ethylene glycol oxalate) resin as claimed in claim 1, wherein bio-CO and methyl nitrite are synthesized into bio-dimethyl oxalate at 100-; the biological ethylene glycol is synthesized by hydrogenating the biological dimethyl oxalate at the temperature of 190 ℃ and the pressure of 1.0-1.5MPa, and a rare earth lanthanum, cerium, copper and chromium composite solid catalyst is adopted.
10. The method of preparing bio-based poly (ethylene oxalate) resin according to claim 9, wherein the molar ratio of bio-CO to methyl nitrite is 1:2, the molar ratio of NO, oxygen, and methanol is 4:1:4, and the molar ratio of bio-dimethyl oxalate to hydrogen is 2: 3.
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Citations (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1090958A2 (en) * | 1999-10-05 | 2001-04-11 | Nippon Shokubai Co., Ltd. | Biodegradable polyester resin composition and its use |
| JP2002047340A (en) * | 2000-08-02 | 2002-02-12 | Mitsubishi Chemicals Corp | Method for manufacturing polyester resin and the same obtained thereby |
| CN101387084A (en) * | 2007-09-10 | 2009-03-18 | 中粮集团有限公司 | Method for steam blasting cellulose-containing material |
| CN101492370A (en) * | 2008-12-18 | 2009-07-29 | 中国石油化工股份有限公司 | Method for producing oxalic ester with CO coupling |
| CN101501201A (en) * | 2006-05-26 | 2009-08-05 | 艾尔萨姆纸业有限公司 | Method for syngas-production from liquefied biomass |
| CN101716524A (en) * | 2009-12-08 | 2010-06-02 | 金发科技股份有限公司 | High-activity titanium complex catalyst, preparation method and application thereof in copolyester synthesis |
| CN101870638A (en) * | 2009-04-21 | 2010-10-27 | 北京金骄生物质化工有限公司 | Method for preparing ethylene alcohol by plant straws |
| CN101993344A (en) * | 2009-08-31 | 2011-03-30 | 中国石油化工股份有限公司上海石油化工研究院 | Method for preparing ethylene glycol from synthesis gas |
| CN102492121A (en) * | 2011-12-13 | 2012-06-13 | 南昌航空大学 | Preparation method and use of rare earth coated titanium polyesterification catalyst |
| CN102718948A (en) * | 2012-07-03 | 2012-10-10 | 常州大学 | Method for preparing aliphatic polyoxalate |
| CN103788352A (en) * | 2012-10-30 | 2014-05-14 | 中国石油化工股份有限公司 | Polyoxalates and preparation method |
| CN106029732A (en) * | 2013-12-24 | 2016-10-12 | 东洋制罐集团控股株式会社 | Polyoxalate and method for producing same |
| CN107216452A (en) * | 2016-03-21 | 2017-09-29 | 中国科学院理化技术研究所 | Preparation method of nano titanium rare earth composite catalyst and application of nano titanium rare earth composite catalyst in synthesis of polyester and copolyester |
| CN108246289A (en) * | 2018-01-25 | 2018-07-06 | 宁波中科远东催化工程技术有限公司 | The catalyst of CO gas phase coupling synthesizing dimethyl oxalates, preparation method and application |
-
2021
- 2021-05-17 CN CN202110533601.9A patent/CN113372542A/en active Pending
Patent Citations (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1090958A2 (en) * | 1999-10-05 | 2001-04-11 | Nippon Shokubai Co., Ltd. | Biodegradable polyester resin composition and its use |
| JP2002047340A (en) * | 2000-08-02 | 2002-02-12 | Mitsubishi Chemicals Corp | Method for manufacturing polyester resin and the same obtained thereby |
| CN101501201A (en) * | 2006-05-26 | 2009-08-05 | 艾尔萨姆纸业有限公司 | Method for syngas-production from liquefied biomass |
| CN101387084A (en) * | 2007-09-10 | 2009-03-18 | 中粮集团有限公司 | Method for steam blasting cellulose-containing material |
| CN101492370A (en) * | 2008-12-18 | 2009-07-29 | 中国石油化工股份有限公司 | Method for producing oxalic ester with CO coupling |
| CN101870638A (en) * | 2009-04-21 | 2010-10-27 | 北京金骄生物质化工有限公司 | Method for preparing ethylene alcohol by plant straws |
| CN101993344A (en) * | 2009-08-31 | 2011-03-30 | 中国石油化工股份有限公司上海石油化工研究院 | Method for preparing ethylene glycol from synthesis gas |
| CN101716524A (en) * | 2009-12-08 | 2010-06-02 | 金发科技股份有限公司 | High-activity titanium complex catalyst, preparation method and application thereof in copolyester synthesis |
| CN102492121A (en) * | 2011-12-13 | 2012-06-13 | 南昌航空大学 | Preparation method and use of rare earth coated titanium polyesterification catalyst |
| CN102718948A (en) * | 2012-07-03 | 2012-10-10 | 常州大学 | Method for preparing aliphatic polyoxalate |
| CN103788352A (en) * | 2012-10-30 | 2014-05-14 | 中国石油化工股份有限公司 | Polyoxalates and preparation method |
| CN106029732A (en) * | 2013-12-24 | 2016-10-12 | 东洋制罐集团控股株式会社 | Polyoxalate and method for producing same |
| CN107216452A (en) * | 2016-03-21 | 2017-09-29 | 中国科学院理化技术研究所 | Preparation method of nano titanium rare earth composite catalyst and application of nano titanium rare earth composite catalyst in synthesis of polyester and copolyester |
| CN108246289A (en) * | 2018-01-25 | 2018-07-06 | 宁波中科远东催化工程技术有限公司 | The catalyst of CO gas phase coupling synthesizing dimethyl oxalates, preparation method and application |
Non-Patent Citations (3)
| Title |
|---|
| RUSSBUELDT, BERNHARD M. E.等: ""New rare earth oxide catalysts for the transesterification of triglycerides with methanol resulting in biodiesel and pure glycerol"", 《JOURNAL OF CATALYSIS》 * |
| 田俊凯等: "" 熔融缩聚/固相缩聚合成聚草酸乙二醇酯及其性能表征"", 《高分子通报》 * |
| 邱建辉等: "《高分子合成化学实验》", 31 August 2008, 国防工业出版社 * |
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