WO2020215561A1 - 一种利用木质素降解产物制备分散剂的方法和应用 - Google Patents

一种利用木质素降解产物制备分散剂的方法和应用 Download PDF

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WO2020215561A1
WO2020215561A1 PCT/CN2019/102964 CN2019102964W WO2020215561A1 WO 2020215561 A1 WO2020215561 A1 WO 2020215561A1 CN 2019102964 W CN2019102964 W CN 2019102964W WO 2020215561 A1 WO2020215561 A1 WO 2020215561A1
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lignin
dispersant
degradation products
lignin degradation
preparing
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PCT/CN2019/102964
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English (en)
French (fr)
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刘明华
黄映芳
吴敏雅
刘以凡
吕源财
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福州大学
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Priority to US16/967,720 priority Critical patent/US11479722B2/en
Publication of WO2020215561A1 publication Critical patent/WO2020215561A1/zh

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
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    • C—CHEMISTRY; METALLURGY
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    • C04B20/00—Use of materials as fillers for mortars, concrete or artificial stone according to more than one of groups C04B14/00 - C04B18/00 and characterised by shape or grain distribution; Treatment of materials according to more than one of the groups C04B14/00 - C04B18/00 specially adapted to enhance their filling properties in mortars, concrete or artificial stone; Expanding or defibrillating materials
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    • C04B35/63—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B using additives specially adapted for forming the products, e.g.. binder binders
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    • C08G12/00—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
    • C08G12/02—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes
    • C08G12/04—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with acyclic or carbocyclic compounds
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    • C08G12/00—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
    • C08G12/02—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes
    • C08G12/04—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with acyclic or carbocyclic compounds
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    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G12/00—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
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    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L97/00—Compositions of lignin-containing materials
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
    • C09B67/006—Preparation of organic pigments
    • C09B67/0066—Aqueous dispersions of pigments containing only dispersing agents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
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    • B01J19/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
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    • C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
    • C04B2103/30—Water reducers, plasticisers, air-entrainers, flow improvers
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    • C—CHEMISTRY; METALLURGY
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    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
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    • C10L10/00—Use of additives to fuels or fires for particular purposes
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Definitions

  • the invention belongs to the technical field of dispersants, and specifically relates to a method and application for preparing a dispersant by using lignin degradation products.
  • Lignin, cellulose and hemicellulose are important components in plant tissues [1] and are important biomass resources.
  • lignin is widely distributed in nature and contains a rich and unique phenylpropane structure. It is a potential raw material for phenol production [2] and is also the main by-product of the pulp and paper industry.
  • more than 95% of industrial lignin is only It is simply treated as waste, such as burning to obtain low-grade heat, with extremely low utilization and wasting a lot of resources.
  • Lignin is mainly a class of complex phenolic polymers composed of 3 basic structural units (sinapyl alcohol, coniferyl alcohol, and coumarol) [3] .
  • active functional groups in lignin macromolecules such as aromatic groups, methoxy groups, and hydroxyl groups
  • the overall activity is not high, and the high quality field is limited.
  • important chemical raw materials such as phenols, alcohols, acids and hydrocarbons can be obtained [4] .
  • the ease of degradation depends on the overall The degree of etherification and condensation [5] .
  • the degradation methods of lignin are all through weakening and breaking the chemical bonds in lignin, or generating some easily reactive groups or active sites to increase the reactivity of lignin, thereby reducing the weight average molecular weight of lignin.
  • the steric hindrance of the reaction is reduced to achieve the purpose of degradation [6] .
  • the degradation of lignin mainly adopts chemical degradation methods, among which hydrothermal degradation, oxidative degradation and liquefaction degradation are the most commonly used [7] .
  • these methods generally have defects such as low degradation efficiency, harsh reaction conditions, and high cost.
  • Patent CN201710045540.5 reports a method for the preparation of moso bamboo lignin monophenol compounds with high efficiency and low pollution, which is to separate natural moso bamboo by enzymatic hydrolysis/mild acid hydrolysis to separate lignin, and then use acetic anhydride as the acetylating agent and peroxygen Acetic acid is used as a degradation agent to treat lignin to obtain monophenol compounds.
  • the method has low pollution and obtains high-yield low-molecular degradation products of lignin that retain the aromatic ring structure, but requires complicated acetylation pretreatment.
  • Patent CN201710067650.1 reports a method for preparing monophenol compounds using ammonia complexes to catalyze the degradation of lignin. Metal salts and ammonia water are used to form a stable ammonia complex solution under alkaline conditions, and oxidation is achieved under peroxide Degradation, but the overall reaction time is long, requiring high pressure conditions.
  • lignin degradation products mainly includes polyurethane foam materials, phenolic resins, epoxy resins, adhesives, biofuels, etc., which are used in molecular additives such as dispersants. Potential, but little research.
  • Xue et al. [8] used NaOH as a catalyst to degrade corncob lignin in isopropanol-water mixtures, and used degradation products to replace polyols to prepare biomass-based rigid polyurethane foams. Due to the high complexity of lignin's own structure, the yield of monophenol compounds reported in most literature on lignin degradation is generally about 10%. Therefore, improving the degradation efficiency of lignin and directional conversion of lignin gives it a greater advantage in the preparation of new high value-added products, which will greatly improve the resource utilization of lignin and provide theoretical guidance for subsequent industrial production.
  • the existing technology for degradation of lignin has a long overall reaction time, and some require the use of high temperature and high pressure conditions, special solvents and precious metal catalysts, which have high costs and even secondary pollution.
  • This patent uses lignin as a raw material to degrade and modify it into a low-molecular-weight degradation product, which is convenient for subsequent molecular reforming and chemical modification, and the product is rich in phenolic hydroxyl groups, has high chemical reaction activity, and is beneficial to the preparation of dispersant products. Used in ceramic additives, concrete water reducers, dye dispersants and coal water slurry additives, etc., it can reduce costs and broaden the use of lignin, which is of great significance to the sustainable development of social economy.
  • the present invention provides a method and application for preparing a dispersant using lignin degradation products.
  • the method for preparing the dispersant has simple process, low cost, and is suitable for industrialized production.
  • a method for preparing a dispersant using lignin degradation products includes the following steps:
  • the lignin degradation product is prepared by molecular reforming and chemical modification.
  • the step (1) preparation of lignin degradation products includes the following specific steps:
  • the step (2) preparation of dispersant includes the following specific steps:
  • the preparation step of the lignin degradation product based on the sum of mass percentages being 100%, the added mass fraction of each component is:
  • the added mass fraction of each component is:
  • the lignin includes one of bamboo, corn cob, corn stover, bagasse, cotton stalk, rice straw, wheat straw, curved willow, stalk, poplar, reed, eucalyptus, oak, birch, and masson pine Or several organic solvent lignin, enzymatic hydrolyzed lignin, ground wood lignin, sulfate lignin, sulfonate lignin, alkali lignin prepared by solvent extraction, enzymatic hydrolysis, mechanical, sulfite method or alkaline method Or natural lignin.
  • the alkali activator is one of NaOH, KOH, LiOH, Na 2 CO 3 , K 2 CO 3 and NaAlO 2 or a mixture of several in any ratio.
  • the catalyst is one of zirconium oxide, molybdenum oxide, zinc oxide, titanium oxide, and niobium oxide or several mixed in any ratio.
  • the monomer is one of sulfamic acid, p-aminobenzene sulfonic acid, sodium p-aminobenzene sulfonate, sodium cyclamate, calcium cyclamate or several mixed in any ratio .
  • crosslinking agent is one of formaldehyde, acetaldehyde, glutaraldehyde, acrolein, and trioxane, or several mixed in any ratio.
  • the relative molecular mass Mn of the dispersant prepared by the above method is 6000-30000.
  • the dispersant prepared by the above method is used as a ceramic additive, concrete water reducing agent, dye dispersant and coal water slurry additive.
  • the beneficial effects of the present invention are: the lignin is degraded into small molecular substances by microwave-assisted alkali activation and metal oxide catalytic degradation modification, the degradation process is simple, the cycle is short, and the degradation rate is high; the degradation products are directly used to pass through the molecules.
  • the dispersant is prepared after reforming and chemical modification, and the cost is low, and the prepared dispersant has good water reducing, dispersing and strengthening functions, and can be used in ceramic additives, concrete water reducers, dye dispersants and coal water slurry additives, etc.
  • Field The method effectively utilizes renewable biomass resource lignin as a raw material, and has a wide range of raw material sources, low cost, and has important socio-economic and environmental protection significance.
  • Figure 1 A flow chart of the method for preparing a dispersant using lignin degradation products in the present invention.
  • Figure 2 The relative molecular mass diagram of the dispersant prepared in Example 3.
  • a method for preparing a dispersant using lignin degradation products includes the following steps:
  • the lignin degradation product is prepared by molecular reforming and chemical modification.
  • the step (1) preparation of lignin degradation products includes the following specific steps:
  • the step (2) preparation of dispersant includes the following specific steps:
  • the preparation step of the lignin degradation product based on the sum of mass percentages being 100%, the added mass fraction of each component is:
  • the added mass fraction of each component is:
  • Isocyanate Isocyanate 0.25% ⁇ 1.25%
  • the lignin includes one of bamboo, corn cob, corn stover, bagasse, cotton stalk, rice straw, wheat straw, curved willow, awn stalk, poplar, reed, eucalyptus, oak, birch, and masson pine.
  • the alkali activator is one of NaOH, KOH, LiOH, Na 2 CO 3 , K 2 CO 3 and NaAlO 2 or a mixture of several in any ratio.
  • the catalyst is one of zirconium oxide, molybdenum oxide, zinc oxide, titanium oxide, and niobium oxide or several mixed in any ratio.
  • the monomer is one of sulfamic acid, p-aminobenzene sulfonic acid, sodium p-aminobenzene sulfonate, sodium cyclamate, calcium cyclamate or several mixed in any ratio .
  • crosslinking agent is one of formaldehyde, acetaldehyde, glutaraldehyde, acrolein, and trioxane, or several mixed in any ratio.
  • the relative molecular mass Mn of the dispersant prepared by the above method is 6000-30000.
  • the dispersant prepared by the above method is used as a ceramic additive, concrete water reducing agent, dye dispersant and coal water slurry additive.
  • the present invention is a method for preparing a dispersant using lignin degradation products.
  • the flowchart is shown in Figure 1.
  • a method for preparing a dispersant using lignin degradation products includes the following specific steps:
  • step (3) Add 40 kg of sodium p-aminobenzene sulfonate to 430 kg of lignin degradation product obtained in step (3), and make the solution react at 60°C and 250 rpm for 40 minutes;
  • step (4) Add 20kg of formaldehyde (effective content) to the reaction solution in step (4), stir and react for 3h at 95°C, then slowly add 6.25kg of urea and 3.75kg of isocyanate, and continue the condensation reaction for 4h;
  • a method for preparing a dispersant using lignin degradation products includes the following specific steps:
  • step (3) Add 62.5kg of sulfamic acid to 400kg of lignin degradation product obtained in step (3), and make the solution react at 50°C and 250rpm for 30min;
  • step (4) Add 27.5kg of acetaldehyde (effective content) to the reaction solution in step (4), stir and react for 4h at 90°C, then slowly add 7.5kg of urea and 2.5kg of isocyanate, and continue the reaction for 4h;
  • a method and application for preparing a dispersant using lignin degradation products which includes the following steps:
  • step (3) Add 50kg of p-aminobenzenesulfonic acid to 410kg of lignin degradation product obtained in step (3), and make the solution react at 70°C and 250rpm for 50min;
  • step (4) Add 25kg of glutaraldehyde (effective content) to the reacted solution in step (4), stir and react for 2.5h at 85°C, then slowly add 8.75kg of urea, 6.25kg of isocyanate, and continue the condensation reaction for 4h;
  • the relative molecular weight of the dispersant prepared in this example uses gel chromatography (Waters 2414, USA Waters Company) used polystyrene (PS) as the standard sample and THF as the mobile phase. The results are shown in Figure 1.
  • a method and application for preparing a dispersant using lignin degradation products which includes the following steps:
  • step (3) Add 55kg of sodium cyclamate to 420kg of lignin degradation product obtained in step (3), and make the solution react at 60°C and 250rpm for 40min;
  • step (4) Add 15kg acrolein (effective content) to the reaction solution in step (4), stir and react for 3.5h at 80°C, then slowly add 8.0kg urea and 2.0kg isocyanate, and continue the reaction for 4h;
  • a method and application for preparing a dispersant using lignin degradation products which includes the following steps:
  • step (3) Add 45kg of calcium cyclamate to 410kg of lignin degradation product obtained in step (3), and make the solution react at 55°C and 250rpm for 30min;
  • a method for preparing a dispersant using lignin degradation products includes the following specific steps:
  • step (3) Add 50kg of sodium p-aminobenzene sulfonate to 420kg of lignin degradation product obtained in step (3), and make the solution react at 50°C and 250rpm for 50min;
  • step (4) Add 12.5kg of formaldehyde (effective content) to the reaction solution in step (4), carry out a stirring reaction at 95°C for 3.5h, then slowly add 12.5kg of urea and 5.0kg of isocyanate, and continue the condensation reaction for 4h;
  • a method for preparing a dispersant using lignin degradation products includes the following specific steps:
  • step (3) Add 37.5kg of p-aminobenzenesulfonic acid to 430kg of lignin degradation product obtained in step (3), and make the solution react at 70°C and 250rpm for 40min;
  • step (4) Add 22.5kg of formaldehyde (effective content) to the reaction solution in step (4), stir and react for 3h at 90°C, then slowly add 8.75kg of urea and 1.25kg of isocyanate, and continue the condensation reaction for 4h;
  • the crushed, ground and classified clay materials are placed in a ball mill tank, 0.6wt% of the total mass of the clay is added to the prepared dispersant product, and an appropriate amount of water is added to adjust the water content of the slurry to 40wt%. Grind with a fast grinder for 10 minutes. After the ball milling is completed, the slurry fluidity test is performed and the blank is made into a 120mm ⁇ 60mm ⁇ 5mm specimen for green flexural strength test. The test results are shown in Table 1.
  • the dispersant prepared in the present invention tests the heat resistance stability of vat dyes and disperse dyes, refer to HG/T3507-2008 "Sodium Lignosulfonate Dispersant” and GB/T27597-2011 “Dyestuffs” Measurement of Diffusion Performance", the test results are shown in Table 3 and Table 4. It can be seen from the results in Table 3 and Table 4 that the product of the present invention has excellent dispersibility and heat resistance stability to dyes.
  • Table 3 shows the effect of the dispersant on the heat-resistant stability of reduced olive T at different temperatures.
  • Table 4 shows the application effects of dispersants on the 150°C heat stability of different dyes.
  • the dispersant prepared in the present invention tests the dispersibility and stability of the coal water slurry.
  • Select Shenhua coal as the research object after crushing, grinding, screening and grading, add a certain amount of water and dispersant product (addition amount is 0.4wt%), stir evenly to obtain coal water slurry of different concentrations, and use viscosity
  • the viscosity of the coal water slurry was measured by a meter, and the stability of the coal water slurry was tested by the drop test method. It can be seen from the results in Table 5 that the product of the present invention has good dispersibility and stability for coal water slurry.

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Abstract

本发明公开了一种利用木质素降解产物制备分散剂的方法和应用，以木质素为原料，通过微波辅助碱活化、金属氧化物催化降解木质素得到降解产物，并以降解产物为原料，利用氨基磺酸类单体、醛类、尿素、异氰酸酯类进行分子重整和化学修饰等反应制得相对分子质量Mn为6000～30000的分散剂。本发明的方法降解木质素简单高效、得到的降解产物分子量小，并且用降解产物制得的分散剂具有良好的分散性能，同时兼具增强和稳定性能，能用于陶瓷添加剂、混凝土减水剂、染料分散剂和水煤浆添加剂等诸多领域，推广应用前景广阔。

Description

一种利用木质素降解产物制备分散剂的方法和应用 技术领域
本发明属于分散剂技术领域，具体涉及一种利用木质素降解产物制备分散剂的方法和应用。
 背景技术
随着世界经济和工业的发展，石油煤炭等不可再生资源储量越来越少，以及生态环境问题的日益突出，利用可再生的生物质资源制取燃料和化学品已成为未来发展趋势。木质素、纤维素和半纤维素是植物组织中的重要组分 [1]，是重要的生物质资源。其中，木质素在自然界中的分布广泛，含有丰富独特的苯丙烷结构，是潜在的苯酚生产原料 [2]，同时也是制浆造纸工业的主要副产物，但目前大于95%的工业木质素只是简单作为废料处理，如燃烧获取低等级热量，利用率极低，浪费了大量资源。
木质素主要是由3种基本结构单元（芥子醇、松柏醇、香豆醇）构成的一类复杂酚类高聚物 [3]。木质素大分子中虽然有不少活性官能团，诸如芳香基、甲氧基和羟基等，可是其整体活性不高，高质化领域有限。木质素经过降解反应可以得到酚类、醇类、酸类和烃类等重要的化工原料 [4]。即使不同木质素的单体聚合类型都不一样，但仍有规律可循，它大致是由2/3的醚键与1/3的缩合键连接形成，因此，降解的难易度取决于总体的醚化和缩合程度 [5]。目前，木质素的降解方法都是通过将木质素中的化学键弱化、断裂，或者产生一些易于反应的基团或活性位点，增加木质素的反应活性，从而使木质素的重均分子量降低、反应空间位阻降低，达到降解的目的 [6]。目前木质素的降解主要采用化学降解法，而其中又以水热降解、氧化降解和液化降解三种最为常用 [7]。但是这些方法普遍存在降解效率低、反应条件苛刻、成本高等缺陷。专利CN201710045540.5报道了一种高效低污染制备毛竹木质素单酚化合物的方法，是将天然毛竹首先用酶解/温和酸解法分离出木质素，然后选用乙酸酐为乙酰化剂，以过氧乙酸为降解剂处理木质素得到单酚化合物。该方法低污染，得到了高得率、保留芳环结构的木质素低分子降解产物，但是需要用到复杂的乙酰化预处理。专利CN201710067650.1报道了一种利用氨络合物催化木质素降解制备单酚化合物的方法，利用金属盐和氨水在碱性条件下形成稳定的氨络合物溶液，并在过氧化剂下实现氧化降解，但是整体反应时间长，需使用高压条件。
近几年来，对于木质素降解产物的高质化利用研究，目前主要有聚氨酯泡沫材料、酚醛树脂、环氧树脂、胶黏剂、生物燃料等，在分子助剂如分散剂等方面有应用的潜力，但研究很少。Xue等 [8]在异丙醇-水混合物中，以NaOH为催化剂降解玉米芯木质素，并用降解产物替代多元醇制备生物质基硬质聚氨酯泡沫。由于木质素自身结构的高度复杂性，绝大多数关于木质素降解的文献报道的单酚化合物的收率一般为10%左右。因此提高木质素降解效率并且定向转化木质素，让其在制备新的高附加值产品具备更大优势，这将极大地改善了木质素的资源化途径，对后续的工业化生产提供理论指导意义。
技术问题
现有关于木质素降解的技术工艺整体反应时间长，有的需使用高温高压条件、特殊溶剂以及贵金属催化剂，成本较高，甚至存在二次污染。本专利以木质素为原料，对其进行降解改性成低分子量的降解产物，便于后续分子重整和化学修饰，并且产物含有丰富的酚羟基，化学反应活性高，有利于制备分散剂产品，应用于陶瓷添加剂、混凝土减水剂、染料分散剂和水煤浆添加剂等领域，能降低成本，拓宽木质素的利用途径，对社会经济的可持续发展意义重大。
 技术解决方案
为了解决现有技术的不足，本发明提供一种利用木质素降解产物制备分散剂的方法和应用。本发明制备分散剂的工艺简单、成本低廉、且适用于工业化生产。
为了实现上述的目的，本发明的技术方案为：
一种利用木质素降解产物制备分散剂的方法，包括以下步骤：
（1）木质素降解产物的制备：以木质素为原料，通过微波辅助碱活化、金属氧化物催化降解得到木质素降解产物；
（2）分散剂的制备：将木质素降解产物通过分子重整和化学修饰后制备出分散剂。
一种利用木质素降解产物制备分散剂的方法中，所述步骤（1）木质素降解产物的制备，包括以下具体步骤：
1）按质量比，把木质素、碱活化剂和金属氧化物催化剂悬浮于水中搅拌均匀；
2）在反应温度为120～200℃、微波功率为200～400W下反应0.5～2h；
3）待反应液冷却后，抽滤，除去固体残渣，即得木质素降解产物；
所述步骤（2）分散剂的制备，包括以下具体步骤：
1）在上述步骤（1）制备所得的木质素降解产物中加入单体，在50～70℃下反应30～50min后，缓慢加入交联剂，并在80～100℃条件下，进行搅拌反应2.5～4.5h，反应完成后，加入尿素和异氰酸酯继续缩合反应4h；
2）将上述缩合反应完的液体产物调节pH值至9.5～10.5，降温至室温出料即制得分散剂。
上述方法中，所述步骤（1）木质素降解产物的制备步骤中，按质量百分比之和为100%计，各组分添加的质量分数为：
木质素                      8.0%～12.0%；
碱活化剂                4.0%～16.0%；
催化剂                   0.1%～0.5%；
水                         75.5%～85.6%；
所述步骤（2）分散剂的制备步骤中，按质量百分比之和为100%计，各组分添加的质量分数为：
单体                         7.5%～12.5%；
木质素降解产物            80.0%～86.0%；
交联剂                      2.5%～6.25%；
尿素                         1.25%～2.5%；
异氰酸酯                        0.25%～1.25%
进一步的，所述木质素包括由竹子、玉米芯、玉米秸秆、蔗渣、棉花秸秆、稻草、麦草、曲柳、芒杆、杨木、芦苇、桉木、柞木、桦木、马尾松中的一种或几种通过溶剂提取、酶解、机械、亚硫酸盐法或碱法制得的有机溶剂木质素、酶解木质素、磨木木质素、硫酸盐木质素、磺酸盐木质素、碱木质素或天然木质素。
进一步的，所述的碱活化剂为NaOH、KOH、LiOH、Na 2CO 3、K 2CO 3和NaAlO 2中的一种或者任意比例的几种混合。
进一步的，所述的催化剂为氧化锆、氧化钼、氧化锌、氧化钛、氧化铌中的一种或任意比例混合的几种。
进一步的，所述的单体为氨基磺酸、对氨基苯磺酸、对氨基苯磺酸钠、环己基氨基磺酸钠、环己基氨基磺酸钙中的一种或任意比例混合的几种。
进一步的，所述的交联剂为甲醛、乙醛、戊二醛、丙烯醛、三聚甲醛中的一种或任意比例混合的几种。
上述方法制备所得分散剂的相对分子质量Mn为6000～30000。
上述方法制备所得分散剂作为陶瓷添加剂、混凝土减水剂、染料分散剂和水煤浆添加剂的应用。
 有益效果
本发明的有益效果为：通过对木质素进行微波辅助碱活化和金属氧化物催化降解改性，使其降解成小分子物质，降解工艺简单，周期短，降解率高；直接利用降解产物通过分子重整和化学修饰后制备分散剂，成本低，且制备的分散剂具备良好的减水、分散、增强等作用，能应用于陶瓷添加剂、混凝土减水剂、染料分散剂和水煤浆添加剂等领域；该方法通过有效利用可再生生物质资源木质素作为原料，原料来源广泛，成本低廉，具有重要的社会经济和环保意义。
 附图说明
图1：本发明利用木质素降解产物制备分散剂的方法的流程图。
图2：实施例3制备所得分散剂的相对分子质量图。
 本发明的实施方式
一种利用木质素降解产物制备分散剂的方法，包括以下步骤：
（1）木质素降解产物的制备：以木质素为原料，通过微波辅助碱活化、金属氧化物催化降解得到木质素降解产物；
（2）分散剂的制备：将木质素降解产物通过分子重整和化学修饰后制备出分散剂。
一种利用木质素降解产物制备分散剂的方法中，所述步骤（1）木质素降解产物的制备，包括以下具体步骤：
1）按质量比，把木质素、碱活化剂和金属氧化物催化剂悬浮于水溶液中搅拌均匀；
2）在反应温度为120～200℃、微波功率为200～400W下反应0.5～2h；
3）待反应液冷却后，抽滤，除去固体残渣，即得降解产物；
所述步骤（2）分散剂的制备，包括以下具体步骤：
1）在上述步骤（1）制备的所得的木质素降解产物中加入水混匀，在加入单体，在50～70℃下反应30～50min后，缓慢加入交联剂，并在80～100℃条件下，进行搅拌反应2.5～4.5h，反应完成后，加入尿素和异氰酸酯继续缩合反应4h；
2）将上述缩合反应完的液体产物调节pH值至9.5～10.5，降温至室温出料即制得分散剂。
上述方法中，所述步骤（1）木质素降解产物的制备步骤中，按质量百分比之和为100%计，各组分添加的质量分数为：
木质素                      8.0%～12.0%；
碱活化剂                4.0%～16.0%；
催化剂                   0.1%～0.5%；
水                        75.5%～85.6%；
所述步骤（2）分散剂的制备步骤中，按质量百分比之和为100%计，各组分添加的质量分数为：
单体                          7.5%～12.5%；
木质素降解产物            80.0%～86.0%；
交联剂                       2.5%～6.25%；
尿素                          1.25%～2.5%；
异氰酸酯                        0.25%～1.25%；
进一步的，所述的木质素包括由竹子、玉米芯、玉米秸秆、蔗渣、棉花秸秆、稻草、麦草、曲柳、芒杆、杨木、芦苇、桉木、柞木、桦木、马尾松中的一种或几种通过溶剂提取、酶解、机械、亚硫酸盐法或碱法制得的有机溶剂木质素、酶解木质素、磨木木质素、硫酸盐木质素、磺酸盐木质素、碱木质素或天然木质素。
进一步的，所述的碱活化剂为NaOH、KOH、LiOH、Na 2CO 3、K 2CO 3和NaAlO 2中的一种或者任意比例混合的几种。
进一步的，所述的催化剂为氧化锆、氧化钼、氧化锌、氧化钛、氧化铌中的一种或任意比例混合的几种。
进一步的，所述的单体为氨基磺酸、对氨基苯磺酸、对氨基苯磺酸钠、环己基氨基磺酸钠、环己基氨基磺酸钙中的一种或任意比例混合的几种。
进一步的，所述的交联剂为甲醛、乙醛、戊二醛、丙烯醛、三聚甲醛中的一种或任意比例混合的几种。
上述方法制备所得分散剂的相对分子质量Mn为6000～30000。
上述方法制备所得分散剂作为陶瓷添加剂、混凝土减水剂、染料分散剂和水煤浆添加剂的应用。
本发明一种利用木质素降解产物制备分散剂的方法，其流程图见图1。
实施例 1
一种利用木质素降解产物制备分散剂的方法，包括以下具体步骤：
（1）将40kg竹浆碱木质素、30kgNaOH和10kgNaAlO 2、1.2kg氧化锆催化剂、418.8kg水混合搅拌均匀；
（2）将上述混合溶液倒进微波反应罐，设置反应温度180℃、微波功率300W，反应1h后，降温出料，过滤除去固体残渣，即得木质素降解产物；
（3）往步骤（3）所得木质素降解产物430kg中加入40kg对氨基苯磺酸钠，并使溶液在60℃、250rpm下进行反应40min；
（4）往步骤（4）反应后的溶液中加入20kg甲醛（有效含量），在95℃条件下，进行搅拌反应3h，再缓慢加入6.25kg尿素和3.75kg异氰酸酯，继续缩合反应4h；
（5）将上述缩合反应完的液体产物调节pH值至10.0，降温出料即得分散剂，其相对分子质量为17600。
实施例 2
一种利用木质素降解产物制备分散剂的方法，包括以下具体步骤：
（1）将50kg稻壳有机溶剂木质素、15kgNaOH和5kgKOH、2kg氧化钼催化剂、428kg水混合搅拌均匀；
（2）将上述混合溶液倒进微波反应罐，设置反应温度160℃、微波功率200W，反应2h后，降温出料，过滤除去固体残渣，即得木质素降解产物；
（3）往步骤（3）所得木质素降解产物400kg加入62.5kg氨基磺酸，并使溶液在50℃、250rpm下进行反应30min；
（4）往步骤（4）反应后的溶液中加入27.5kg乙醛（有效含量），在90℃条件下，进行搅拌反应4h，再缓慢加入7.5kg尿素和2.5kg异氰酸酯，继续反应4h；
（5）将上述缩合反应完的液体产物调节pH值至9.5，降温出料即可制得分散剂，相对分子质量为10500。
实施例 3
一种利用木质素降解产物制备分散剂的方法和应用，其包括以下步骤：
（1）将60Kg桉木磨木木质素、30kgNaOH和30kgNa 2CO 3、0.5kg氧化锌催化剂、379.5kg水混合搅拌均匀；
（2）将上述混合溶液倒进微波反应罐，设置反应温度120℃、微波功率400W，反应0.5h后，降温出料，过滤除去固体残渣，即得木质素降解产物；
（3）往步骤（3）所得木质素降解产物410kg加入50kg对氨基苯磺酸，并使溶液在70℃、250rpm下进行反应50min；
（4）往步骤（4）反应后的溶液中加入25kg戊二醛（有效含量），在85℃条件下，进行搅拌反应2.5h，再缓慢加入8.75kg尿素6.25kg异氰酸酯，继续缩合反应4h；
（5）将上述缩合反应完的液体产物调节pH值至10.5，降温出料即得分散剂，相对分子质量为8800。
本实施例制备所得分散剂的相对分子量采用凝胶色谱仪（Waters2414，美国 Waters 公司）进行测定，用聚苯乙烯（PS）作为标样，以THF为流动相，结果见图1。
实施例 4
一种利用木质素降解产物制备分散剂的方法和应用，其包括以下步骤：
（1）将40kg玉米芯酶解木质素、60kgNaOH和20kgK 2CO 3、2.5kg氧化钛催化剂、377.5kg水混合搅拌均匀；
（2）将上述混合溶液倒进微波反应罐，设置反应温度200℃、微波功率300W，反应1h后，降温出料，过滤除去固体残渣，即得木质素降解产物；
（3）往步骤（3）所得木质素降解产物420kg加入55kg环己基氨基磺酸钠，并使溶液在60℃、250rpm下进行反应40min；
（4）往步骤（4）反应后的溶液中加入15kg丙烯醛（有效含量），在80℃条件下，进行搅拌反应3.5h，再缓慢加入8.0kg尿素和2.0kg异氰酸酯，继续反应4h；
（5）将上述缩合反应完的液体产物调节pH值至10.0，降温出料即得分散剂，相对分子质量为12300。
实施例 5
一种利用木质素降解产物制备分散剂的方法和应用，其包括以下步骤：
（1）将50kg马尾松硫酸盐木质素、50kgNaOH、1.5kg氧化铌催化剂、398.5kg水混合搅拌均匀；
（2）将上述混合溶液倒进微波反应罐，设置反应温度140℃、微波功率200W，反应0.5h后，降温出料，过滤除去固体残渣，即得木质素降解产物；
（3）往步骤（3）所得木质素降解产物410kg加入45kg环己基氨基磺酸钙，并使溶液在55℃、250rpm下进行反应30min；
（4）往步骤（4）反应后的溶液中加入31.25kg三聚甲醛（有效含量），在100℃条件下，进行搅拌反应4.5h，再缓慢加入10.0kg尿素和3.75kg异氰酸酯，继续反应4h；
（5）将上述缩合反应完的液体产物调节pH值至10.5，降温出料即得分散剂，相对分子质量为11500。
实施例 6
一种利用木质素降解产物制备分散剂的方法，包括以下具体步骤：
（1）将60kg棉花秸秆磺酸盐木质素、30kgNaOH和10kgNaAlO 2、1.0kg氧化铌催化剂、399kg水混合搅拌均匀；
（2）将上述混合溶液倒进微波反应罐，设置反应温度150℃、微波功率400W，反应2h后，降温出料，过滤除去固体残渣，即得木质素降解产物；
（3）往步骤（3）所得木质素降解产物420kg加入50kg对氨基苯磺酸钠，并使溶液在50℃、250rpm下进行反应50min；
（4）往步骤（4）反应后的溶液中加入12.5kg甲醛（有效含量），在95℃条件下，进行搅拌反应3.5h，再缓慢加入12.5kg尿素和5.0kg异氰酸酯，继续缩合反应4h；
（5）将上述缩合反应完的液体产物调节pH值至9.5，降温出料即得分散剂，相对分子质量为10980。
实施例 7
一种利用木质素降解产物制备分散剂的方法，包括以下具体步骤：
（1）将40kg碱法制浆木质素（芦苇和麦草按1:2比例混合）、30kgKOH和10kgLiOH、1.8kg氧化锆催化剂、418.2kg水混合搅拌均匀；
（2）将上述混合溶液倒进微波反应罐，设置反应温度170℃、微波功率300W，反应1h后，降温出料，过滤除去固体残渣，即得木质素降解产物；
（3）往步骤（3）所得木质素降解产物430kg加入37.5kg对氨基苯磺酸，并使溶液在70℃、250rpm下进行反应40min；
（4）往步骤（4）反应后的溶液中加入22.5kg甲醛（有效含量），在90℃条件下，进行搅拌反应3h，再缓慢加入8.75kg尿素和1.25kg异氰酸酯，继续缩合反应4h；
（5）将上述缩合反应完的液体产物调节pH值至10.0，降温出料即得分散剂，相对分子质量为14900。
性能测试
1、陶瓷添加剂
以陶瓷添加剂为例，将破碎粉磨分级的陶土原料置于球磨罐中，按陶土总质量的0.6wt%加入上述制得的分散剂产品并加入适量水调节浆料的含水量为40wt%，用快速研磨机进行研磨10min，球磨完毕后，进行浆料流动性测试和将坯料制成120mm×60mm×5mm规格的试样进行生坯抗折强度测试，其测试结果见表1。
实施对照例
将破碎粉磨分级的陶土原料置于球磨罐中，按陶土总质量的0.6wt%加入三聚磷酸钠陶瓷添加剂并加入适量水调节坯料的含水量为40wt%，用快速研磨机进行研磨10min，球磨完毕后，进行浆料流动性和黏度测试和将坯料制成120mm×60mm×5mm规格的试样进行生坯抗折强度测试。
上述实施例1～7和实施对照例的测试结果如下表1所示，由表1的结果可见，在添加剂掺量相同的条件下，本发明产品对陶瓷浆料具有良好的分散性，并且增强性能优于三聚磷酸钠，可满足陶瓷工业制浆的要求。
Figure dest_path_image001
2、混凝土减水剂
以混凝土减水剂为例，参照GBT8077-2012《混凝土外加剂匀质性试验方法》和GB50119《混凝土外加剂应用技术规范》，本发明制备所得的分散剂与其他同类产品对水泥净浆流动度（mm）影响比较情况见表2。由表2的结果知，本发明产品对不同水泥品种的混凝土具有良好的减水分散性能
表2 本发明制备所得的分散剂与其他同类产品对水泥净浆流动度影响情况
Figure 379574dest_path_image002
3、染料分散剂
以染料分散剂为例，本发明制备所得分散剂对还原染料和分散染料的耐热稳定性进行测试，参照HG/T3507-2008《木质素磺酸钠分散剂》和GB/T27597-2011《染料扩散性能的测定》，测试结果见表3和表4。由表3、表4的结果可见，本发明产品对染料具有优良的分散性和耐热稳定性。
表3为不同温度下分散剂对还原橄榄T在耐热稳定性上的应用效果。
Figure dest_path_image003
表4为分散剂对不同的染料150℃耐热稳定性的应用效果。
Figure 467353dest_path_image004
4、水煤浆添加剂
以水煤浆添加剂为例，本发明制备所得分散剂对水煤浆的分散性和稳定性进行测试。选用神华煤为研究对象，通过破碎、磨矿、筛选和级配后，加入一定量的水和分散剂产品（添加量为0.4wt%），搅拌均匀，得到不同浓度的水煤浆，利用粘度计测定水煤浆黏度，并采用落棒试验法来检验水煤浆的稳定性，测试结果见表5。由表5的结果可见，本发明产品对水煤浆具有良好的分散性和稳定性。
表5
Figure dest_path_image005
以上所述为本发明的实施例，对于本领域的普通技术人员而言，根据本发明的教导，在不脱离本发明的原理和精神的情况下凡依本发明申请专利范围所做的均等变化、修改、替换和变型，皆应属本发明的涵盖范围。
参考文献
[1]  Hill C A S. Wood modification: chemical, thermal and other processes[M]. John Wiley & Sons, 2007.
[2]  Azadi P, Inderwildi O R, Farnood R, et al. Liquid fuels, hydrogen and chemicals from lignin: A critical review[J]. Renewable & Sustainable Energy Reviews, 2013, 21(5):506-523.
[3]  Feghali E, Cantat T. Unprecedented organocatalytic reduction of lignin model compounds to phenols and primary alcohols using hydrosilanes[J]. Chemical Communications, 2014, 50(7): 862-865.
[4]  卢婷婷, 房桂干, 卓治非, 等. 木素化学改性及其在聚氨酯合成中的应用[J]. 纸和造纸, 2013, 32(11):55-58.
[5]  Pandey M P, Kim C S. Lignin depolymerization and conversion: a review of thermochemical methods[J]. Chemical Engineering & Technology, 2011, 34(1): 29-41.
[6] Shao, Yi, Xia, et al. Selective production of arenes via direct lignin upgrading over a niobium-based catalyst[J]. Nature Communications, 2017, 8:16104.
[7]  Huang J, Zhang L, Wei H, et al. Soy protein isolate/kraft lignin composites compatibilized with methylene diphenyldiisocyanate[J]. Journal of applied polymer science, 2004, 93(2): 624-629.
[8] Xue B L , Huang P L , Sun Y C , et al. Hydrolytic depolymerization of corncob lignin in the view of a bio-based rigid polyurethane foam synthesis[J]. Rsc Advances, 2017, 7(10):6123-6130.

Claims (10)

  1. 一种利用木质素降解产物制备分散剂的方法，其特征在于，包括以下步骤：
    （1）木质素降解产物的制备：木质素为原料，通过微波辅助碱活化、金属氧化物催化降解得到木质素降解产物；
    （2）分散剂的制备：将步骤（1）所得木质素降解产物通过分子重整和化学修饰后制备出分散剂。
  2. 根据权利要求1所述的一种利用木质素降解产物制备分散剂的方法，其特征在于：所述步骤（1）木质素降解产物的制备，包括以下具体步骤：
    1）按质量比，把木质素、碱活化剂和金属氧化物催化剂悬浮于水溶液中搅拌均匀；
    2）在反应温度为120～200℃、微波功率为200～400W下反应0.5～2h；
    3）待反应液冷却后，抽滤，去除固体残渣，即得木质素降解产物；
    所述步骤（2）分散剂的制备，包括以下具体步骤：
    1）在上述步骤（1）制备所得的木质素降解产物中加入单体，在50～70℃下反应30～50min后，缓慢加入交联剂，并在80～100℃条件下，进行搅拌反应2.5～4.5h，反应完成后，加入尿素和异氰酸酯继续缩合反应4h；
    2）将上述缩合反应完的液体产物调节pH值至9.5～10.5，降温至室温出料即制得分散剂。
  3. 根据权利要求2所述的一种利用木质素降解产物制备分散剂的方法，其特征在于：所述步骤（1）木质素的降解产物的制备步骤中，按质量百分比之和为100%计，各组分添加的质量分数为：
    木质素                   8.0%～12.0%；
    碱活化剂                4.0%～16.0%；
    催化剂                   0.1%～0.5%；
    水                         75.5%～85.6%；
    所述步骤（2）分散剂的制备步骤中，按质量百分比之和为100%计，各组分添加的质量分数为：
    单体                          7.5%～12.5%；
    木质素降解产物          80.0%～86.0%；
    交联剂                       2.5%～6.25%；
    尿素                          1.25%～2.5%；
    异氰酸酯                   0.25%～1.25%
  4. 根据权利要求3所述的一种利用木质素降解产物制备分散剂的方法，其特征在于：所述木质素包括由竹子、玉米芯、玉米秸秆、蔗渣、棉花秸秆、稻草、麦草、曲柳、芒杆、杨木、芦苇、桉木、柞木、桦木、马尾松中的一种或几种通过溶剂提取、酶解、机械、亚硫酸盐法或碱法制得的有机溶剂木质素、酶解木质素、磨木木质素、硫酸盐木质素、磺酸盐木质素、碱木质素或天然木质素。
  5. 根据权利要求3所述的一种利用木质素降解产物制备分散剂的方法，其特征在于：所述的碱活化剂为NaOH、KOH、LiOH、Na 2CO 3、K 2CO 3和NaAlO 2中的一种或者任意比例的几种混合。
  6. 根据权利要求3所述的一种利用木质素降解产物制备分散剂的方法，其特征在于：所述的催化剂为氧化锆、氧化钼、氧化锌、氧化钛、氧化铌中的一种或任意比例混合的几种。
  7. 根据权利要求3所述的一种利用木质素降解产物制备分散剂的方法，其特征在于：所述的单体为氨基磺酸、对氨基苯磺酸、对氨基苯磺酸钠、环己基氨基磺酸钠、环己基氨基磺酸钙中的一种或任意比例混合的几种。
  8. 根据权利要求3所述的一种利用木质素降解产物制备分散剂的方法，其特征在于：所述的交联剂为甲醛、乙醛、戊二醛、丙烯醛、三聚甲醛中的一种或任意比例混合的几种。
  9. 一种如权利要求1-8所述的一种利用木质素降解产物制备分散剂的方法制备所得的分散剂，其相对分子质量Mn为6000～30000。
  10. 根据权利要求9所述的分散剂作为陶瓷添加剂、混凝土减水剂、染料分散剂和水煤浆添加剂的应用。
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