CN103772693A - Method for preparing lignin polyether polyols - Google Patents
Method for preparing lignin polyether polyols Download PDFInfo
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- CN103772693A CN103772693A CN201410032943.2A CN201410032943A CN103772693A CN 103772693 A CN103772693 A CN 103772693A CN 201410032943 A CN201410032943 A CN 201410032943A CN 103772693 A CN103772693 A CN 103772693A
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- lignin
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- weight
- polyether polyol
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- 229920005610 lignin Polymers 0.000 title claims abstract description 40
- 229920005862 polyol Polymers 0.000 title claims abstract description 29
- 150000003077 polyols Chemical class 0.000 title claims abstract description 29
- 239000004721 Polyphenylene oxide Substances 0.000 title claims abstract description 22
- 229920000570 polyether Polymers 0.000 title claims abstract description 22
- 238000000034 method Methods 0.000 title description 5
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000003513 alkali Substances 0.000 claims abstract description 18
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000007788 liquid Substances 0.000 claims abstract description 14
- 238000002360 preparation method Methods 0.000 claims abstract description 14
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 12
- XPFVYQJUAUNWIW-UHFFFAOYSA-N furfuryl alcohol Chemical compound OCC1=CC=CO1 XPFVYQJUAUNWIW-UHFFFAOYSA-N 0.000 claims abstract description 12
- 240000008042 Zea mays Species 0.000 claims abstract description 9
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 claims abstract description 9
- 235000002017 Zea mays subsp mays Nutrition 0.000 claims abstract description 9
- 235000005822 corn Nutrition 0.000 claims abstract description 9
- 239000006227 byproduct Substances 0.000 claims abstract description 8
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 claims abstract description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000003054 catalyst Substances 0.000 claims abstract description 7
- 238000003756 stirring Methods 0.000 claims abstract description 5
- 108010059892 Cellulase Proteins 0.000 claims abstract description 4
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229940106157 cellulase Drugs 0.000 claims abstract description 4
- 239000002994 raw material Substances 0.000 claims abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims abstract 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 12
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 12
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical class CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims 3
- 238000010792 warming Methods 0.000 claims 2
- 238000001976 enzyme digestion Methods 0.000 claims 1
- 230000000704 physical effect Effects 0.000 abstract description 4
- 239000006261 foam material Substances 0.000 abstract description 3
- 229910001873 dinitrogen Inorganic materials 0.000 abstract 1
- 239000002699 waste material Substances 0.000 description 3
- 238000006047 enzymatic hydrolysis reaction Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 125000003158 alcohol group Chemical group 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- WQZGKKKJIJFFOK-DVKNGEFBSA-N alpha-D-glucose Chemical group OC[C@H]1O[C@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-DVKNGEFBSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000002440 industrial waste Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
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- Polyethers (AREA)
- Preparation Of Compounds By Using Micro-Organisms (AREA)
Abstract
本发明涉及一种木质素聚醚多元醇的制备方法，包括以下步骤：1)将以下重量份数的原料投入反应器：碱木质素30-120，水20-150，纤维素酶0.5-10，氢氧化钠0.5-3，糠醇0.1-50，糠醛1-15；将反应器升温至30-65℃，搅拌2-6小时，制得酶解改性碱木质素；2)将经过步骤1)制得的酶解改性碱木质素及液态多元醇、双金属催化剂、二甘醇、丙三醇按以下重量份数投入反应器；搅拌升温至80-120℃，由反应器底部通入少量氮气鼓泡反应，之后抽真空，向反应器中添加0.01-12份的环氧丙烷，常压密闭反应1-6小时，制得木质素聚醚多元醇。本发明的木质素聚醚多元醇的制备方法步骤简单，能够合理利用玉米深加工副产物，所制备的木质素聚醚多元醇物理性能稳定，能够用来作为新型泡沫材料，不易变形。The invention relates to a preparation method of lignin polyether polyol, comprising the following steps: 1) Putting the following raw materials into a reactor in parts by weight: 30-120 parts by weight of alkali lignin, 20-150 parts of water, and 0.5-10 parts by weight of cellulase , sodium hydroxide 0.5-3, furfuryl alcohol 0.1-50, furfural 1-15; the reactor is heated to 30-65 ° C, stirred for 2-6 hours, and the enzymolysis modified alkali lignin is obtained; 2) after step 1 ) prepared enzymatically modified alkali lignin and liquid polyol, bimetallic catalyst, diethylene glycol, and glycerol are put into the reactor according to the following parts by weight; stir and heat up to 80-120°C, and pass into the reactor bottom A small amount of nitrogen gas is bubbled for reaction, and then vacuumized, 0.01-12 parts of propylene oxide is added to the reactor, and the reaction is sealed under normal pressure for 1-6 hours to prepare lignin polyether polyol. The preparation method of the lignin polyether polyol of the present invention has simple steps, can rationally utilize by-products of corn deep processing, and the prepared lignin polyether polyol has stable physical properties, can be used as a new foam material, and is not easily deformed.
Description
技术领域technical field
本发明涉及一种木质素聚醚多元醇的制备方法。The invention relates to a preparation method of lignin polyether polyol.
背景技术Background technique
目前在制备乙二醇、丙二醇、丁醇等醇类物质时主要通过玉米制备而成，在制备过程中所产生的副产物无法合理利用，例如所产生的玉米糖渣和玉米醇渣，不管是液体或者固态，以往都属于工业废料，无法利用，并且如何安全无害处理这些废料，也是个行业难题；因此急需一种利用玉米深加工副产物来制备木质素聚醚多元醇的制备方法。At present, alcohols such as ethylene glycol, propylene glycol, and butanol are mainly prepared from corn, and the by-products produced during the preparation process cannot be rationally utilized, such as the corn sugar residue and corn alcohol residue produced, whether it is Liquid or solid, in the past, belonged to industrial waste and could not be used, and how to dispose of these waste safely and harmlessly is also an industry problem; therefore, there is an urgent need for a preparation method of using corn deep processing by-products to prepare lignin polyether polyols.
发明内容Contents of the invention
为解决上述技术问题，本发明提供一种木质素聚醚多元醇的制备方法，制备工艺简单，所制备的木质素聚醚多元醇具有很好的物理性能。In order to solve the above technical problems, the present invention provides a method for preparing lignin polyether polyol, the preparation process is simple, and the prepared lignin polyether polyol has good physical properties.
本发明的木质素聚醚多元醇的制备方法，包括以下步骤：The preparation method of lignin polyether polyol of the present invention may further comprise the steps:
1)将以下重量份数的原料投入反应器：碱木质素30-120，水20-150，纤维素酶0.5-10，氢氧化钠0.5-3，糠醇0.1-50，糠醛1-15；将反应器升温至30-65℃，搅拌2-6小时，使碱木质素发生酶解反应，制得酶解改性碱木质素；1) Put the following raw materials into the reactor in parts by weight: alkali lignin 30-120, water 20-150, cellulase 0.5-10, sodium hydroxide 0.5-3, furfuryl alcohol 0.1-50, furfural 1-15; The reactor is heated to 30-65°C and stirred for 2-6 hours, so that the alkali lignin undergoes an enzymatic hydrolysis reaction, and the enzymatically hydrolyzed modified alkali lignin is obtained;
2)将经过步骤1)制得的酶解改性碱木质素及液态多元醇、双金属催化剂、二甘醇、丙三醇按以下重量份数投入反应器：酶解改性碱木质素60-130，液态多元醇40-70，双金属催化剂0-0.003，二甘醇20-110，丙三醇30-50；搅拌升温至80-120℃，由反应器底部通入少量氮气鼓泡反应，之后抽真空，向反应器中添加0.01-12份的环氧丙烷，常压密闭反应1-6小时，制得木质素聚醚多元醇。2) Put the enzymatically modified alkali lignin and liquid polyol, bimetallic catalyst, diethylene glycol, and glycerol prepared in step 1) into the reactor in the following parts by weight: enzymatically modified alkali lignin 60 -130, liquid polyol 40-70, bimetallic catalyst 0-0.003, diethylene glycol 20-110, glycerol 30-50; stir and heat up to 80-120°C, and a small amount of nitrogen bubbles from the bottom of the reactor to react , and then vacuumize, add 0.01-12 parts of propylene oxide to the reactor, and react under normal pressure for 1-6 hours to obtain lignin polyether polyol.
本发明的木质素聚醚多元醇的制备方法，在步骤2)中：所述液态多元醇为由玉米加工丙二醇、乙二醇、丁醇的液态副产物。In the preparation method of the lignin polyether polyol of the present invention, in step 2): the liquid polyol is a liquid by-product of processing propylene glycol, ethylene glycol, and butanol from corn.
与现有技术相比本发明的有益效果为：本发明的木质素聚醚多元醇的制备方法步骤简单，能够合理利用玉米深加工副产物，工艺简单，所制备的木质素聚醚多元醇物理性能稳定，能够用来作为新型泡沫材料，不易变形，能够实现废物再利用，环保。Compared with the prior art, the beneficial effects of the present invention are: the preparation method of the lignin polyether polyol of the present invention has simple steps, can rationally utilize the by-products of corn deep processing, the process is simple, and the physical properties of the prepared lignin polyether polyol are Stable, can be used as a new type of foam material, not easy to deform, can realize waste reuse, and is environmentally friendly.
具体实施方式Detailed ways
下面结合实施例，对本发明的具体实施方式作进一步详细描述。以下实施例用于说明本发明，但不用来限制本发明的范围。Below in conjunction with the examples, the specific implementation of the present invention will be further described in detail. The following examples are used to illustrate the present invention, but are not intended to limit the scope of the present invention.
一种木质素聚醚多元醇的制备方法，包括以下步骤：A preparation method of lignin polyether polyol, comprising the following steps:
1)将以下重量份数的原料投入反应器：碱木质素30-120，水20-150，纤维素酶0.5-10，氢氧化钠0.5-3，糠醇0.1-50，糠醛1-15；将反应器升温至30-65℃，搅拌2-6小时，使碱木质素发生酶解反应，制得酶解改性碱木质素；1) Put the following raw materials into the reactor in parts by weight: alkali lignin 30-120, water 20-150, cellulase 0.5-10, sodium hydroxide 0.5-3, furfuryl alcohol 0.1-50, furfural 1-15; The reactor is heated to 30-65°C and stirred for 2-6 hours, so that the alkali lignin undergoes an enzymatic hydrolysis reaction, and the enzymatically hydrolyzed modified alkali lignin is obtained;
2)将经过步骤1)制得的酶解改性碱木质素及液态多元醇、双金属催化剂、二甘醇、丙三醇按以下重量份数投入反应器：酶解改性碱木质素60-130，液态多元醇40-70，双金属催化剂0-0.003，二甘醇20-110，丙三醇30-50；搅拌升温至80-120℃，由反应器底部通入少量氮气鼓泡反应，之后抽真空，向反应器中添加0.01-12份的环氧丙烷，常压密闭反应1-6小时，制得木质素聚醚多元醇。2) Put the enzymatically modified alkali lignin and liquid polyol, bimetallic catalyst, diethylene glycol, and glycerol prepared in step 1) into the reactor in the following parts by weight: enzymatically modified alkali lignin 60 -130, liquid polyol 40-70, bimetallic catalyst 0-0.003, diethylene glycol 20-110, glycerol 30-50; stir and heat up to 80-120°C, and a small amount of nitrogen is bubbled from the bottom of the reactor to react , and then vacuumize, add 0.01-12 parts of propylene oxide to the reactor, and react under normal pressure for 1-6 hours to obtain lignin polyether polyol.
本发明的木质素聚醚多元醇的制备方法，在步骤2)中：所述液态多元醇为由玉米加工丙二醇、乙二醇、丁醇的液态副产物。In the preparation method of the lignin polyether polyol of the present invention, in step 2): the liquid polyol is a liquid by-product of processing propylene glycol, ethylene glycol, and butanol from corn.
本发明的木质素聚醚多元醇的制备方法步骤简单，能够合理利用玉米深加工副产物，工艺简单，所制备的木质素聚醚多元醇物理性能稳定，能够用来作为新型泡沫材料，不易变形，能够实现废物再利用，环保。The preparation method of the lignin polyether polyol of the present invention has simple steps, can rationally utilize by-products of corn deep processing, and has a simple process, and the prepared lignin polyether polyol has stable physical properties, can be used as a new type of foam material, and is not easily deformed. Can realize waste reuse, environmental protection.
以上所述仅是本发明的优选实施方式，应当指出，对于本技术领域的普通技术人员来说，在不脱离本发明技术原理的前提下，还可以做出若干改进和变型，这些改进和变型也应视为本发明的保护范围。The above is only a preferred embodiment of the present invention, it should be pointed out that for those of ordinary skill in the art, without departing from the technical principle of the present invention, some improvements and modifications can also be made, these improvements and modifications It should also be regarded as the protection scope of the present invention.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105504203A (en) * | 2016-02-03 | 2016-04-20 | 广西吉顺能源科技有限公司 | Polyurethane rigid foam |
| CN105504204A (en) * | 2016-02-03 | 2016-04-20 | 广西吉顺能源科技有限公司 | Polyurethane heat preservation material |
| CN105504218A (en) * | 2016-02-03 | 2016-04-20 | 广西吉顺能源科技有限公司 | Solar hard foam heat-preservation material |
| CN105542104A (en) * | 2016-02-03 | 2016-05-04 | 广西吉顺能源科技有限公司 | Polyurethane hard foam thermal-insulation material |
| CN105585687A (en) * | 2016-02-03 | 2016-05-18 | 广西吉顺能源科技有限公司 | Solar thermal-insulation material |
| CN105601868A (en) * | 2016-02-03 | 2016-05-25 | 广西吉顺能源科技有限公司 | Rigid foam polyurethane thermal insulation material |
| CN105601869A (en) * | 2016-02-03 | 2016-05-25 | 广西吉顺能源科技有限公司 | Solar rigid polyurethane foam thermal insulation material |
| CN105669930A (en) * | 2016-02-03 | 2016-06-15 | 广西吉顺能源科技有限公司 | Thermal insulation material |
| CN105693973A (en) * | 2016-02-03 | 2016-06-22 | 广西吉顺能源科技有限公司 | Rigid foam thermal insulation material |
| CN105693975A (en) * | 2016-02-03 | 2016-06-22 | 广西吉顺能源科技有限公司 | Rigid polyurethane foam thermal insulation material |
| CN105693974A (en) * | 2016-02-03 | 2016-06-22 | 广西吉顺能源科技有限公司 | Solar polyurethane thermal insulation material |
| CN105693976A (en) * | 2016-02-03 | 2016-06-22 | 广西吉顺能源科技有限公司 | Polyurethane foam thermal insulation material |
| CN106562119A (en) * | 2016-10-27 | 2017-04-19 | 重庆文洪水产品养殖有限公司 | Degradable multi-stage controlled-release aquatic-product attractant particles and preparation method thereof |
| CN109265672A (en) * | 2018-09-20 | 2019-01-25 | 南京林业大学 | A method of cellulose base polyether polyol is prepared by raw material of alkali cellulose |
| CN110372854A (en) * | 2019-06-10 | 2019-10-25 | 广东奥克化学有限公司 | A kind of lignin-base polyoxyethylene ether of branched structure and preparation method thereof |
| WO2020109460A1 (en) | 2018-11-29 | 2020-06-04 | Fundacion Tecnalia Research & Innovation | Lignin-based polyols |
| CN113105261A (en) * | 2021-05-25 | 2021-07-13 | 单成敏 | Light self preservation temperature wall body |
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| CN105693974A (en) * | 2016-02-03 | 2016-06-22 | 广西吉顺能源科技有限公司 | Solar polyurethane thermal insulation material |
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| CN105542104A (en) * | 2016-02-03 | 2016-05-04 | 广西吉顺能源科技有限公司 | Polyurethane hard foam thermal-insulation material |
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| CN105504203A (en) * | 2016-02-03 | 2016-04-20 | 广西吉顺能源科技有限公司 | Polyurethane rigid foam |
| CN105693975A (en) * | 2016-02-03 | 2016-06-22 | 广西吉顺能源科技有限公司 | Rigid polyurethane foam thermal insulation material |
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| CN106562119A (en) * | 2016-10-27 | 2017-04-19 | 重庆文洪水产品养殖有限公司 | Degradable multi-stage controlled-release aquatic-product attractant particles and preparation method thereof |
| CN109265672A (en) * | 2018-09-20 | 2019-01-25 | 南京林业大学 | A method of cellulose base polyether polyol is prepared by raw material of alkali cellulose |
| WO2020109460A1 (en) | 2018-11-29 | 2020-06-04 | Fundacion Tecnalia Research & Innovation | Lignin-based polyols |
| US12195491B2 (en) | 2018-11-29 | 2025-01-14 | Fundacion Tecnalia Research & Innovation | Lignin-based polyols |
| CN110372854A (en) * | 2019-06-10 | 2019-10-25 | 广东奥克化学有限公司 | A kind of lignin-base polyoxyethylene ether of branched structure and preparation method thereof |
| CN113105261A (en) * | 2021-05-25 | 2021-07-13 | 单成敏 | Light self preservation temperature wall body |
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