JP7056987B1 - Method for preparing amphipathic lignin nanomaterials from pulped black liquor, amphipathic lignin nanomaterials, sludge cleaner - Google Patents
Method for preparing amphipathic lignin nanomaterials from pulped black liquor, amphipathic lignin nanomaterials, sludge cleaner Download PDFInfo
- Publication number
- JP7056987B1 JP7056987B1 JP2020187661A JP2020187661A JP7056987B1 JP 7056987 B1 JP7056987 B1 JP 7056987B1 JP 2020187661 A JP2020187661 A JP 2020187661A JP 2020187661 A JP2020187661 A JP 2020187661A JP 7056987 B1 JP7056987 B1 JP 7056987B1
- Authority
- JP
- Japan
- Prior art keywords
- lignin
- amphipathic
- nanomaterial
- nanoparticles
- pulped
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 229920005610 lignin Polymers 0.000 title claims abstract description 170
- 239000002086 nanomaterial Substances 0.000 title claims abstract description 56
- 239000010802 sludge Substances 0.000 title claims abstract description 45
- 238000000034 method Methods 0.000 title claims description 32
- 238000011282 treatment Methods 0.000 claims abstract description 66
- 239000002105 nanoparticle Substances 0.000 claims abstract description 60
- 239000002245 particle Substances 0.000 claims abstract description 52
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 42
- 239000000126 substance Substances 0.000 claims abstract description 41
- 230000000694 effects Effects 0.000 claims abstract description 13
- 239000004094 surface-active agent Substances 0.000 claims abstract description 13
- 238000000926 separation method Methods 0.000 claims abstract description 10
- 238000000498 ball milling Methods 0.000 claims abstract description 9
- 238000000265 homogenisation Methods 0.000 claims abstract description 8
- 239000007788 liquid Substances 0.000 claims description 38
- 230000004913 activation Effects 0.000 claims description 33
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 30
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 18
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 16
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 16
- 239000000463 material Substances 0.000 claims description 16
- 239000011734 sodium Substances 0.000 claims description 16
- -1 polyoxyethylene octylphenyl ether Polymers 0.000 claims description 14
- 239000008367 deionised water Substances 0.000 claims description 13
- 229910021641 deionized water Inorganic materials 0.000 claims description 13
- 125000002947 alkylene group Chemical group 0.000 claims description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 claims description 11
- 238000006011 modification reaction Methods 0.000 claims description 10
- 239000012459 cleaning agent Substances 0.000 claims description 9
- 229920002114 octoxynol-9 Polymers 0.000 claims description 9
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 8
- 229910017053 inorganic salt Inorganic materials 0.000 claims description 8
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 8
- 239000011780 sodium chloride Substances 0.000 claims description 8
- 239000000945 filler Substances 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 5
- 238000003916 acid precipitation Methods 0.000 claims description 5
- 239000002994 raw material Substances 0.000 claims description 5
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 4
- 239000002244 precipitate Substances 0.000 claims description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 4
- QIKIJFUVHGOQOK-UHFFFAOYSA-M (3-chloro-2-hydroxypropyl)-dimethyl-octadecylazanium;chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCCCC[N+](C)(C)CC(O)CCl QIKIJFUVHGOQOK-UHFFFAOYSA-M 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims 3
- 230000003213 activating effect Effects 0.000 claims 1
- 239000010779 crude oil Substances 0.000 abstract description 9
- 239000003599 detergent Substances 0.000 abstract description 8
- 239000007787 solid Substances 0.000 abstract description 8
- 239000011435 rock Substances 0.000 abstract description 7
- 239000003208 petroleum Substances 0.000 abstract description 5
- 230000004048 modification Effects 0.000 abstract description 4
- 238000012986 modification Methods 0.000 abstract description 4
- 238000011221 initial treatment Methods 0.000 abstract description 2
- 230000001737 promoting effect Effects 0.000 abstract description 2
- 230000029936 alkylation Effects 0.000 abstract 1
- 238000005804 alkylation reaction Methods 0.000 abstract 1
- 229910052785 arsenic Inorganic materials 0.000 abstract 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 abstract 1
- 238000010586 diagram Methods 0.000 abstract 1
- 150000003839 salts Chemical class 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 64
- 239000003921 oil Substances 0.000 description 27
- BDHFUVZGWQCTTF-UHFFFAOYSA-N sulfonic acid Chemical compound OS(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-N 0.000 description 24
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 18
- 239000000203 mixture Substances 0.000 description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 8
- 238000004140 cleaning Methods 0.000 description 8
- 230000008569 process Effects 0.000 description 7
- 235000011121 sodium hydroxide Nutrition 0.000 description 6
- 125000000542 sulfonic acid group Chemical group 0.000 description 6
- 230000010354 integration Effects 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- 241000609240 Ambelania acida Species 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 239000003513 alkali Substances 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 239000010905 bagasse Substances 0.000 description 4
- 238000005119 centrifugation Methods 0.000 description 4
- 238000000921 elemental analysis Methods 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 238000006386 neutralization reaction Methods 0.000 description 4
- 238000005502 peroxidation Methods 0.000 description 4
- 229920001732 Lignosulfonate Polymers 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 230000018109 developmental process Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 150000007522 mineralic acids Chemical class 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000006467 substitution reaction Methods 0.000 description 3
- 229920001046 Nanocellulose Polymers 0.000 description 2
- 239000010426 asphalt Substances 0.000 description 2
- JXLHNMVSKXFWAO-UHFFFAOYSA-N azane;7-fluoro-2,1,3-benzoxadiazole-4-sulfonic acid Chemical compound N.OS(=O)(=O)C1=CC=C(F)C2=NON=C12 JXLHNMVSKXFWAO-UHFFFAOYSA-N 0.000 description 2
- 238000000502 dialysis Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000004108 freeze drying Methods 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000005416 organic matter Substances 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- ODLMAHJVESYWTB-UHFFFAOYSA-N propylbenzene Chemical compound CCCC1=CC=CC=C1 ODLMAHJVESYWTB-UHFFFAOYSA-N 0.000 description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 1
- 229920002488 Hemicellulose Polymers 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000005238 degreasing Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 238000005188 flotation Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000005339 levitation Methods 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 231100000219 mutagenic Toxicity 0.000 description 1
- 230000003505 mutagenic effect Effects 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000004537 pulping Methods 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 231100000378 teratogenic Toxicity 0.000 description 1
- 230000003390 teratogenic effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
Landscapes
- Treatment Of Sludge (AREA)
- Detergent Compositions (AREA)
- Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
Abstract
【課題】パルプ化黒液に基づいて両親媒性リグニンナノ材料を調製する方法、両親媒性リグニンナノ材料、スラッジ洗浄剤を提供すること。【解決手段】石油産業における化学的スラッジ除去の技術分野に属し、アルカリリグニンをボールミリングや高圧ジェット均質化処理などの物理的な初期処理により、アルカリリグニンの分子量やサイズを調整することで、均一な粒子サイズのアルカリリグニンナノ粒子を得て、これに基づいて、アルキル化グラフト修飾などの化学的処理により、親水性と親油性の両方の性質を持つ両親媒性リグニンナノ粒子が調製される。ナノサイズ効果により、両親媒性リグニンナノ材料の比表面積が大幅に増加し、表面性能が効果的に向上し、これにより、油水界面張力を低減し、原油を乳化して岩石粒子の表面から剥離して、油－固体分離の目的を達成する。さらに、両親媒性のリグニンナノ材料は、界面活性剤と塩を配合して岩石粒子の表面の濡れ性を改善し、岩石粒子の表面を親油性から親水性にして、原油の分離を促進する。【選択図】なしPROBLEM TO BE SOLVED: To provide an amphipathic lignin nanomaterial, an amphipathic lignin nanomaterial, and a sludge detergent based on a pulped black liquor. SOLUTION: It belongs to the technical field of chemical sludge removal in the petroleum industry, and is uniform by adjusting the molecular weight and size of alkaline lignin by physical initial treatment such as ball milling and high pressure jet homogenization treatment. Alkaline lignin nanoparticles having a large particle size are obtained, and based on this, chemical treatments such as alkylation graft modification are performed to prepare arsenic lignin nanoparticles having both hydrophilic and lipophilic properties. The nanosize effect significantly increases the specific surface area of the amphipathic lignin nanomaterial, effectively improving surface performance, which reduces oil-water interfacial tension and emulsifies crude oil to separate it from the surface of rock particles. To achieve the purpose of oil-solid separation. In addition, amphipathic lignin nanomaterials combine surfactants and salts to improve the wettability of the surface of rock particles, making the surface of rock particles hydrophilic from lipophilic to promoting crude oil separation. [Selection diagram] None
Description
本発明は石油産業における化学的スラッジ除去の技術分野、特にパルプ化黒液に基づいて両親媒性リグニンナノ材料を調製する方法、両親媒性リグニンナノ材料、スラッジ洗浄剤に関する。 The present invention relates to a technical field of chemical sludge removal in the petroleum industry, particularly a method for preparing an amphipathic lignin nanomaterial based on pulped black liquor, an amphipathic lignin nanomaterial, a sludge cleaning agent.
重要な資源として、石油は国民経済の発展において重要な位置を占めている。過去３年間で、中国の原油生産量は増加してきて過去最高の年間１億９，４００万トンに達し、国家のエネルギー安全保障の確保と産業経済の持続可能な発展の促進に重要な役割を果たしてきた。しかしながら、石油資源の開発と使用中による環境汚染も無視できない問題であり、たとえば、石油の採掘と加工の過程で生成される４００万トン近くの油性スラッジには、何百種類もの有毒で有害な化合物が含まれ、一部の多環芳香族炭化水素成分及び重金属イオンには変異原性、発がん性、催奇形性があり、油性スラッジを適切に処理できなければ、自然環境や人間に取り返しのつかない害を及ぼす。 As an important resource, oil occupies an important position in the development of the national economy. Over the past three years, China's crude oil production has increased to a record high of 194 million tonnes, playing an important role in ensuring national energy security and promoting the sustainable development of the industrial economy. I've done it. However, environmental pollution from the development and use of petroleum resources is also a non-negligible problem, for example, hundreds of toxic and harmful to nearly 4 million tons of oily sludge produced during the process of oil mining and processing. Compounds are included, some polycyclic aromatic hydrocarbon components and heavy metal ions are mutagenic, carcinogenic and teratogenic, and if oily sludge cannot be properly treated, it will be restored to the natural environment and humans. It does no harm.
現在、スラッジ処理技術は主に熱分解吸収、熱水洗浄、超臨界水熱酸化技術、コンディショニング－遠心分離、溶媒抽出、電気化学技術、生物学的処理などを含む。そのうち、熱水洗浄は、主に熱アルカリ水溶液または界面活性剤を適度な濃度で含む熱水溶液を用いてスラッジを複数回洗浄し、次に空気浮選やサイクロンなどの処理設備により油、水、泥の三相分離を実現し、様々なスラッジの処理に適し、脱油効果は理想的であり、スラッジの削減と連続処理を実現でき、操作が簡単で低コストである。油性スラッジが界面活性剤の熱水溶液と混合されると、界面活性剤の高い表面活性化エネルギーは、油水層の界面張力を大幅に低減し、原油の粘性抵抗を低減し、原油の剥離と流動を容易にする。また、界面活性剤は原油を乳化し、砂表面の濡れ性を変化させる強力な能力を持って、低表面張力の作用下で、油滴が変形しやすく、細孔内の移動速度を加速し、細孔によって分離されるエネルギーを減少させ、そして熱水洗浄のスラッジ溶出効果を大幅に改善する。 Currently, sludge treatment technologies mainly include pyrolysis absorption, hot water cleaning, supercritical water thermal oxidation technology, conditioning-centrifugation, solvent extraction, electrochemical technology, biological treatment and the like. Of these, hot water washing mainly uses a hot alkaline aqueous solution or a hot aqueous solution containing a surfactant at an appropriate concentration to wash the sludge multiple times, and then oil, water, etc. using a treatment facility such as air levitation or cyclone. It realizes three-phase separation of mud, is suitable for treating various sludges, has an ideal degreasing effect, can realize sludge reduction and continuous treatment, and is easy to operate and low cost. When the oily sludge is mixed with the hot aqueous solution of the surfactant, the high surface activation energy of the surfactant significantly reduces the interfacial tension of the oil-water layer, reduces the viscous resistance of the crude oil, and the peeling and flow of the crude oil. To facilitate. In addition, surfactants have the powerful ability to emulsify crude oil and change the wettability of the sand surface, and under the action of low surface tension, oil droplets are easily deformed and accelerate the movement speed in the pores. The energy separated by the pores is reduced, and the sludge elution effect of hot water washing is greatly improved.
ナノ材料は、比表面積が大きく、表面反応性が高く、吸着能力が強いなどの優れた特性を備えており、石油産業で広く使用されている。たとえば、Ｌｉらは、カナダのオイルサンドの浮選抽出プロセス中に一定量の親水性Ｆｅ３Ｏ４ナノ粒子を追加して、鉱物表面の濡れ性を改善し、アスファルトと水の界面張力を低減し、アスファルトの回収率は１２％増加した。Ｌｉらは、研究対象としてバイオマス高分子ナノセルロースを使用し、修飾された両親媒性ナノセルロースは岩石表面にウェッジ吸着され、油膜を剥がすことができ、表面の濡れ性を変化させ、原油を乳化し、Ｏ／Ｗエマルションを形成し、流体の流れ能力を向上させる。ナノ材料が石油スラッジ分離に優れた応用の見通しを持っていることを示している。 Nanomaterials have excellent properties such as large specific surface area, high surface reactivity, and strong adsorption capacity, and are widely used in the petroleum industry. For example, Li et al. Added a certain amount of hydrophilic Fe 3 O 4 nanoparticles during the Canadian oil sands flotation process to improve the wettability of the mineral surface and reduce the interfacial tension between asphalt and water. However, the asphalt recovery rate increased by 12%. Li et al. Used biomass polymer nanocellulose as a research subject, and the modified amphipathic nanocellulose was wedge-adsorbed on the rock surface, the oil film could be peeled off, the wettability of the surface was changed, and the crude oil was emulsified. Then, an O / W emulsion is formed to improve the flow capacity of the fluid. It shows that nanomaterials have excellent application prospects for petroleum sludge separation.
リグニンは自然界で最も豊富な天然芳香族化合物であり、年間生産量は約１５００億トンである。パルプと紙の製造プロセスだけでも、リグノスルホネートやアルカリリグニンなどの約５，０００万トンという大量のリグニン副産物が毎年リサイクルされ、燃やされるか、付加価値製品に使用される。そのうち、アルカリリグニンは天然リグニンの化学構造をよりよく保持し、有機溶媒または強アルカリ水溶液に溶解でき、フェニルプロパン構造単位の疎水性骨格は疎水性を示し、フェノール性水酸基を含む弱電離基はある程度の親水性を示し、ある程度の両親媒性を示し、界面活性剤として使用される可能性がある。 Lignin is the most abundant natural aromatic compound in nature, with an annual production of about 150 billion tonnes. In the pulp and paper manufacturing process alone, large quantities of about 50 million tonnes of lignin by-products, such as lignosulfonate and alkaline lignin, are recycled, burned or used in value-added products each year. Of these, alkaline lignin better retains the chemical structure of natural lignin and can be dissolved in organic solvents or strong alkaline aqueous solutions, the hydrophobic skeleton of the phenylpropane structural unit is hydrophobic, and there are some weak ionizing groups containing phenolic hydroxyl groups. Shows hydrophilicity, shows some amphipathicity, and may be used as a surfactant.
従来技術では、製紙パルプ化黒液中のリグニンが使用される場合、改質剤は、一般に、製紙パルプ化黒液に直接注入されて、パルプ化黒液中のリグニンを修飾し、最終的に修飾リグニンを含む混合溶液の形で使用された。しかしながら製紙パルプ化黒液には、リグニン以外にも他の物質が含まれており、これらの物質の存在は、改質リグニンの性能に直接影響し、油除去に適用すると非効率的になる。 In the prior art, when lignin in paper pulped black liquor is used, the modifier is generally injected directly into the paper pulped black liquor to modify the lignin in the pulped black liquor and finally. It was used in the form of a mixed solution containing modified lignin. However, the paper pulped black liquor contains other substances besides lignin, and the presence of these substances directly affects the performance of the modified lignin, which makes it inefficient when applied to oil removal.
これを考慮して、本発明は、パルプ化黒液から両親媒性リグニンナノ材料を調製する方法、両親媒性リグニンナノ材料、スラッジ洗浄剤を提供することを目的とする。本発明では、パルプ化黒液からアルカリリグニンを直接精製して修飾し、パルプ化黒液の利用率を向上させている。その後、アルカリリグニンの修飾を継続し、得られた両親媒性リグニンナノ材料を他の物質と組み合わせることにより、高い油除去率のスラッジ洗浄剤を得る。 In view of this, it is an object of the present invention to provide a method for preparing an amphipathic lignin nanomaterial from pulped black liquor, an amphipathic lignin nanomaterial, and a sludge detergent. In the present invention, alkaline lignin is directly purified and modified from the pulped black liquor to improve the utilization rate of the pulped black liquor. Then, the modification of alkaline lignin is continued, and the obtained amphipathic lignin nanomaterial is combined with other substances to obtain a sludge cleaning agent having a high oil removal rate.
上記発明の目的を達成するために、本発明は以下の技術解決手段を提供する。 In order to achieve the object of the above invention, the present invention provides the following technical solutions.
本発明は、
パルプ化黒液を、酸沈殿、固液分離、およびボールミルして、アルカリリグニン粒子を得るステップと、
前記アルカリリグニン粒子、過酸化水素、水を混合して活性化処理液を得るステップと、前記活性化処理液を順次活性化処理、マイクロジェット均質化処理して、活性化アルカリリグニンナノ粒子を得るステップと、
活性化アルカリリグニンナノ粒子、Ｎａ２ＳＯ３、ＨＣＨＯ、および脱イオン水を混合して、スルホン化処理溶液を得て、前記スルホン化処理液をスルホメチル化修飾反応に供し、親水性スルホン酸リグニンナノ粒子を得るステップと、
前記親水性スルホン酸リグニンナノ粒子、長鎖アルキレンオキシド、イソプロパノールを混合し、化学グラフト処理液を得て、前記化学グラフト処理液を化学的にグラフトして、両親媒性のリグニンナノ材料を得るステップと
を含む、パルプ化黒液に基づいて両親媒性リグニンナノ材料を調製する方法を提供する。
The present invention
The steps of acid precipitation, solid-liquid separation, and ball milling of the pulped black liquor to obtain alkaline lignin particles,
The step of mixing the alkaline lignin particles, hydrogen peroxide, and water to obtain an activation treatment liquid, and the activation treatment liquid are sequentially activated and microjet homogenized to obtain activated alkaline lignin nanoparticles. Steps and
Activated alkaline lignin nanoparticles, Na 2 SO 3 , HCHO, and deionized water are mixed to obtain a sulfonated solution, and the sulfonated solution is subjected to a sulfomethylation modification reaction to carry out hydrophilic sulphonate lignin nanoparticles. And the steps to get
The step of mixing the hydrophilic sulfonic acid lignin nanoparticles, long-chain alkylene oxide, and isopropanol to obtain a chemical graft-treated solution, and then chemically grafting the chemical graft-treated solution to obtain an amphoteric lignin nanomaterial. Provided are methods of preparing an amphipathic lignin nanomaterial based on a pulped black liquor, including.
好ましくは、前記酸沈殿のｐＨ値は２～３である。 Preferably, the pH value of the acid precipitate is 2-3.
好ましくは、前記ボールミルのパラメータにおいては、ミルタンク内のフィラーの体積分率が２０～２５％、ボールと材料の比率が（３～６）：１、回転速度が４００～５００ｒ／ｍｉｎ、時間が４～８ｈである。 Preferably, in the parameters of the ball mill, the volume fraction of the filler in the mill tank is 20 to 25%, the ratio of the ball to the material is (3 to 6): 1, the rotation speed is 400 to 500 r / min, and the time is 4. It is ~ 8h.
好ましくは、前記活性化処理液において、アルカリリグニン粒子の質量濃度は５～１０ｇ／Ｌ、過酸化水素の体積分率は０．２～０．５％、過酸化水素の質量濃度は３０％、前記活性化処理の温度は５５～６５℃、時間は０．２～１ｈである。 Preferably, in the activation treatment liquid, the mass concentration of the alkaline lignin particles is 5 to 10 g / L, the volume fraction of hydrogen peroxide is 0.2 to 0.5%, and the mass concentration of hydrogen peroxide is 30%. The activation treatment has a temperature of 55 to 65 ° C. and a time of 0.2 to 1 h.
好ましくは、前記マイクロジェット均質化処理の圧力は３０～５０ＭＰａである。 Preferably, the pressure of the microjet homogenization treatment is 30 to 50 MPa.
好ましくは、前記スルホン化処理液において、Ｎａ２ＳＯ３の質量分率は０．１～０．４％、ＨＣＨＯの体積分率は０．２～０．５％、活性化アルカリリグニンナノ粒子の質量濃度は１０ｇ／Ｌ、前記スルホメチル化修飾反応の温度は７０～１２０℃、時間は１～４ｈである。 Preferably, in the sulfonated solution, Na 2 SO 3 has a mass fraction of 0.1 to 0.4%, HCHO has a body integration ratio of 0.2 to 0.5%, and activated alkaline lignin nanoparticles. The mass concentration is 10 g / L, the temperature of the sulfomethylation modification reaction is 70 to 120 ° C., and the time is 1 to 4 hours.
好ましくは、前記化学グラフト処理液において、親水性スルホン酸リグニンナノ粒子の質量濃度は１０ｇ／Ｌ、長鎖アルキレンオキシドの体積分率は０．２～１．０％であり、前記長鎖アルキレンオキシドは２－エポキシプロピルドデシルジメチルアンモニウムクロリド又は３－クロロ－２－ヒドロキシプロピルジメチルオクタデシルアンモニウムクロリドである。 Preferably, in the chemical graft treatment liquid, the mass concentration of the hydrophilic lignin nanoparticles sulfonic acid is 10 g / L, the volume fraction of the long-chain alkylene oxide is 0.2 to 1.0%, and the long-chain alkylene oxide is the long-chain alkylene oxide. 2-Epoxypropyldodecyldimethylammonium chloride or 3-chloro-2-hydroxypropyldimethyloctadecylammonium chloride.
好ましくは、前記化学グラフト反応のｐＨ値は１０～１２、温度は５０～６０℃、時間は１～２ｈである。 Preferably, the pH value of the chemical graft reaction is 10 to 12, the temperature is 50 to 60 ° C., and the time is 1 to 2 hours.
本発明はまた、上記技術的解決手段に記載の方法で得られた両親媒性リグニンナノ材料を提供し、前記両親媒性リグニンナノ材料の粒径は２０～１００ｎｍである。 The present invention also provides an amphipathic lignin nanomaterial obtained by the method described in the above technical solution, wherein the amphipathic lignin nanomaterial has a particle size of 20 to 100 nm.
本発明はさらにスラッジ洗浄剤を提供し、上記技術的解決手段に記載の両親媒性リグニンナノ材料１～５％、界面活性剤０．２～２％、無機塩１～１．２％、残量の水という質量百分率の成分を含む。前記界面活性剤はポリオキシエチレンオクチルフェニルエーテル及び／又はポリオキシエチレンノニルフェニルエーテルである。前記無機塩は、塩化ナトリウム、炭酸ナトリウム、および塩化マグネシウムのうちの１つまたは複数種を含む。 The present invention further provides a sludge cleaner, wherein the amphipathic lignin nanomaterials 1-5%, surfactant 0.2-2%, inorganic salt 1-1.2%, residual amount described in the above technical solution. Contains a mass-percentage component of water. The surfactant is polyoxyethylene octylphenyl ether and / or polyoxyethylene nonylphenyl ether. The inorganic salt comprises one or more of sodium chloride, sodium carbonate, and magnesium chloride.
本発明は、パルプ化黒液に基づいて両親媒性リグニンナノ材料を調製する方法を提供し、パルプ化黒液を、酸沈殿、固液分離、およびボールミルして、アルカリリグニン粒子を得るステップと、前記アルカリリグニン粒子、過酸化水素、水を混合して活性化処理液を得るステップと、前記活性化処理液を順次活性化処理、マイクロジェット均質化処理して、活性化アルカリリグニンナノ粒子を得るステップと、活性化アルカリリグニンナノ粒子、Ｎａ２ＳＯ３、ＨＣＨＯ、および脱イオン水を混合して、スルホン化処理溶液を得て、前記スルホン化処理液をスルホメチル化修飾反応に供し、親水性スルホン酸リグニンナノ粒子を得るステップと、前記親水性スルホン酸リグニンナノ粒子、長鎖アルキレンオキシド、イソプロパノールを混合し、化学グラフト処理液を得て、前記化学グラフト処理液を化学的にグラフトして、両親媒性のリグニンナノ材料を得るステップとを含む。 The present invention provides a method for preparing an amphoteric lignin nanomaterial based on a pulped black liquor, wherein the pulped black liquor is acid-precipitated, solid-liquid separated, and ball milled to obtain alkaline lignin particles. The step of mixing the alkaline lignin particles, hydrogen peroxide, and water to obtain an activation treatment liquid, and the activation treatment liquid are sequentially activated and microjet homogenized to obtain activated alkaline lignin nanoparticles. The step is mixed with activated alkaline lignin nanoparticles, Na 2 SO 3 , HCHO, and deionized water to obtain a sulfonated solution, and the sulfonated solution is subjected to a sulfomethylation modification reaction to carry out a hydrophilic sulfone. The step of obtaining acid lignin nanoparticles is mixed with the hydrophilic lignin sulfonate nanoparticles, long-chain alkylene oxide, and isopropanol to obtain a chemical graft-treated solution, and the chemical graft-treated solution is chemically grafted to be amphoteric. Includes steps to obtain lignin nanomaterials.
本発明では、パルプ化黒液におけるリグニンをボールミリングや高圧ジェット均質化処理などの物理的な初期処理により、アルカリリグニンの分子量やサイズを調整することで、均一な粒子サイズのアルカリリグニンナノ粒子を得て、ナノサイズ効果により、両親媒性リグニンナノ材料の比表面積が大幅に増加し、表面性能が効果的に向上し、これにより、油水界面張力を低減し、原油を乳化して岩石粒子の表面から剥離して、油固分離の目的を達成する。同時に、両親媒性リグニンナノ材料の導入により、岩石粒子の表面の濡れ性が向上し、岩石粒子の表面が親油性から親水性になり、原油の分離が促進される。 In the present invention, lignin in pulped black liquor is subjected to physical initial treatment such as ball milling or high-pressure jet homogenization treatment to adjust the molecular weight and size of alkaline lignin to produce alkaline lignin nanoparticles having a uniform particle size. As a result, the nanosize effect significantly increases the specific surface area of the amphoteric lignin nanomaterial and effectively improves the surface performance, thereby reducing the oil-water interfacial tension and emulsifying the crude oil to the surface of the rock particles. To achieve the purpose of oil solid separation. At the same time, the introduction of the amphipathic lignin nanomaterial improves the wettability of the surface of the rock particles, changes the surface of the rock particles from lipophilic to hydrophilic, and promotes the separation of crude oil.
本発明はまた、上記技術的解決手段に記載の方法で得られた両親媒性リグニンナノ材料を提供し、上記の方法により、本発明は、黒色パルプ化液中のアルカリリグニン成分を抽出し、次いでスルホン化および化学グラフト反応を受けて、アルカリリグニンに親水性および親油性基をグラフトし、最終的なリグニンナノ材料を両親媒性にし、スラッジ洗浄液に使用すると効果的に油を除去できる。 The present invention also provides an amphipathic lignin nanomaterial obtained by the method described in the above technical solution, wherein the present invention extracts the alkaline lignin component in the black pulped liquid and then by the above method. After undergoing sulfonated and chemically grafted reactions, hydrophilic and lipophilic groups are grafted onto alkaline lignin, the final lignin nanomaterial is amphipathic, and oil can be effectively removed when used in sludge cleaning solutions.
本発明はさらにスラッジ洗浄剤を提供し、上記技術的解決手段によって提供される両親媒性リグニンナノ材料をポリオキシエチレンオクチルフェニルエーテル及び／又はポリオキシエチレンノニルフェニルエーテルと組み合わせて使用すると、スラッジに対する洗浄剤の油除去率が向上する。 The present invention further provides a sludge cleaning agent, and when the amphipathic lignin nanomaterial provided by the above technical solution is used in combination with polyoxyethylene octylphenyl ether and / or polyoxyethylene nonylphenyl ether, cleaning against sludge. The oil removal rate of the agent is improved.
本発明は、
パルプ化黒液を、酸沈殿、固液分離、およびボールミルして、アルカリリグニン粒子を得るステップと、
前記アルカリリグニン粒子、過酸化水素、水を混合して活性化処理液を得るステップと、前記活性化処理液を順次活性化処理、マイクロジェット均質化処理して、活性化アルカリリグニンナノ粒子を得るステップと、
活性化アルカリリグニンナノ粒子、Ｎａ２ＳＯ３、ＨＣＨＯ、および脱イオン水を混合して、スルホン化処理溶液を得て、前記スルホン化処理液をスルホメチル化修飾反応に供し、親水性スルホン酸リグニンナノ粒子を得るステップと、
前記親水性スルホン酸リグニンナノ粒子、長鎖アルキレンオキシド、イソプロパノールを混合し、化学グラフト処理液を得て、前記化学グラフト処理液を化学的にグラフトして、両親媒性のリグニンナノ材料を得るステップと
を含む、パルプ化黒液に基づいて両親媒性リグニンナノ材料を調製する方法を提供する。
The present invention
The steps of acid precipitation, solid-liquid separation, and ball milling of the pulped black liquor to obtain alkaline lignin particles,
The step of mixing the alkaline lignin particles, hydrogen peroxide, and water to obtain an activation treatment liquid, and the activation treatment liquid are sequentially activated and microjet homogenized to obtain activated alkaline lignin nanoparticles. Steps and
Activated alkaline lignin nanoparticles, Na 2 SO 3 , HCHO, and deionized water are mixed to obtain a sulfonated solution, and the sulfonated solution is subjected to a sulfomethylation modification reaction to carry out hydrophilic sulfonic acid lignin nanoparticles. And the steps to get
The step of mixing the hydrophilic sulfonic acid lignin nanoparticles, long-chain alkylene oxide, and isopropanol to obtain a chemical graft-treated solution, and then chemically grafting the chemical graft-treated solution to obtain an amphoteric lignin nanomaterial. Provided are methods of preparing an amphoteric lignin nanomaterial based on a pulped black liquor, including.
本発明のパルプ化黒液を、酸沈殿、固液分離、およびボールミルして、アルカリリグニン粒子を得る。 The pulped black liquor of the present invention is acid-precipitated, solid-liquid separated, and ball-milled to obtain alkaline lignin particles.
本発明において、前記パルプ化黒液は、好ましくは苛性ソーダパルプ化からのものであり、前記パルプ化黒液の固形分は、好ましくは２０～３０％のアルカリリグニン、３５～５０％の有機物、および３０～３５％の無機物という質量百分率の物質を含む。前記有機物は、好ましくはセルロース、ヘミセルロース、有機酸または色素を含む。 In the present invention, the pulped black liquor is preferably from caustic soda pulping, and the solid content of the pulped black liquor is preferably 20 to 30% alkaline lignin, 35 to 50% organic matter, and It contains 30-35% inorganic substances with a mass percentage. The organic matter preferably contains cellulose, hemicellulose, an organic acid or a dye.
本発明において、前記酸沈殿のｐＨは、好ましくは２～３、より好ましくは２．５である。前記酸沈殿のための試薬は、好ましくは無機酸であり、本発明は、パルプ化黒液のｐＨを２～３に調整することができれば、前記無機酸の具体的な種類、無機酸の濃度、添加量を特に限定しない。 In the present invention, the pH of the acid precipitate is preferably 2-3, more preferably 2.5. The reagent for acid precipitation is preferably an inorganic acid, and in the present invention, if the pH of the pulped black liquid can be adjusted to 2 to 3, the specific type of the inorganic acid and the concentration of the inorganic acid can be adjusted. , The amount of addition is not particularly limited.
本発明では、酸沈殿後、好ましくは得られた原料液を熟成し、前記熟成の温度は、好ましくは室温、時間は、好ましくは１～３ｈである。本発明において、前記酸沈殿はパルプ化黒液中のアルカリリグニン成分を精製および分離し、両親媒性リグニンの油除去効率を効果的に改善できる。 In the present invention, after acid precipitation, the obtained raw material liquid is preferably aged, and the aging temperature is preferably room temperature and the time is preferably 1 to 3 hours. In the present invention, the acid precipitate can purify and separate the alkaline lignin component in the pulped black liquor, and can effectively improve the oil removal efficiency of the amphoteric lignin.
本発明において、前記固液分離は、好ましくは遠心分離、遠心分離の回転速度は、好ましくは４０００ｒ／ｍｉｎ、遠心分離時間は、好ましくは２０ｍｉｎである。 In the present invention, the solid-liquid separation is preferably centrifugation, the rotation speed of centrifugation is preferably 4000 r / min, and the centrifugation time is preferably 20 min.
本発明では、固液分離後、好ましくは得られた固体を洗浄し、前記洗浄試薬は、好ましくは水、前記洗浄回数は、好ましくは３～６回である。 In the present invention, after solid-liquid separation, the obtained solid is preferably washed, the washing reagent is preferably water, and the number of washings is preferably 3 to 6 times.
洗浄後、本発明は好ましくは洗浄された製品を乾燥させ、本発明は、その中のすべての水を除去することができる限り、前記乾燥パラメータを特に限定しない。 After washing, the present invention preferably dries the washed product, and the present invention does not particularly limit the drying parameters as long as all the water in the washed product can be removed.
本発明において、前記ボールミルのパラメータについては、ミルタンク内のフィラーの体積分率が好ましくは２０～２５％、より好ましくは２２～２３％、ボールと材料の比率が好ましくは（３～６）：１、より好ましくは（４～５）：１、回転速度が好ましくは４００～５００ｒ／ｍｉｎ、時間が好ましくは４～８ｈである。本発明において、ボールミル粉砕後、得られるアルカリリグニン粒子の粒径は、好ましくは１０～８０μｍである。本発明において、前記ボールミルは、アルカリリグニンの粒径を小さくすることができ、これは、後続のマイクロジェット均質化処理に便利である。 In the present invention, regarding the parameters of the ball mill, the volume fraction of the filler in the mill tank is preferably 20 to 25%, more preferably 22 to 23%, and the ratio of the ball to the material is preferably (3 to 6): 1. , More preferably (4 to 5): 1, the rotation speed is preferably 400 to 500 r / min, and the time is preferably 4 to 8 h. In the present invention, the particle size of the alkaline lignin particles obtained after pulverizing with a ball mill is preferably 10 to 80 μm. In the present invention, the ball mill can reduce the particle size of alkaline lignin, which is convenient for the subsequent microjet homogenization treatment.
アルカリリグニン粒子が得られた後、本発明は、前記アルカリリグニン粒子、過酸化水素および水を混合して、活性化処理溶液を得る。前記活性化処理液を順次活性化処理、マイクロジェット均質化処理して、活性化アルカリリグニンナノ粒子を得る。 After the alkaline lignin particles are obtained, the present invention mixes the alkaline lignin particles, hydrogen peroxide and water to obtain an activation treatment solution. The activation treatment liquid is sequentially activated and microjet homogenized to obtain activated alkaline lignin nanoparticles.
本発明において、前記活性化処理液において、アルカリリグニン粒子の質量濃度は、好ましくは５～１０ｇ／Ｌ、過酸化水素の体積分率は、好ましくは０．２～０．５％、より好ましくは０．３～０．４％、前記過酸化水素の質量濃度は、好ましくは３０％である。本発明において、前記活性化処理の温度は、好ましくは５５～６５℃、時間は、好ましくは０．２～１ｈである。本発明において、前記活性化により、アルカリリグニン粒子の分子量が減少し、フェノール性水酸基の数が増加し、後続の化学グラフト修飾ステップでのアルカリリグニンの反応活性が向上できる。 In the present invention, in the activation treatment liquid, the mass concentration of the alkaline lignin particles is preferably 5 to 10 g / L, and the volume fraction of hydrogen peroxide is preferably 0.2 to 0.5%, more preferably. The mass concentration of hydrogen peroxide is 0.3 to 0.4%, preferably 30%. In the present invention, the temperature of the activation treatment is preferably 55 to 65 ° C., and the time is preferably 0.2 to 1 h. In the present invention, the activation reduces the molecular weight of the alkaline lignin particles, increases the number of phenolic hydroxyl groups, and improves the reaction activity of alkaline lignin in the subsequent chemical graft modification step.
本発明では、活性化処理が終了した後、好ましくは活性化処理により得られた材料に直接マイクロジェット均質化処理を施す。 In the present invention, after the activation treatment is completed, preferably, the material obtained by the activation treatment is directly subjected to the microjet homogenization treatment.
本発明において、前記マイクロジェット均質化処理は、好ましくは高圧マイクロジェットホモジナイザーで行われる。前記マイクロジェット均質化処理の圧力は、好ましくは３０～５０ＭＰａ、より好ましくは４０ＭＰａである。本発明において、活性化処理により得られた材料は、好ましくは、高圧マイクロジェットホモジナイザーで６～８回循環均質化する。本発明は、高剪断、高エネルギー衝突（乱流衝突）、キャビテーション効果、および高圧マイクロジェットの他の力を使用して、活性化されたアルカリリグニン粒子をナノ処理し、アルカリリグニン粒径をさらに減少させ、ナノレベルで、かつ均一に分散した活性化アルカリリグニンナノ粒子を得ることができる。 In the present invention, the microjet homogenization treatment is preferably carried out with a high pressure microjet homogenizer. The pressure of the microjet homogenization treatment is preferably 30 to 50 MPa, more preferably 40 MPa. In the present invention, the material obtained by the activation treatment is preferably circulated and homogenized 6 to 8 times with a high pressure microjet homogenizer. The present invention uses high shear, high energy collisions (turbulent collisions), cavitation effects, and other forces of high pressure microjets to nanoprocess the activated alkaline lignin particles to further increase the alkaline lignin particle size. Activated alkaline lignin nanoparticles that are reduced and dispersed at the nano level and uniformly can be obtained.
本発明において、前記活性化アルカリリグニンナノ顆粒の直径は、好ましくは２０～１００ｎｍ、重量平均分子量は、好ましくは１０００～３０００である。 In the present invention, the diameter of the activated alkaline lignin nanogranule is preferably 20 to 100 nm, and the weight average molecular weight is preferably 1000 to 3000.
活性化アルカリリグニンナノ顆粒を得た後、本発明は前記活性化アルカリリグニンナノ粒子、Ｎａ２ＳＯ３、ＨＣＨＯ、および脱イオン水を混合して、スルホン化処理溶液を得て、前記スルホン化処理液をスルホメチル化修飾反応に供し、親水性スルホン酸リグニンナノ粒子を得る。 After obtaining activated alkaline lignin nanoparticles, the present invention mixes the activated alkaline lignin nanoparticles, Na 2SO 3 , HCHO, and deionized water to obtain a sulfonated solution, and the sulfonated treatment. The solution is subjected to a sulfomethylation modification reaction to obtain hydrophilic lignin nanoparticles sulfonate.
本発明において、前記スルホン化処理液において、Ｎａ２ＳＯ３の質量分率は、好ましくは０．１～０．４％、より好ましくは０．２～０．３％である。ＨＣＨＯの体積分率は、好ましくは０．２～０．５％、より好ましくは０．３～０．４％である。活性化アルカリリグニンナノ粒子の質量濃度は、好ましくは１０ｇ／Ｌである。本発明において、前記スルホメチル化修飾反応の温度は、好ましくは７０～１２０℃、時間は、好ましくは１～４時間である。 In the present invention, the mass fraction of Na 2 SO 3 in the sulfonated solution is preferably 0.1 to 0.4%, more preferably 0.2 to 0.3%. The volume fraction of HCHO is preferably 0.2 to 0.5%, more preferably 0.3 to 0.4%. The mass concentration of the activated alkaline lignin nanoparticles is preferably 10 g / L. In the present invention, the temperature of the sulfomethylation modification reaction is preferably 70 to 120 ° C., and the time is preferably 1 to 4 hours.
本発明は、スルホン化処理液がスルホメチル化修飾反応を行った後、好ましくは得られた反応原料液を後処理することを含む。前記後処理は、好ましくは得られた反応原料液を４０００ｒ／ｍｉｎで２０ｍｉｎ遠心分離して不溶物を除去し、溶液のｐＨ値を２～３に調整し、リグニンを沈殿させ、真空フィルターでろ過し、５０℃の一定温度で乾燥させて親水性スルホン酸リグニンナノ粒子を得るステップを含む。 The present invention comprises post-treating the reaction raw material solution preferably obtained after the sulfonated solution undergoes a sulfomethylation modification reaction. In the post-treatment, preferably, the obtained reaction raw material solution is centrifuged at 4000 r / min for 20 minutes to remove insoluble matter, the pH value of the solution is adjusted to 2 to 3, lignin is precipitated, and the mixture is filtered through a vacuum filter. It comprises the step of drying at a constant temperature of 50 ° C. to obtain hydrophilic lignin sulfonate nanoparticles.
本発明において、得られた親水性スルホン酸リグニンナノ粒子のスルホン酸基含有量は、好ましくは１．２０～２．４０ｍｍｏｌ／ｇである。 In the present invention, the sulfonic acid group content of the obtained hydrophilic lignin nanoparticles of sulfonic acid is preferably 1.20 to 2.40 mmol / g.
本発明において、前記スルホメチル化修飾反応は、親水性スルホン酸基をリグニンベンゼン環の構造単位に導入して、スルホン酸リグニンナノ粒子に特定の親水性を付与することができる。 In the present invention, the sulfomethylation modification reaction can introduce a hydrophilic sulfonic acid group into the structural unit of the ligninbenzene ring to impart specific hydrophilicity to the sulphonic acid lignin nanoparticles.
親水性スルホン酸リグニンナノ粒子を得た後、本発明は前記親水性スルホン酸リグニンナノ粒子、長鎖アルキレンオキシド、イソプロパノールを混合し、化学グラフト処理液を得て、前記化学グラフト処理液を化学的にグラフトして、両親媒性のリグニンナノ材料を得る。 After obtaining hydrophilic sulphonic acid lignin nanoparticles, the present invention mixes the hydrophilic sulphonic acid lignin nanoparticles, long-chain alkylene oxide, and isopropanol to obtain a chemical graft treatment solution, and chemically grafts the chemical graft treatment solution. Then, a parenteral lignin nanomaterial is obtained.
本発明において、前記化学グラフト処理液において、親水性スルホン酸リグニンナノ粒子の質量濃度は、好ましくは１０ｇ／Ｌ、長鎖アルキレンオキシドの体積分率は、好ましくは０．２～１．０％、より好ましくは０．３～０．９％、さらに好ましくは０．４～０．８％である。前記長鎖アルキレンオキシドは、好ましくは２－エポキシプロピルドデシルジメチルアンモニウムクロリド又は３－クロロ－２－ヒドロキシプロピルジメチルオクタデシルアンモニウムクロリドである。 In the present invention, in the chemical graft treatment liquid, the mass concentration of the hydrophilic lignin nanoparticles sulfonate is preferably 10 g / L, and the volume fraction of the long-chain alkylene oxide is preferably 0.2 to 1.0%. It is preferably 0.3 to 0.9%, more preferably 0.4 to 0.8%. The long chain alkylene oxide is preferably 2-epoxypropyldodecyldimethylammonium chloride or 3-chloro-2-hydroxypropyldimethyloctadecylammonium chloride.
本発明において、前記化学グラフト反応のｐＨ値は、好ましくは１０～１２、温度は、好ましくは５０～６０℃、時間は、好ましくは１～２ｈである。本発明において、前記化学グラフト反応のｐＨ値を調整するための試薬は、好ましくは、質量分率が２０％のＮａＯＨ溶液である。 In the present invention, the pH value of the chemical graft reaction is preferably 10 to 12, the temperature is preferably 50 to 60 ° C., and the time is preferably 1 to 2 hours. In the present invention, the reagent for adjusting the pH value of the chemical graft reaction is preferably a NaOH solution having a mass fraction of 20%.
本発明において、前記化学的グラフト化は、好ましくはマイクロ波シンセサイザーで行われる。 In the present invention, the chemical grafting is preferably performed on a microwave synthesizer.
化学的グラフト化が完了した後、本発明は、好ましくは、得られた原料液を透析および凍結乾燥に供する。前記透析の分子量カットオフは、好ましくは１０００Ｄａ、前記凍結乾燥の温度は、好ましくは－５０℃、時間は、好ましくは２４ｈである。 After the chemical grafting is complete, the present invention preferably subject the resulting feedstock to dialysis and lyophilization. The molecular weight cutoff of the dialysis is preferably 1000 Da, the freeze-drying temperature is preferably −50 ° C., and the time is preferably 24 hours.
本発明において、前記化学的グラフト化は親水性スルホン酸リグニンナノ粒子に特定の親油性を与えることができる。 In the present invention, the chemical grafting can impart specific lipophilicity to hydrophilic lignin nanoparticles sulphonate.
本発明はまた、上記技術的解決手段から得られた方法で得られた両親媒性リグニンナノ材料を提供し、前記両親媒性リグニンナノ材料の粒径は２０～１００ｎｍである。 The present invention also provides an amphipathic lignin nanomaterial obtained by the method obtained from the above technical solution, wherein the amphipathic lignin nanomaterial has a particle size of 20 to 100 nm.
本発明はさらにスラッジ洗浄剤を提供し、上記技術的解決手段に記載の両親媒性リグニンナノ材料１～５％、界面活性剤０．２～２％、無機塩１～１．２％、残量の水という質量百分率の成分を含む。前記界面活性剤はポリオキシエチレンオクチルフェニルエーテル及び／又はポリオキシエチレンノニルフェニルエーテルである。前記無機塩は、塩化ナトリウム、炭酸ナトリウム、および塩化マグネシウムのうちの１つまたは複数種を含む。 The present invention further provides a sludge cleaner, wherein the amphipathic lignin nanomaterials 1-5%, surfactant 0.2-2%, inorganic salt 1-1.2%, residual amount described in the above technical solution. Contains a mass-percentage component of water. The surfactant is polyoxyethylene octylphenyl ether and / or polyoxyethylene nonylphenyl ether. The inorganic salt comprises one or more of sodium chloride, sodium carbonate, and magnesium chloride.
本発明によって提供されるスラッジ洗浄剤は、上記技術的解決手段に記載の、質量百分率が１～５％である両親媒性リグニンナノ材料を含み、好ましくは２～４％、より好ましくは３％である。 The sludge cleaner provided by the present invention comprises an amphipathic lignin nanomaterial having a mass percentage of 1-5%, preferably 2-4%, more preferably 3%, as described in the technical solution. be.
本発明が提供するスラッジ洗浄剤は、質量百分率が０．２～２％、好ましくは１．０～１．５％の界面活性剤を含む。前記界面活性剤はポリオキシエチレンオクチルフェニルエーテル及び／又はポリオキシエチレンノニルフェニルエーテルである。 The sludge detergent provided by the present invention contains a surfactant having a mass percentage of 0.2 to 2%, preferably 1.0 to 1.5%. The surfactant is polyoxyethylene octylphenyl ether and / or polyoxyethylene nonylphenyl ether.
本発明により提供されるスラッジ洗浄剤は、質量百分率が１．０～１．２％の無機塩を含み、好ましくは１．１％である。前記無機塩は、好ましくは塩化ナトリウム、炭酸ナトリウム、および塩化マグネシウムのうちの１つまたは複数種を含む。 The sludge detergent provided by the present invention contains an inorganic salt having a mass percentage of 1.0 to 1.2%, preferably 1.1%. The inorganic salt preferably comprises one or more of sodium chloride, sodium carbonate, and magnesium chloride.
本発明は、前記スラッジ洗浄剤の調製方法を特に限定するものではなく、当業者に周知の混合物調製方法により調製すればよい。 The present invention does not particularly limit the method for preparing the sludge detergent, and may be prepared by a mixture preparation method well known to those skilled in the art.
本発明をさらに説明するために、本発明によって提供されるパルプ化黒液に基づいて両親媒性リグニンナノ材料を調製する方法、両親媒性リグニンナノ材料、およびスラッジ洗浄剤を実施例と併せて以下に詳細に説明し、それらは、本発明の保護範囲を限定するものと見なされることはできない。 To further illustrate the invention, a method of preparing an amphipathic lignin nanomaterial based on the pulped black liquor provided by the present invention, an amphipathic lignin nanomaterial, and a sludge cleaning agent are described below together with examples. Explained in detail, they cannot be considered to limit the scope of protection of the invention.
実施例１：
撹拌されているバガスアルカリパルプ化黒液に塩酸または硫酸を滴下し、溶液のｐＨ値を３に調整し、２ｈ熟成させ、４０００ｒ／ｍｉｎで２０分間遠心分離し、得られた固形分を水洗して中性とした後、４０℃で乾燥させ、乾燥した材料を遊星ボールミルに移し、処理プロセスは次のとおりであった。ボールミルタンクフィラーの体積分率は２５％、ボールミル回転速度は４００ｒ／ｍｉｎ、ボールミリング時間は４ｈ、ボールと材料の比率は３：１で、粒径８０μｍのアルカリリグニン粒子が得られた。
Example 1:
Hydrochloric acid or sulfuric acid is added dropwise to the stirred bagasse alkaline pulped black liquor, the pH value of the solution is adjusted to 3, the mixture is aged for 2 hours, centrifuged at 4000 r / min for 20 minutes, and the obtained solid content is washed with water. After neutralization, the material was dried at 40 ° C. and the dried material was transferred to a planetary ball mill, and the treatment process was as follows. The volume fraction of the ball mill tank filler was 25%, the ball mill rotation speed was 400 r / min, the ball milling time was 4 hours, the ratio of the ball to the material was 3: 1, and alkaline lignin particles having a particle size of 80 μm were obtained.
アルカリリグニン粒子、過酸化水素（質量濃度が３０％）を脱イオン水と混合し、活性化処理液を得て、前記活性化処理液において、アルカリリグニン粒子の質量濃度は１０ｇ／Ｌ、過酸化水素の体積分率は０．２％であり、前記活性化処理液を５５℃で０．２ｈ活性化した後、高圧マイクロジェットホモジナイザーに移し、３０ＭＰａの圧力下で６回均質化し、直径１００ｎｍ、分子量３０００の活性化アルカリリグニンナノ粒子が得られた。 Alkaline lignin particles and hydrogen peroxide (mass concentration is 30%) are mixed with deionized water to obtain an activation treatment liquid. In the activation treatment liquid, the mass concentration of the alkali lignin particles is 10 g / L and peroxidation. The volume fraction of hydrogen is 0.2%, and the activation treatment liquid is activated at 55 ° C. for 0.2 h, transferred to a high-pressure microjet homogenizer, homogenized 6 times under a pressure of 30 MPa, and has a diameter of 100 nm. Activated alkaline lignin nanoparticles having a molecular weight of 3000 were obtained.
活性化アルカリリグニンナノ粒子、Ｎａ２ＳＯ３、ＨＣＨＯ、および脱イオン水を混合して、スルホン化処理溶液を得て、前記スルホン化処理液において、活性化アルカリリグニンナノ粒子の質量濃度は１０ｇ／Ｌ、Ｎａ２ＳＯ３の質量分率は０．１％、ＨＣＨＯの体積分率は０．２％であり、スルホン化処理液を７０℃で４ｈスルホメチル化により修飾した後、親水性スルホン酸リグニンナノ粒子が得られ、前記親水性スルホン酸リグニンナノ粒子のスルホン酸基含有量は、１．２０ｍｍｏｌ／ｇであった。 Activated alkaline lignin nanoparticles, Na 2 SO 3 , HCHO, and deionized water were mixed to obtain a sulfonated solution, and in the sulfonated solution, the mass concentration of the activated alkaline lignin nanoparticles was 10 g / g. The mass fraction of L and Na 2 SO 3 is 0.1%, the body integration ratio of HCHO is 0.2%, and after modifying the sulfonated solution by 4h sulfomethylation at 70 ° C., the hydrophilic sulphonic acid lignin nano The particles were obtained, and the sulfonic acid group content of the hydrophilic sulphonic acid lignin nanoparticles was 1.20 mmol / g.
前記親水性スルホン酸リグニンナノ粒子、２－エポキシプロピルドデシルジメチルアンモニウムクロリド及びイソプロパノールを混合し、化学グラフト処理液を得て、前記化学グラフト処理液において、親水性スルホン酸リグニンナノ粒子の濃度は１０ｇ／Ｌ、２－エポキシプロピルドデシルジメチルアンモニウムクロリドの体積分率は０．２％であり、質量比率２０％ＮａＯＨ溶液を使用して、化学グラフト処理液のｐＨを１２に調整し、マイクロ波シンセサイザーで５０℃に昇温し、１ｈ反応させた後、透析して－５０℃で２４ｈ凍結乾燥して、両親媒性リグニンナノ材料を得て、元素分析によるＮ含有量は２．０％であった。 The hydrophilic sulfonic acid lignin nanoparticles, 2-epoxypropyldodecyldimethylammonium chloride and isopropanol were mixed to obtain a chemical graft-treated solution, and the concentration of the hydrophilic sulfonic acid lignin nanoparticles in the chemical graft-treated solution was 10 g / L. 2-Epoxypropyldodecyldimethylammonium chloride has a volume fraction of 0.2% and a 20% mass ratio NaOH solution is used to adjust the pH of the chemical graft treatment to 12 and to 50 ° C. with a microwave synthesizer. The temperature was raised, the reaction was carried out for 1 h, and the mixture was dialyzed and freeze-dried at −50 ° C. for 24 hours to obtain an amphoteric lignin nanomaterial, and the N content by elemental analysis was 2.0%.
スラッジ洗浄剤であって、得られた両親媒性リグニンナノ材料０．１％、ポリオキシエチレンオクチルフェニルエーテル０．０２％、塩化ナトリウム０．５％及び残量の洗浄水という質量分率の成分を含む。 A sludge cleaning agent containing 0.1% of the obtained amphipathic lignin nanomaterial, 0.02% of polyoxyethylene octylphenyl ether, 0.5% of sodium chloride, and the remaining amount of cleaning water. include.
スラッジ洗浄剤の油除去率試験には、
油性スラッジを１０５℃で一定の重量になるまで乾燥させ、粉砕して８０メッシュのふるいに通して、油性スラッジの粉末を取得し、重量を量ってｍ０として記録したステップＳ１と、
１００ｇの油性スラッジ粉末を１００ｇのスラッジ洗浄剤と混合し、ｐＨを１０に調整し、７０℃の一定温度で６０ｍｉｎ撹拌し、遠心機に移し、２０００ｒｍｐで１５ｍｉｎ遠心し、油層、水層、泥層を取得し、油層と水層を取り除いた後、下部の沈殿物をオーブンに入れて一定の重量になるまで乾燥させ、重量を量ってｍ１として記録し、対照群は等量の蒸留水であった。油除去率Ｒ％は次式により算出し、結果を表１に示したステップＳ２と
を含む。
For the oil removal rate test of sludge cleaner,
Step S1 in which the oily sludge was dried at 105 ° C. to a certain weight, crushed and passed through an 80 mesh sieve to obtain the oily sludge powder, weighed and recorded as m0 .
Mix 100 g of oily sludge powder with 100 g of sludge cleaner, adjust the pH to 10, stir for 60 min at a constant temperature of 70 ° C., transfer to a centrifuge, centrifuge at 2000 rpm for 15 min, oil layer, water layer, mud layer. After removing the oil layer and the aqueous layer, the lower sediment was placed in an oven and dried to a certain weight, weighed and recorded as m 1 , and the control group was an equal amount of distilled water. Met. The oil removal rate R% is calculated by the following formula, and the result includes step S2 shown in Table 1.
表１のデータは、油性スラッジを洗浄するプロセスに特定の質量のスラッジ洗浄剤を追加すると、油の除去率が大幅に向上することを示し、高い表面活性を有する両親媒性リグニンナノ材料は、土壌表面のスラッジとの良好な結合効果を有し、界面張力を低減することにより、良好な油除去効果が達成されることを示していた。 The data in Table 1 show that the addition of a specific mass of sludge cleaner to the process of cleaning oily sludge significantly improves the oil removal rate, and the amphipathic lignin nanomaterials with high surface activity are soil. It has been shown that it has a good bonding effect with surface sludge and a good oil removing effect is achieved by reducing the interfacial tension.
実施例２：
撹拌されているバガスアルカリパルプ化黒液に塩酸または硫酸を滴下し、溶液のｐＨ値を３に調整し、２ｈ熟成させ、４０００ｒ／ｍｉｎで２０分間遠心分離し、得られた固形分を水洗して中性とした後、４０℃で乾燥させ、乾燥した材料を遊星ボールミルに移し、処理プロセスは次のとおりであった。ボールミルタンクフィラーの体積分率は２４％、ボールミル回転速度は４２５ｒ／ｍｉｎ、ボールミリング時間は５ｈ、ボールと材料の比率は４：１で、粒径６０μｍのアルカリリグニン粒子が得られた。
Example 2:
Hydrochloric acid or sulfuric acid is added dropwise to the stirred bagasse alkaline pulped black liquor, the pH value of the solution is adjusted to 3, the mixture is aged for 2 hours, centrifuged at 4000 r / min for 20 minutes, and the obtained solid content is washed with water. After neutralization, the material was dried at 40 ° C. and the dried material was transferred to a planetary ball mill, and the treatment process was as follows. The volume fraction of the ball mill tank filler was 24%, the ball mill rotation speed was 425 r / min, the ball milling time was 5 hours, the ratio of the ball to the material was 4: 1, and alkaline lignin particles having a particle size of 60 μm were obtained.
アルカリリグニン粒子、過酸化水素（質量濃度が３０％）を脱イオン水と混合し、活性化処理液を得て、前記活性化処理液において、アルカリリグニン粒子の質量濃度は１０ｇ／Ｌ、過酸化水素の体積分率は０．３％であり、前記活性化処理液を８０℃で０．６ｈ活性化した後、高圧マイクロジェットホモジナイザーに移し、４０ＭＰａの圧力下で６回均質化し、直径１００ｎｍ、分子量２２００の活性化アルカリリグニンナノ粒子が得られた。 Alkaline lignin particles and hydrogen peroxide (mass concentration is 30%) are mixed with deionized water to obtain an activation treatment liquid. In the activation treatment liquid, the mass concentration of the alkali lignin particles is 10 g / L and peroxidation. The volume fraction of hydrogen is 0.3%, and the activation treatment liquid is activated at 80 ° C. for 0.6 h, transferred to a high-pressure microjet homogenizer, homogenized 6 times under a pressure of 40 MPa, and has a diameter of 100 nm. Activated alkaline lignin nanoparticles with a molecular weight of 2200 were obtained.
活性化アルカリリグニンナノ粒子、Ｎａ２ＳＯ３、ＨＣＨＯ、および脱イオン水を混合して、スルホン化処理溶液を得て、前記スルホン化処理液において、活性化アルカリリグニンナノ粒子の質量濃度は１０ｇ／Ｌ、Ｎａ２ＳＯ３の質量分率は０．２％、ＨＣＨＯの体積分率は０．３％であり、スルホン化処理液を８０℃で２ｈスルホメチル化により修飾した後、親水性スルホン酸リグニンナノ粒子が得られ、前記親水性スルホン酸リグニンナノ粒子のスルホン酸基含有量は、１．８６ｍｍｏｌ／ｇであった。 Activated alkaline lignin nanoparticles, Na 2 SO 3 , HCHO, and deionized water were mixed to obtain a sulfonated solution, and in the sulfonated solution, the mass concentration of the activated alkaline lignin nanoparticles was 10 g / g. The mass fraction of L and Na 2 SO 3 is 0.2%, the body integration ratio of HCHO is 0.3%, and after modifying the sulfonated solution by 2h sulfomethylation at 80 ° C., the hydrophilic sulphonic acid lignin nano The particles were obtained, and the sulfonic acid group content of the hydrophilic sulphonic acid lignin nanoparticles was 1.86 mmol / g.
前記親水性スルホン酸リグニンナノ粒子、２－エポキシプロピルドデシルジメチルアンモニウムクロリド及びイソプロパノールを混合し、化学グラフト処理液を得て、前記化学グラフト処理液において、親水性スルホン酸リグニンナノ粒子の濃度は１０ｇ／Ｌ、２－エポキシプロピルドデシルジメチルアンモニウムクロリドの体積分率は１％であり、質量分率２０％ＮａＯＨ溶液を使用して、化学グラフト処理液のｐＨを１２に調整し、マイクロ波シンセサイザーで６０℃に昇温し、２ｈ反応させた後、透析して－５０℃で２４ｈ凍結乾燥して、両親媒性リグニンナノ材料を得て、元素分析によるＮ含有量は４．２％であった。 The hydrophilic sulfonic acid lignin nanoparticles, 2-epoxypropyldodecyldimethylammonium chloride and isopropanol were mixed to obtain a chemical graft treatment solution, and the concentration of the hydrophilic sulfonic acid lignin nanoparticles in the chemical graft treatment solution was 10 g / L. The volume fraction of 2-epoxypropylddecyldimethylammonium chloride is 1%, the pH of the chemical graft treatment solution is adjusted to 12 using a NaOH solution with a mass fraction of 20%, and the temperature is raised to 60 ° C. with a microwave synthesizer. After warming and reacting for 2 hours, the mixture was dialyzed and freeze-dried at −50 ° C. for 24 hours to obtain an amphoteric lignin nanomaterial, and the N content by elemental analysis was 4.2%.
スラッジ洗浄剤であって、得られた両親媒性リグニンナノ材料０．１％、ポリオキシエチレンオクチルフェニルエーテル０．０２％、塩化ナトリウム０．５％及び残量の洗浄水という質量分率の成分を含む。 A sludge cleaning agent containing 0.1% of the obtained amphipathic lignin nanomaterial, 0.02% of polyoxyethylene octylphenyl ether, 0.5% of sodium chloride, and the remaining amount of cleaning water. include.
実施例１の方法により、得られたスラッジ洗浄剤の油除去率を試験し、結果を表２に示した。 The oil removal rate of the obtained sludge detergent was tested by the method of Example 1, and the results are shown in Table 2.
表２のデータは、両親媒性リグニンナノ材料の直径が減少し、表面官能基の置換度が増加すると、両親媒性リグニンナノ材料の表面活性が大幅に増加し、油性スラッジの油分除去に役立ち、油分除去率がさらに向上することを示していた。 The data in Table 2 show that as the diameter of the amphipathic lignin nanomaterial decreases and the degree of substitution of surface functional groups increases, the surface activity of the amphipathic lignin nanomaterial increases significantly, helping to remove oil from oily sludge, and oil content. It was shown that the removal rate was further improved.
実施例３：
撹拌されいるバガスアルカリパルプ化黒液に塩酸または硫酸を滴下し、溶液のｐＨ値を３に調整し、２ｈ熟成させ、４０００ｒ／ｍｉｎで２０分間遠心分離し、得られた固形分を水洗して中性とした後、４０℃で乾燥させ、乾燥した材料を遊星ボールミルに移し、処理プロセスは次のとおりであった。ボールミルタンクフィラーの体積分率は２２％、ボールミル回転速度は４８０ｒ／ｍｉｎ、ボールミリング時間は６ｈ、ボールと材料の比率は５：１で、粒径３０μｍのアルカリリグニン粒子が得られた。
Example 3:
Hydrochloric acid or sulfuric acid is added dropwise to the stirred bagasse alkaline pulped black liquor, the pH value of the solution is adjusted to 3, the mixture is aged for 2 hours, centrifuged at 4000 r / min for 20 minutes, and the obtained solid content is washed with water. After neutralization, it was dried at 40 ° C. and the dried material was transferred to a planetary ball mill and the treatment process was as follows. The volume fraction of the ball mill tank filler was 22%, the ball mill rotation speed was 480 r / min, the ball milling time was 6 hours, the ratio of the ball to the material was 5: 1, and alkaline lignin particles having a particle size of 30 μm were obtained.
アルカリリグニン粒子、過酸化水素（質量濃度が３０％）を脱イオン水と混合し、活性化処理液を得て、前記活性化処理液において、アルカリリグニン粒子の質量濃度は１０ｇ／Ｌ、過酸化水素の体積分率は０．５％であり、前記活性化処理液を６０℃で０．８ｈ活性化した後、高圧マイクロジェットホモジナイザーに移し、５０ＭＰａの圧力下で６回均質化し、直径４０ｎｍ、分子量１７００の活性化アルカリリグニンナノ粒子が得られた。 Alkaline lignin particles and hydrogen peroxide (mass concentration is 30%) are mixed with deionized water to obtain an activation treatment liquid. In the activation treatment liquid, the mass concentration of the alkali lignin particles is 10 g / L and peroxidation. The volume fraction of hydrogen is 0.5%, and the activation treatment liquid is activated at 60 ° C. for 0.8 h, transferred to a high-pressure microjet homogenizer, homogenized 6 times under a pressure of 50 MPa, and has a diameter of 40 nm. Activated alkaline lignin nanoparticles with a molecular weight of 1700 were obtained.
活性化アルカリリグニンナノ粒子、Ｎａ２ＳＯ３、ＨＣＨＯ、および脱イオン水を混合して、スルホン化処理溶液を得て、前記スルホン化処理液において、活性化アルカリリグニンナノ粒子の質量濃度は１０ｇ／Ｌ、Ｎａ２ＳＯ３の質量分率は０．３％、ＨＣＨＯの体積分率は０．４％であり、スルホン化処理液を９０℃で６ｈスルホメチル化により修飾した後、親水性スルホン酸リグニンナノ粒子が得られ、前記親水性スルホン酸リグニンナノ粒子のスルホン酸基含有量は、２．４１ｍｍｏｌ／ｇであった。 Activated alkaline lignin nanoparticles, Na 2 SO 3 , HCHO, and deionized water were mixed to obtain a sulfonated solution, and in the sulfonated solution, the mass concentration of the activated alkaline lignin nanoparticles was 10 g / g. The mass fraction of L and Na 2 SO 3 is 0.3%, the body integration factor of HCHO is 0.4%, and after modifying the sulfonated solution by 6h sulfomethylation at 90 ° C., the hydrophilic sulphonic acid lignin nano The particles were obtained, and the sulfonic acid group content of the hydrophilic sulphonic acid lignin nanoparticles was 2.41 mmol / g.
前記親水性スルホン酸リグニンナノ粒子、２－エポキシプロピルドデシルジメチルアンモニウムクロリド及びイソプロパノールを混合し、化学グラフト処理液を得て、前記化学グラフト処理液において、親水性スルホン酸リグニンナノ粒子の濃度は１０ｇ／Ｌ、２－エポキシプロピルドデシルジメチルアンモニウムクロリドの体積分率は０．５％であり、質量分率２０％ＮａＯＨ溶液を使用して、化学グラフト処理液のｐＨを１２に調整し、マイクロ波シンセサイザーで６０℃に昇温し、１ｈ反応させた後、透析して－５０℃で２４ｈ凍結乾燥して、両親媒性リグニンナノ材料を得て、元素分析によるＮ含有量は３．５％であった。 The hydrophilic sulfonic acid lignin nanoparticles, 2-epoxypropyldodecyldimethylammonium chloride and isopropanol were mixed to obtain a chemical graft treatment solution, and the concentration of the hydrophilic sulfonic acid lignin nanoparticles in the chemical graft treatment solution was 10 g / L. 2-Epoxypropyldodecyldimethylammonium chloride has a volume fraction of 0.5%, a mass fraction of 20% NaOH solution was used to adjust the pH of the chemical graft treatment solution to 12, and a microwave synthesizer at 60 ° C. After the reaction was carried out for 1 h, the mixture was dialyzed and freeze-dried at −50 ° C. for 24 hours to obtain an amphoteric lignin nanomaterial, and the N content by elemental analysis was 3.5%.
スラッジ洗浄剤であって、得られた両親媒性リグニンナノ材料０．１％、ポリオキシエチレンオクチルフェニルエーテル０．０２％、塩化ナトリウム０．５％及び残量の洗浄水という質量分率の成分を含む。 A sludge cleaning agent containing 0.1% of the obtained amphipathic lignin nanomaterial, 0.02% of polyoxyethylene octylphenyl ether, 0.5% of sodium chloride, and the remaining amount of cleaning water. include.
実施例１の方法により、得られたスラッジ洗浄剤の油除去率を試験し、結果を表３に示した。 The oil removal rate of the obtained sludge detergent was tested by the method of Example 1, and the results are shown in Table 3.
表３のデータは、両親媒性リグニンナノ材料の直径が減少し、表面官能基の置換度が増加すると伴って、両親媒性リグニンナノ材料の表面活性が大幅に増加し、油性スラッジの油分除去に役立ち、油分除去率がさらに向上することを示していた。 The data in Table 3 show that as the diameter of the amphipathic lignin nanomaterial decreases and the degree of substitution of surface functional groups increases, the surface activity of the amphipathic lignin nanomaterial increases significantly, which helps to remove oil from oily sludge. It was shown that the oil removal rate was further improved.
実施例４：
撹拌されているバガスアルカリパルプ化黒液に塩酸または硫酸を滴下し、溶液のｐＨ値を３に調整し、２ｈ熟成させ、４０００ｒ／ｍｉｎで２０分間遠心分離し、得られた固形分を水洗して中性とした後、４０℃で乾燥させ、乾燥した材料を遊星ボールミルに移し、処理プロセスは次のとおりであった。ボールミルタンクフィラーの体積分率は２０％、ボールミル回転速度は５００ｒ／ｍｉｎ、ボールミリング時間は８ｈ、ボールと材料の比率は６：１で、粒径１０μｍのアルカリリグニン粒子が得られた。
Example 4:
Hydrochloric acid or sulfuric acid is added dropwise to the stirred bagasse alkaline pulped black liquor, the pH value of the solution is adjusted to 3, the mixture is aged for 2 hours, centrifuged at 4000 r / min for 20 minutes, and the obtained solid content is washed with water. After neutralization, the material was dried at 40 ° C. and the dried material was transferred to a planetary ball mill, and the treatment process was as follows. The volume fraction of the ball mill tank filler was 20%, the ball mill rotation speed was 500 r / min, the ball milling time was 8 hours, the ratio of the ball to the material was 6: 1, and alkaline lignin particles having a particle size of 10 μm were obtained.
アルカリリグニン粒子、過酸化水素（質量濃度が３０％）を脱イオン水と混合し、活性化処理液を得て、前記活性化処理液において、アルカリリグニン粒子の質量濃度は１０ｇ／Ｌ、過酸化水素の体積分率は０．５％であり、前記活性化処理液を７０℃で０．４ｈ活性化した後、高圧マイクロジェットホモジナイザーに移し、５０ＭＰａの圧力下で６回均質化し、直径２０ｎｍ、分子量１０００の活性化アルカリリグニンナノ粒子が得られた。 Alkaline lignin particles and hydrogen peroxide (mass concentration is 30%) are mixed with deionized water to obtain an activation treatment liquid. In the activation treatment liquid, the mass concentration of the alkali lignin particles is 10 g / L and peroxidation. The volume fraction of hydrogen is 0.5%, and the activation treatment liquid is activated at 70 ° C. for 0.4 h, transferred to a high-pressure microjet homogenizer, homogenized 6 times under a pressure of 50 MPa, and has a diameter of 20 nm. Activated alkaline lignin nanoparticles having a molecular weight of 1000 were obtained.
活性化アルカリリグニンナノ粒子、Ｎａ２ＳＯ３、ＨＣＨＯ、および脱イオン水を混合して、スルホン化処理溶液を得て、前記スルホン化処理液において、活性化アルカリリグニンナノ粒子の質量濃度は１０ｇ／Ｌ、Ｎａ２ＳＯ３の質量分率は０．４％、ＨＣＨＯの体積分率は０．５％であり、スルホン化処理液を１００℃で４ｈスルホメチル化により修飾した後、親水性スルホン酸リグニンナノ粒子が得られ、前記親水性スルホン酸リグニンナノ粒子のスルホン酸基含有量は、２．４０ｍｍｏｌ／ｇであった。 Activated alkaline lignin nanoparticles, Na 2 SO 3 , HCHO, and deionized water were mixed to obtain a sulfonated solution, and in the sulfonated solution, the mass concentration of the activated alkaline lignin nanoparticles was 10 g / g. The mass fraction of L and Na 2 SO 3 is 0.4%, the body integration ratio of HCHO is 0.5%, and after modifying the sulfonated solution by 4h sulfomethylation at 100 ° C., the hydrophilic sulphonic acid lignin nano The particles were obtained, and the sulfonic acid group content of the hydrophilic sulphonic acid lignin nanoparticles was 2.40 mmol / g.
前記親水性スルホン酸リグニンナノ粒子、２－エポキシプロピルドデシルジメチルアンモニウムクロリド及びイソプロパノールを混合し、化学グラフト処理液を得て、前記化学グラフト処理液において、親水性スルホン酸リグニンナノ粒子の濃度は１０ｇ／Ｌ、２－エポキシプロピルドデシルジメチルアンモニウムクロリドの体積分率は１．０％であり、質量分率２０％ＮａＯＨ溶液を使用して、化学グラフト処理液のｐＨを１２に調整し、マイクロ波シンセサイザーで６０℃に昇温し、１ｈ反応させた後、透析して－５０℃で２４ｈ凍結乾燥して、両親媒性リグニンナノ材料を得て、元素分析によるＮ含有量は１．５％であった。 The hydrophilic sulfonic acid lignin nanoparticles, 2-epoxypropyldodecyldimethylammonium chloride and isopropanol were mixed to obtain a chemical graft treatment solution, and the concentration of the hydrophilic sulfonic acid lignin nanoparticles in the chemical graft treatment solution was 10 g / L. The volume fraction of 2-epoxypropylddecyldimethylammonium chloride is 1.0%, the pH of the chemical graft treatment solution is adjusted to 12 using a NaOH solution with a mass fraction of 20%, and the temperature is 60 ° C. with a microwave synthesizer. After the reaction was carried out for 1 h, the mixture was dialyzed and freeze-dried at −50 ° C. for 24 hours to obtain an amphoteric lignin nanomaterial, and the N content by elemental analysis was 1.5%.
スラッジ洗浄剤であって、得られた両親媒性リグニンナノ材料０．１％、ポリオキシエチレンオクチルフェニルエーテル０．０２％、塩化ナトリウム０．５％及び残量の洗浄水という質量分率の成分を含む。 A sludge cleaning agent containing 0.1% of the obtained amphipathic lignin nanomaterial, 0.02% of polyoxyethylene octylphenyl ether, 0.5% of sodium chloride, and the remaining amount of cleaning water. include.
実施例１の方法により、得られたスラッジ洗浄剤の油除去率を試験し、結果を表４に示した。 The oil removal rate of the obtained sludge detergent was tested by the method of Example 1, and the results are shown in Table 4.
表４のデータは、両親媒性リグニンナノ材料の直径が減少し、表面官能基の置換度が増加すると伴って、両親媒性リグニンナノ材料の表面活性が大幅に増加し、油性スラッジの油分除去に役立ち、油分除去率がさらに向上することを示していた。 The data in Table 4 show that as the diameter of the amphipathic lignin nanomaterial decreases and the degree of substitution of surface functional groups increases, the surface activity of the amphipathic lignin nanomaterial increases significantly, which helps to remove oil from oily sludge. It was shown that the oil removal rate was further improved.
上記は本発明の好ましい実施形態にすぎず、いかなる形で本発明を限定するものではない。当業者にとって、本発明の原理から逸脱することなく、いくつかの改良および修正を行うことができ、これらの改良および修正もまた、本発明の保護範囲である。
The above is merely a preferred embodiment of the invention and does not limit the invention in any way. For those skilled in the art, some improvements and modifications can be made without departing from the principles of the invention, which are also within the scope of the invention.
Claims (10)
パルプ化黒液を、酸沈殿、固液分離、およびボールミルして、アルカリリグニン粒子を得るステップと、
前記アルカリリグニン粒子、過酸化水素、水を混合して活性化処理液を得て、前記活性化処理液を順次活性化処理、マイクロジェット均質化処理して、活性化アルカリリグニンナノ粒子を得るステップと、
前記活性化アルカリリグニンナノ粒子、Ｎａ２ＳＯ３、ＨＣＨＯ、および脱イオン水を混合して、スルホン化処理溶液を得て、前記スルホン化処理溶液をスルホメチル化修飾反応に供し、親水性スルホン酸リグニンナノ粒子を得るステップと、
前記親水性スルホン酸リグニンナノ粒子、長鎖アルキレンオキシド、イソプロパノールを混合し、化学グラフト処理液を得て、前記化学グラフト処理液を化学的にグラフトして、両親媒性のリグニンナノ材料を得るステップとを含み、
前記長鎖アルキレンオキシドは、２－エポキシプロピルドデシルジメチルアンモニウムクロリド又は３－クロロ－２－ヒドロキシプロピルジメチルオクタデシルアンモニウムクロリドである
ことを特徴とするパルプ化黒液を原料として両親媒性リグニンナノ材料を調製する方法。 A method for preparing amphipathic lignin nanomaterials using pulped black liquor as a raw material.
The steps of acid precipitation, solid-liquid separation, and ball milling of the pulped black liquor to obtain alkaline lignin particles,
A step of mixing the alkaline lignin particles, hydrogen peroxide, and water to obtain an activation treatment liquid, and sequentially activating and microjet homogenizing the activation treatment liquid to obtain activated alkaline lignin nanoparticles. When,
The activated alkaline lignin nanoparticles, Na 2 SO 3 , HCHO, and deionized water are mixed to obtain a sulfonated solution, and the sulfonated solution is subjected to a sulfomethylation modification reaction to carry out a hydrophilic sulfonic acid lignin nano. Steps to get particles and
The step of mixing the hydrophilic sulfonic acid lignin nanoparticles, long-chain alkylene oxide, and isopropanol to obtain a chemical graft-treated solution, and then chemically grafting the chemical graft-treated solution to obtain an amphoteric lignin nanomaterial. Including,
The long chain alkylene oxide is 2-epoxypropyldodecyldimethylammonium chloride or 3-chloro-2-hydroxypropyldimethyloctadecylammonium chloride.
A method for preparing an amphipathic lignin nanomaterial using pulped black liquor as a raw material.
請求項１に記載の方法。 The method according to claim 1, wherein the pH value of the acid precipitate is 2 to 3.
請求項１に記載の方法。 The parameters of the ball mill are that the volume fraction of the filler in the mill tank is 20 to 25%, the ratio of the ball to the material is (3 to 6): 1, the rotation speed is 400 to 500 r / min, and the time is 4 to 8 hours . be
The method according to claim 1.
請求項１に記載の方法。 In the activation treatment liquid, the mass concentration of the alkaline lignin particles was 5 to 10 g / L, the volume fraction of hydrogen peroxide was 0.2 to 0.5%, the mass concentration of hydrogen peroxide was 30%, and the activation. The method according to claim 1, wherein the treatment temperature is 55 to 65 ° C. and the time is 0.2 to 1 h.
請求項１または４に記載の方法。 The method according to claim 1 or 4, wherein the pressure of the microjet homogenization treatment is 30 to 50 MPa.
請求項１に記載の方法。 In the sulfonated solution , the mass fraction of Na 2 SO 3 is 0.1 to 0.4%, the volume fraction of HCHO is 0.2 to 0.5%, and the mass concentration of activated alkaline lignin nanoparticles is. The method according to claim 1, wherein the temperature of the sulfomethylation modification reaction is 10 g / L, the temperature is 70 to 120 ° C., and the time is 1 to 4 hours.
請求項１に記載の方法。 In the chemical graft treatment liquid, the mass concentration of the hydrophilic lignin nanoparticles sulfonic acid is 10 g / L, and the volume fraction of the long chain alkylene oxide is 0.2 to 1.0% .
The method according to claim 1.
請求項１または７に記載の方法。 The method according to claim 1 or 7, wherein the pH value of the reaction for chemically grafting the chemical graft treatment liquid is 10 to 12, the temperature is 50 to 60 ° C., and the time is 1 to 2 hours.
前記両親媒性リグニンナノ材料の粒径は２０～１００ｎｍである
ことを特徴とする両親媒性リグニンナノ材料。 An amphipathic lignin nanomaterial obtained by the method according to any one of claims 1 to 8.
An amphipathic lignin nanomaterial characterized in that the particle size of the amphipathic lignin nanomaterial is 20 to 100 nm.
請求項９に記載の両親媒性リグニンナノ材料１～５％、界面活性剤０．２～２％、無機塩１～１．２％、残量の水という質量百分率の成分を含み、前記界面活性剤はポリオキシエチレンオクチルフェニルエーテル及び／又はポリオキシエチレンノニルフェニルエーテルである。前記無機塩は、塩化ナトリウム、炭酸ナトリウム、および塩化マグネシウムのうちの１つまたは複数種を含む
ことを特徴とするスラッジ洗浄剤。
It ’s a sludge cleaner,
The above-mentioned surface activity contains 1 to 5% of the amphipathic lignin nanomaterial according to claim 9, 0.2 to 2% of a surfactant, 1 to 1.2% of an inorganic salt, and a remaining amount of water, which are components having a mass percentage. The agent is polyoxyethylene octylphenyl ether and / or polyoxyethylene nonylphenyl ether. The sludge cleaning agent, wherein the inorganic salt contains one or more of sodium chloride, sodium carbonate, and magnesium chloride.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2020187661A JP7056987B1 (en) | 2020-11-11 | 2020-11-11 | Method for preparing amphipathic lignin nanomaterials from pulped black liquor, amphipathic lignin nanomaterials, sludge cleaner |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2020187661A JP7056987B1 (en) | 2020-11-11 | 2020-11-11 | Method for preparing amphipathic lignin nanomaterials from pulped black liquor, amphipathic lignin nanomaterials, sludge cleaner |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP7056987B1 true JP7056987B1 (en) | 2022-04-19 |
| JP2022077047A JP2022077047A (en) | 2022-05-23 |
Family
ID=81291675
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2020187661A Active JP7056987B1 (en) | 2020-11-11 | 2020-11-11 | Method for preparing amphipathic lignin nanomaterials from pulped black liquor, amphipathic lignin nanomaterials, sludge cleaner |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP7056987B1 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114890564A (en) * | 2022-05-09 | 2022-08-12 | 广东前进牛仔布有限公司 | Recovery method of denim fabric desizing wastewater |
| CN115414302A (en) * | 2022-11-04 | 2022-12-02 | 广州市高姿化妆品有限公司 | Skin-moistening and nourishing type moisturizing emulsion and preparation method thereof |
| CN116376608A (en) * | 2023-01-05 | 2023-07-04 | 上海昶法新材料有限公司 | Coal water slurry additive taking papermaking black liquor as raw material and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005522529A (en) | 2002-01-17 | 2005-07-28 | ザ プロクター アンド ギャンブル カンパニー | Household cleaning and / or laundry detergent compositions containing lignin inducers |
| WO2019039609A1 (en) | 2017-08-24 | 2019-02-28 | 日本製紙株式会社 | Lignin derivative compound and use thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4764597A (en) * | 1987-06-15 | 1988-08-16 | Westvaco Corporation | Method for methylolation of lignin materials |
-
2020
- 2020-11-11 JP JP2020187661A patent/JP7056987B1/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005522529A (en) | 2002-01-17 | 2005-07-28 | ザ プロクター アンド ギャンブル カンパニー | Household cleaning and / or laundry detergent compositions containing lignin inducers |
| WO2019039609A1 (en) | 2017-08-24 | 2019-02-28 | 日本製紙株式会社 | Lignin derivative compound and use thereof |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114890564A (en) * | 2022-05-09 | 2022-08-12 | 广东前进牛仔布有限公司 | Recovery method of denim fabric desizing wastewater |
| CN115414302A (en) * | 2022-11-04 | 2022-12-02 | 广州市高姿化妆品有限公司 | Skin-moistening and nourishing type moisturizing emulsion and preparation method thereof |
| CN116376608A (en) * | 2023-01-05 | 2023-07-04 | 上海昶法新材料有限公司 | Coal water slurry additive taking papermaking black liquor as raw material and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2022077047A (en) | 2022-05-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP7056987B1 (en) | Method for preparing amphipathic lignin nanomaterials from pulped black liquor, amphipathic lignin nanomaterials, sludge cleaner | |
| AU2020103382A4 (en) | Method for preparing amphiphilic lignin nanoparticle based on pulping black liquor, amphiphilic lignin nanoparticle, and oil sludge detergent | |
| CN112341634B (en) | Method for preparing amphiphilic lignin nano material based on pulping black liquor, amphiphilic lignin nano material and oil sludge cleaning agent | |
| Khoo et al. | Sugarcane bagasse fiber and its cellulose nanocrystals for polymer reinforcement and heavy metal adsorbent: a review | |
| Tian et al. | Cellulose nanosphere: Preparation and applications of the novel nanocellulose | |
| Tian et al. | Pretreatment of microcrystalline cellulose in organic electrolyte solutions for enzymatic hydrolysis | |
| CN103933949A (en) | Carbon nano tube/chitosan mesoporous spherical composite material as well as preparation method thereof | |
| CN105839440A (en) | Preparation method of bagasse nanocellulose | |
| Al-Ajji et al. | Novel insights into the nanoadsorption mechanisms of crystal violet using nano-hazelnut shell from aqueous solution | |
| Culsum et al. | Isolation and characterization of cellulose nanocrystals (CNCs) from industrial denim waste using ammonium persulfate | |
| CN103087553A (en) | Maleic anhydride grafted modified halloysite nanotube and preparation method thereof | |
| CN111303643B (en) | SiO of core-shell structure2@ paraffin nanoparticle and preparation method thereof | |
| Liu et al. | Utilization of lignin separated from pre-hydrolysis liquor via horseradish peroxidase modification as an adsorbent for methylene blue removal from aqueous solution | |
| CN113413885B (en) | Magnetic microsphere adsorbent with core-shell structure and preparation method and application thereof | |
| Wang et al. | Spherical lignin nanostructures synthesis, functionalization, and removal of cationic dyes | |
| Xu et al. | Preparation and optimization of porous regenerated cellulose microspheres from cellulose tetraethyl-ammonium/urea solution for adsorption of cationic methylene blue dy | |
| US11731997B2 (en) | Method for preparing amphiphilic lignin nanomaterial based on pulping black liquor, amphiphilic lignin nanomaterial, and oil sludge detergent | |
| CN114874343B (en) | Spherical nanocrystalline cellulose based on furfural residues and preparation method thereof | |
| Kong et al. | Unveiling the interactions between biomaterials and heterocyclic dyes: a sustainable approach for wastewater treatment | |
| WO2023017687A1 (en) | Type ii unmodified cellulose microfibers, and method for manufacturing type ii unmodified cellulose microfibers and compact of same | |
| CN113292747B (en) | Preparation method and application of biomass lignin nanoshell | |
| Sun et al. | A tailored bifunctional carbon catalyst for efficient glycosidic bond fracture and selective hemicellulose fractionation | |
| CN114887593A (en) | Reversible organic bentonite and preparation method and application thereof | |
| CN112982003A (en) | Method for preparing modified nano-cellulose by ternary eutectic solvent system | |
| Bai et al. | Sucrose hybridization modification of polycationic gel to realize super-high adsorption of lignins for reusable purification of wastewater |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20201111 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20211221 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20220315 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20220329 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20220331 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 7056987 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |