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CN102658578B - Method for manufacturing fiberboard by using laccase-activated lignosulfonate - Google Patents

Method for manufacturing fiberboard by using laccase-activated lignosulfonate Download PDF

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CN102658578B
CN102658578B CN201210142388.XA CN201210142388A CN102658578B CN 102658578 B CN102658578 B CN 102658578B CN 201210142388 A CN201210142388 A CN 201210142388A CN 102658578 B CN102658578 B CN 102658578B
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laccase
lignosulphonates
lignosulfonate
wood
fiberboard
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CN102658578A (en
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金春德
杜春贵
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Tongxiang Beite Technology Co ltd
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Jiyang College of Zhejiang A&F University
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Abstract

本发明涉及一种漆酶活化木素磺酸盐制造纤维板的方法。本发明的目的是提供一种漆酶活化木素磺酸盐制造纤维板的方法,能够大大提高活性氧类自由基的浓度,改善板材物理力学性能。本发明的技术方案是:漆酶活化木素磺酸盐制造纤维板的方法,其特征在于步骤如下:a、将木材或其加工剩余料分离成木纤维并进行干燥;b、将滑石粉与漆酶混合并拌匀,再加入木素磺酸盐混合搅拌均匀,最后加水搅拌均匀得到漆酶粘合剂;c、利用步骤b得到的粘合剂,在搅拌机中对木纤维边喷射边搅拌;d、将步骤c得到的纤维板料进行铺装、预压、热压、后处理。本发明适用于纤维板的制造。The invention relates to a method for laccase activating lignin sulfonate to manufacture fiberboard. The purpose of the present invention is to provide a method for activating lignosulfonate with laccase to manufacture fiberboard, which can greatly increase the concentration of active oxygen free radicals and improve the physical and mechanical properties of the board. The technical solution of the present invention is: the method for laccase activating lignosulfonate to manufacture fiberboard, which is characterized in that the steps are as follows: a. separating wood or its processing residues into wood fibers and drying them; b. mixing talcum powder with lacquer Mix the enzymes and mix well, then add lignosulfonate to mix and stir evenly, finally add water and stir evenly to obtain a laccase adhesive; c, use the adhesive obtained in step b, spray and stir the wood fiber in a mixer; d. Paving, pre-pressing, hot-pressing and post-processing the fiber board material obtained in step c. The invention is applicable to the manufacture of fibreboards.

Description

漆酶活化木素磺酸盐制造纤维板的方法Laccase activated lignin sulfonate manufacturing method for fiberboard

技术领域 technical field

本发明涉及一种木材或非木材植物的加工,特别是一种漆酶活化木素磺酸盐制造纤维板的方法,主要适用于纤维板的制造。The invention relates to the processing of wood or non-wood plants, in particular to a method for activating lignin sulfonate with laccase to manufacture fiberboards, which is mainly applicable to the manufacture of fiberboards.

背景技术 Background technique

不使用胶粘剂利用漆酶处理方法制造人造板是一种生产无甲醛环保型人造板的崭新途径。“酶活化处理条件及其对松木纤维胶合性能的影响初探”(《林业科学》第40卷第4期),报道了漆酶对纤维板制造上的应用理论研究,该方法漆酶处理的时间长,还需用缓冲溶液调节漆酶反应体系的pH值,本发明申请人在以竹刨花为原料研究漆酶处理干法竹刨花板制造工艺过程中发现,漆酶处理竹刨花板产品的物理力学性能与漆酶活化竹刨花时产生的活性氧类自由基浓度紧密相关(北京林业大学学报,第31卷,第2期),且其活性氧类自由基浓度愈高,板材的物理力学性能愈好。Manufacturing wood-based panels without using adhesives and using laccase treatment is a new way to produce formaldehyde-free and environmentally friendly wood-based panels. "A Preliminary Study on the Conditions of Enzyme Activation Treatment and Its Effects on the Gluing Properties of Pine Fibers" ("Forestry Science" Vol. 40, No. 4), reported the theoretical research on the application of laccase to the manufacture of fiberboard. This method takes a long time for laccase treatment. , also need to adjust the pH value of laccase reaction system with buffer solution, the applicant of the present invention finds that the physical and mechanical properties of laccase-treated bamboo particleboard product and The concentration of active oxygen free radicals generated when laccase activated bamboo shavings was closely related (Journal of Beijing Forestry University, Volume 31, Issue 2), and the higher the concentration of active oxygen free radicals, the better the physical and mechanical properties of the board.

发明内容 Contents of the invention

本发明要解决的技术问题是:针对上述存在的问题提供一种漆酶活化木素磺酸盐制造纤维板的方法,能够大大提高活性氧类自由基的浓度,改善板材物理力学性能,同时其粘合剂的制备不必专门预留酶处理时间,并且可以不需调节反应体系pH值,以简化生产工艺,提高工效。The technical problem to be solved in the present invention is: to provide a method for laccase-activated lignosulfonate to manufacture fiberboards in view of the above-mentioned problems, which can greatly increase the concentration of active oxygen free radicals, improve the physical and mechanical properties of the board, and at the same time its stickiness The preparation of the mixture does not need to reserve special time for enzyme treatment, and it is not necessary to adjust the pH value of the reaction system, so as to simplify the production process and improve work efficiency.

本发明所采用的技术方案是:漆酶活化木素磺酸盐制造纤维板的方法,其特征在于步骤如下:The technical scheme adopted in the present invention is: the method for laccase activating lignosulfonate to manufacture fiberboard, it is characterized in that the steps are as follows:

a、将木材或其加工剩余料分离成木纤维并进行干燥,控制含水率为3-5%;a. Separate the wood or its processing residues into wood fibers and dry them to control the moisture content to 3-5%;

b、将滑石粉与漆酶混合并拌匀,再加入木素磺酸盐混合搅拌均匀,最后加水搅拌均匀得到漆酶粘合剂;b. Mix talcum powder and laccase and mix well, then add lignosulfonate and mix well, finally add water and stir well to obtain laccase adhesive;

c、利用步骤b得到的粘合剂,在搅拌机中对木纤维边喷射边搅拌,粘合剂用量按其固体含量占木纤维绝干质量的8-13%比例计算;C, utilize the binding agent that step b obtains, stir while spraying to wood fiber limit in mixer, the binding agent consumption accounts for the 8-13% ratio calculation of wood fiber dry mass by its solid content;

d、将步骤c得到的纤维板料进行铺装、预压、热压、后处理,预压线压力1.5-2.5kN/cm,热压温度170-200℃,热压压力2.0-3.5MPa,预压时间10-30s,热压时间30-60s/mm。d. Paving, pre-pressing, hot-pressing and post-processing the fiber sheet material obtained in step c. The pressing time is 10-30s, and the hot pressing time is 30-60s/mm.

步骤b中制备所述粘合剂的各原料配比为,The ratio of raw materials for preparing the adhesive in step b is,

20-25重量份的木素磺酸盐;20-25 parts by weight of lignosulfonate;

每克重木素磺酸盐绝干粉中添加40-55个酶活力单位的漆酶;Add 40-55 enzyme activity units of laccase per gram of heavy lignosulfonate absolute dry powder;

木素磺酸盐粉质量0.5%-1%的滑石粉;Lignosulfonate powder quality 0.5%-1% talcum powder;

145-200重量份的水。145-200 parts by weight of water.

所述漆酶为干燥的漆酶粉或漆酶液,其中漆酶液的重量计入水的用量中。The laccase is dry laccase powder or laccase liquid, wherein the weight of the laccase liquid is included in the amount of water used.

所述滑石粉的粒度为1000-3000目。The particle size of the talcum powder is 1000-3000 mesh.

所述木素磺酸盐为木素磺酸铵或木素磺酸钠。The lignosulfonate is ammonium lignosulfonate or sodium lignosulfonate.

本发明的有益效果是:本发明在粘合剂原料中加入滑石粉作为漆酶活化反应中的促进剂,在其它处理条件相同的情况下,大大提高了活性氧类自由基的浓度(其活性氧类自由基浓度比没采用滑石粉的反应体系均高1-5倍),从而改善了板材的物理力学性能,即使不使用缓冲液来调节反应体系pH值、不另外专门预留酶处理时间,所得粘合剂制成的植物纤维板强度同样能够达到国标要求;另外,由于省去了缓冲液用量和酶处理时间,不仅节省了成本,而且大大简化了生产工艺,提高了工效。The beneficial effect of the present invention is: the present invention adds talcum powder in the adhesive raw material as the promotor in the laccase activation reaction, under the same situation of other treatment conditions, greatly improved the concentration of active oxygen free radical (its activity The concentration of oxygen free radicals is 1-5 times higher than that of the reaction system without talc powder), thus improving the physical and mechanical properties of the board, even if no buffer is used to adjust the pH value of the reaction system, and no additional enzyme treatment time is reserved , the strength of the plant fiber board made of the obtained adhesive can also meet the requirements of the national standard; in addition, because the amount of buffer solution and the enzyme treatment time are omitted, not only the cost is saved, but also the production process is greatly simplified and the work efficiency is improved.

具体实施方式 Detailed ways

实施例1:本实施例漆酶活化木素磺酸盐制造纤维板的方法包括以下步骤,Embodiment 1: The method for activating lignosulfonate with laccase in this embodiment to manufacture fiberboard comprises the following steps,

a、备料:a. Preparation:

将木材或其加工剩余料,按常规的中密度纤维板生产方法分离成木纤维并进行干燥,控制木纤维含水率为3%;The wood or its processing residues are separated into wood fibers according to the conventional medium density fiberboard production method and dried, and the moisture content of the wood fibers is controlled to 3%;

漆酶,从诺维信(中国)投资有限公司购置含水酶制剂——漆酶NS51003;Laccase, purchased from Novozymes (China) Investment Co., Ltd., an aqueous enzyme preparation - laccase NS51003;

木素磺酸铵,从武汉华东化工有限公司购得,为粉状物;Ammonium lignosulfonate, purchased from Wuhan Huadong Chemical Co., Ltd., is a powder;

滑石粉,从化工商店购得粒度为1000目的滑石粉。Talcum powder, purchased particle size from the chemical store is 1000 mesh talcum powder.

b、漆酶粘合剂原料的计量:漆酶的用量为每克(g)绝干的木素磺酸铵粉需40个酶活力单位(u),滑石粉用量为木素磺酸铵粉质量的0.5%,20重量份的木素磺酸铵和145重量份的水。配制漆酶粘合剂时,先以木素磺酸铵的用量为基数,按其绝干质量40u/g推算出需用酶活力单位(u)的总数,再根据漆酶活性计算出漆酶的用量;滑石粉用量为木素磺酸铵粉质量的0.5%;最后按重量份比确定水的用量,由于本例中漆酶为漆酶液,因此水的用量应包括漆酶液的重量,而且水应最后按145重量份的比例范围内酌定加入。漆酶活性测定可采用ABTS——分光光度计法,用的底物为2,2′-连氮-双-(3-乙基苯并噻唑-6-磺酸)简称ABTS,一个酶活单位(u)指一定反应条件下,每分钟(min)催化1μmol ABTS转化为产物所需的酶量。b. The measurement of laccase binder raw materials: the amount of laccase is 40 enzyme activity units (u) per gram (g) of dry ammonium lignosulfonate powder, and the amount of talcum powder is ammonium lignosulfonate powder 0.5% by mass, 20 parts by weight of ammonium lignosulfonate and 145 parts by weight of water. When preparing laccase adhesive, first use the amount of ammonium lignosulfonate as the base, and calculate the total number of enzyme activity units (u) according to its absolute dry mass of 40u/g, and then calculate the laccase activity according to the laccase activity. The consumption of talcum powder is 0.5% of ammonium lignosulfonate powder quality; Finally, the consumption of water is determined by weight ratio, because laccase is laccase liquid in this example, so the consumption of water should include the weight of laccase liquid , and water should finally be added as appropriate in a proportion of 145 parts by weight. Laccase activity can be determined by ABTS—spectrophotometer method, the substrate used is 2,2′-azino-bis-(3-ethylbenzothiazole-6-sulfonic acid) referred to as ABTS, an enzyme activity unit (u) refers to the amount of enzyme required to catalyze the conversion of 1 μmol ABTS to the product per minute (min) under certain reaction conditions.

c、漆酶粘合剂的制备:按照上述配比称取各原料,先将滑石粉与漆酶液混合,搅拌均匀成糊状物,再将该糊状物与木素磺酸铵混合并搅拌均匀,最后加入水搅拌匀均即可。c. Preparation of laccase adhesive: take each raw material according to the above ratio, first mix talcum powder with laccase liquid, stir to form a paste, then mix the paste with ammonium lignosulfonate and mix Stir well, and finally add water and mix well.

d、漆酶粘合剂与木纤维的混合:利用步骤c得到的粘合剂,在搅拌机中对木纤维边喷射边搅拌,粘合剂用量按其固体含量占木纤维绝干质量的8%比例计算。D, the mixing of laccase binder and wood fiber: utilize the binder that step c obtains, stir while spraying to wood fiber limit in mixer, binder consumption accounts for 8% of wood fiber absolute dry mass by its solid content Proportional calculations.

e、漆酶处理纤维板的压制:将步骤d得到纤维板料用常规的工序即经铺装、预压、热压、后处理即成,预压线压力1.5kN/cm,热压温度170℃,热压压力2.0MPa,预压时间10s,热压时间30s/mm。e. Compression of laccase-treated fiberboard: the fiberboard obtained in step d is prepared by conventional procedures, namely paving, pre-pressing, hot-pressing, and post-treatment. The pre-pressing line pressure is 1.5kN/cm, and the hot-pressing temperature is 170°C. The hot pressing pressure is 2.0MPa, the pre-pressing time is 10s, and the hot pressing time is 30s/mm.

实施例2:本实施例漆酶活化木素磺酸盐制造纤维板的方法包括以下步骤,Embodiment 2: The method for activating lignosulfonate to manufacture fiberboard with laccase in this embodiment comprises the following steps,

a、备料:a. Preparation:

将木材或其加工剩余料,按常规的中密度纤维板生产方法分离成木纤维并进行干燥,控制木纤维含水率为5%;The wood or its processing residues are separated into wood fibers according to the conventional medium density fiberboard production method and dried, and the moisture content of the wood fibers is controlled to 5%;

漆酶,从诺维信(中国)投资有限公司购置含水酶制剂——漆酶NS51003;Laccase, purchased from Novozymes (China) Investment Co., Ltd., an aqueous enzyme preparation - laccase NS51003;

木素磺酸铵,从武汉华东化工有限公司购得,为粉状物;Ammonium lignosulfonate, purchased from Wuhan Huadong Chemical Co., Ltd., is a powder;

滑石粉,从化工商店购得粒度为3000目的滑石粉。Talcum powder, purchased particle size from the chemical store is 3000 mesh talcum powder.

b、漆酶粘合剂原料的计量:漆酶的用量为每克(g)绝干的木素磺酸铵粉需55个酶活力单位(u),滑石粉用量为木素磺酸铵粉质量的1%,25重量份的木素磺酸铵和200重量份的水。配制漆酶粘合剂时,先以木素磺酸铵的用量为基数,按其绝干质量55u/g推算出需用酶活力单位(u)的总数,再根据漆酶活性计算出漆酶的用量;滑石粉用量为木素磺酸铵粉质量的1%;最后按重量份比确定水的用量,由于本例中漆酶为漆酶液,因此水的用量应包括漆酶液的重量,而且水应最后按200重量份的比例范围内酌定加入。漆酶活性测定可采用ABTS——分光光度计法,用的底物为2,2′-连氮-双-(3-乙基苯并噻唑-6-磺酸)简称ABTS,一个酶活单位(u)指一定反应条件下,每分钟(min)催化1μmol ABTS转化为产物所需的酶量。b. The measurement of laccase binder raw materials: the amount of laccase is 55 enzyme activity units (u) per gram (g) of dry ammonium lignosulfonate powder, and the amount of talcum powder is ammonium lignosulfonate powder 1% by mass, 25 parts by weight of ammonium lignosulfonate and 200 parts by weight of water. When preparing laccase adhesive, first use the amount of ammonium lignosulfonate as the base, and calculate the total number of enzyme activity units (u) according to its absolute dry mass of 55u/g, and then calculate the laccase activity according to the laccase activity. The consumption of talcum powder is 1% of the quality of ammonium lignosulfonate powder; Finally, the consumption of water is determined by weight ratio, because laccase is laccase liquid in this example, so the consumption of water should include the weight of laccase liquid , and water should finally be added as appropriate in a proportion of 200 parts by weight. Laccase activity can be determined by ABTS—spectrophotometer method, the substrate used is 2,2′-azino-bis-(3-ethylbenzothiazole-6-sulfonic acid) referred to as ABTS, an enzyme activity unit (u) refers to the amount of enzyme required to catalyze the conversion of 1 μmol ABTS to the product per minute (min) under certain reaction conditions.

c、漆酶粘合剂的制备:按照上述配比称取各原料,先将滑石粉与漆酶液混合,搅拌均匀成糊状物,再将该糊状物与木素磺酸铵混合并搅拌均匀,最后加入水搅拌匀均即可。c. Preparation of laccase adhesive: take each raw material according to the above ratio, first mix talcum powder with laccase liquid, stir to form a paste, then mix the paste with ammonium lignosulfonate and mix Stir well, and finally add water and mix well.

d、漆酶粘合剂与木纤维的混合:利用步骤c得到的粘合剂,在搅拌机中对木纤维边喷射边搅拌,粘合剂用量按其固体含量占木纤维绝干质量的13%比例计算。D, the mixing of laccase binder and wood fiber: utilize the binder that step c obtains, stir while spraying to wood fiber limit in mixer, binder consumption accounts for 13% of wood fiber absolute dry mass by its solid content Proportional calculations.

e、漆酶处理纤维板的压制:将步骤d得到纤维板料用常规的工序即经铺装、预压、热压、后处理即成,预压线压力2.5kN/cm,热压温度200℃,热压压力3.5MPa,预压时间30s,热压时间60s/mm。e. Compression of laccase-treated fiberboard: the fiberboard obtained in step d is prepared by conventional procedures, namely paving, pre-pressing, hot-pressing, and post-treatment. The pre-pressing line pressure is 2.5kN/cm, and the hot-pressing temperature is 200°C. The hot pressing pressure is 3.5MPa, the pre-pressing time is 30s, and the hot pressing time is 60s/mm.

实施例3:本实施例漆酶活化木素磺酸盐制造纤维板的方法包括以下步骤,Embodiment 3: In this embodiment, the method for activating lignosulfonate with laccase to manufacture fiberboard includes the following steps,

a、备料:a. Preparation:

将木材或其加工剩余料,按常规的中密度纤维板生产方法分离成木纤维并进行干燥,控制木纤维含水率为4%;Wood or its processing residues are separated into wood fibers according to conventional medium density fiberboard production methods and dried to control the moisture content of wood fibers to 4%;

漆酶,从诺维信(中国)投资有限公司购置含水酶制剂——漆酶NS51003;Laccase, purchased from Novozymes (China) Investment Co., Ltd., an aqueous enzyme preparation - laccase NS51003;

木素磺酸铵,从武汉华东化工有限公司购得,为粉状物;Ammonium lignosulfonate, purchased from Wuhan Huadong Chemical Co., Ltd., is a powder;

滑石粉,从化工商店购得粒度为2000目的滑石粉。Talcum powder, purchased particle size from the chemical store is 2000 mesh talcum powder.

b、漆酶粘合剂原料的计量:漆酶的用量为每克(g)绝干的木素磺酸铵粉需50个酶活力单位(u),滑石粉用量为木素磺酸铵粉质量的0.75%,22.5重量份的木素磺酸铵和170重量份的水。配制漆酶粘合剂时,先以木素磺酸铵的用量为基数,按其绝干质量50u/g推算出需用酶活力单位(u)的总数,再根据漆酶活性计算出漆酶的用量;滑石粉用量为木素磺酸铵粉质量的0.75%;最后按重量份比确定水的用量,由于本例中漆酶为漆酶液,因此水的用量应包括漆酶液的重量,而且水应最后按170重量份的比例范围内酌定加入。漆酶活性测定可采用ABTS——分光光度计法,用的底物为2,2′-连氮-双-(3-乙基苯并噻唑-6-磺酸)简称ABTS,一个酶活单位(u)指一定反应条件下,每分钟(min)催化1μmol ABTS转化为产物所需的酶量。b. The measurement of laccase binder raw materials: the dosage of laccase is 50 enzyme activity units (u) per gram (g) of dry ammonium lignosulfonate powder, and the dosage of talcum powder is ammonium lignosulfonate powder 0.75% by mass, 22.5 parts by weight of ammonium lignosulfonate and 170 parts by weight of water. When preparing laccase adhesive, first use the amount of ammonium lignosulfonate as the base, and calculate the total number of enzyme activity units (u) according to its absolute dry mass of 50u/g, and then calculate the laccase activity according to the laccase activity. The consumption of talcum powder is 0.75% of ammonium lignosulfonate powder quality; Finally, the consumption of water is determined by weight ratio, because laccase is laccase liquid in this example, so the consumption of water should include the weight of laccase liquid , and water should finally be added as appropriate in a proportion of 170 parts by weight. Laccase activity can be determined by ABTS—spectrophotometer method, the substrate used is 2,2′-azino-bis-(3-ethylbenzothiazole-6-sulfonic acid) referred to as ABTS, an enzyme activity unit (u) refers to the amount of enzyme required to catalyze the conversion of 1 μmol ABTS to the product per minute (min) under certain reaction conditions.

c、漆酶粘合剂的制备:按照上述配比称取各原料,先将滑石粉与漆酶液混合,搅拌均匀成糊状物,再将该糊状物与木素磺酸铵混合并搅拌均匀,最后加入水搅拌匀均即可。c. Preparation of laccase adhesive: take each raw material according to the above ratio, first mix talcum powder with laccase liquid, stir to form a paste, then mix the paste with ammonium lignosulfonate and mix Stir well, and finally add water and mix well.

d、漆酶粘合剂与木纤维的混合:利用步骤c得到的粘合剂,在搅拌机中对木纤维边喷射边搅拌,粘合剂用量按其固体含量占木纤维绝干质量的11%比例计算。D, the mixing of laccase binder and wood fiber: utilize the binder that step c obtains, stir while spraying to wood fiber limit in mixer, binder consumption accounts for 11% of wood fiber absolute dry mass by its solid content Proportional calculations.

e、漆酶处理纤维板的压制:将步骤d得到纤维板料用常规的工序即经铺装、预压、热压、后处理即成,预压线压力2kN/cm,热压温度185℃,热压压力3MPa,预压时间20s,热压时间45s/mm。e. Compression of laccase-treated fiberboard: the fiberboard obtained in step d is prepared by conventional procedures, namely paving, pre-pressing, hot-pressing, and post-treatment. The pre-pressing line pressure is 2kN/cm, and the hot-pressing temperature is 185°C. The pressing pressure is 3MPa, the pre-pressing time is 20s, and the hot pressing time is 45s/mm.

实施例4:本实施例漆酶活化木素磺酸盐制造纤维板的方法包括以下步骤,Embodiment 4: The method for activating lignosulfonate to manufacture fiberboard with laccase in this embodiment includes the following steps,

a、备料:a. Preparation:

将木材或其加工剩余料,按常规的中密度纤维板生产方法分离成木纤维并进行干燥,控制木纤维含水率为4%;Wood or its processing residues are separated into wood fibers according to conventional medium density fiberboard production methods and dried to control the moisture content of wood fibers to 4%;

漆酶,从诺维信(中国)投资有限公司购置含水酶制剂——漆酶NS51003;Laccase, purchased from Novozymes (China) Investment Co., Ltd., an aqueous enzyme preparation - laccase NS51003;

木素磺酸钠,从武汉华东化工有限公司购得,为粉状物;Sodium lignosulfonate, purchased from Wuhan Huadong Chemical Co., Ltd., is a powder;

滑石粉,从化工商店购得粒度为2000目的滑石粉。Talcum powder, purchased particle size from the chemical store is 2000 mesh talcum powder.

b、漆酶粘合剂原料的计量:漆酶的用量为每克(g)绝干的木素磺酸钠粉需45个酶活力单位(u),滑石粉用量为木素磺酸钠粉质量的0.8%,22重量份的木素磺酸钠和180重量份的水。配制漆酶粘合剂时,先以木素磺酸钠的用量为基数,按其绝干质量45u/g推算出需用酶活力单位(u)的总数,再根据漆酶活性计算出漆酶的用量;滑石粉用量为木素磺酸钠粉质量的0.8%;最后按重量份比确定水的用量,由于本例中漆酶为漆酶液,因此水的用量应包括漆酶液的重量,而且水应最后按180重量份的比例范围内酌定加入。漆酶活性测定可采用ABTS——分光光度计法,用的底物为2,2′-连氮-双-(3-乙基苯并噻唑-6-磺酸)简称ABTS,一个酶活单位(u)指一定反应条件下,每分钟(min)催化1μmol ABTS转化为产物所需的酶量。b. The measurement of laccase binder raw materials: the amount of laccase is 45 enzyme activity units (u) per gram (g) of dry sodium lignosulfonate powder, and the amount of talcum powder is sodium lignosulfonate powder 0.8% by mass, 22 parts by weight of sodium lignosulfonate and 180 parts by weight of water. When preparing laccase adhesive, first use the amount of sodium lignosulfonate as the base, and calculate the total number of enzyme activity units (u) according to its absolute dry mass of 45u/g, and then calculate the laccase activity according to the laccase activity. The consumption of talcum powder is 0.8% of sodium lignosulfonate powder quality; Finally, the consumption of water is determined by weight ratio, because laccase is laccase liquid in this example, so the consumption of water should include the weight of laccase liquid , and water should finally be added as appropriate in a proportion of 180 parts by weight. Laccase activity can be determined by ABTS—spectrophotometer method, the substrate used is 2,2′-azino-bis-(3-ethylbenzothiazole-6-sulfonic acid) referred to as ABTS, an enzyme activity unit (u) refers to the amount of enzyme required to catalyze the conversion of 1 μmol ABTS to the product per minute (min) under certain reaction conditions.

c、漆酶粘合剂的制备:按照上述配比称取各原料,先将滑石粉与漆酶液混合,搅拌均匀成糊状物,再将该糊状物与木素磺酸钠混合并搅拌均匀,最后加入水搅拌匀均即可。c. Preparation of laccase adhesive: take each raw material according to the above ratio, first mix talcum powder with laccase liquid, stir to form a paste, then mix the paste with sodium lignosulfonate and mix Stir well, and finally add water and mix well.

d、漆酶粘合剂与木纤维的混合:利用步骤c得到的粘合剂,在搅拌机中对木纤维边喷射边搅拌,粘合剂用量按其固体含量占木纤维绝干质量的10%比例计算。D, the mixing of laccase binder and wood fiber: utilize the binder that step c obtains, stir while spraying to wood fiber limit in mixer, binder consumption accounts for 10% of wood fiber absolute dry mass by its solid content Proportional calculations.

e、漆酶处理纤维板的压制:将步骤d得到纤维板料用常规的工序即经铺装、预压、热压、后处理即成,预压线压力1.8kN/cm,热压温度180℃,热压压力2.5MPa,预压时间20s,热压时间40s/mm。e. Compression of laccase-treated fiberboard: the fiberboard obtained in step d is prepared by conventional procedures, namely paving, pre-pressing, hot-pressing, and post-treatment. The pre-pressing line pressure is 1.8kN/cm, and the hot-pressing temperature is 180°C. The hot pressing pressure is 2.5MPa, the pre-pressing time is 20s, and the hot pressing time is 40s/mm.

实施例5:本实施例漆酶活化木素磺酸盐制造纤维板的方法包括以下步骤,Embodiment 5: The method for activating lignosulfonate to manufacture fiberboard with laccase in this embodiment includes the following steps,

a、备料:a. Preparation:

将木材或其加工剩余料,按常规的中密度纤维板生产方法分离成木纤维并进行干燥,控制木纤维含水率为3%;The wood or its processing residues are separated into wood fibers according to the conventional medium density fiberboard production method and dried, and the moisture content of the wood fibers is controlled to 3%;

漆酶,从诺维信(中国)投资有限公司购置含水酶制剂——漆酶NS51003;Laccase, purchased from Novozymes (China) Investment Co., Ltd., an aqueous enzyme preparation - laccase NS51003;

木素磺酸钠,从武汉华东化工有限公司购得,为粉状物;Sodium lignosulfonate, purchased from Wuhan Huadong Chemical Co., Ltd., is a powder;

滑石粉,从化工商店购得粒度为3000目的滑石粉。Talcum powder, purchased particle size from the chemical store is 3000 mesh talcum powder.

b、漆酶粘合剂原料的计量:漆酶的用量为每克(g)绝干的木素磺酸钠粉需40个酶活力单位(u),滑石粉用量为木素磺酸钠粉质量的0.8%,20重量份的木素磺酸钠和145重量份的水。配制漆酶粘合剂时,先以木素磺酸钠的用量为基数,按其绝干质量40u/g推算出需用酶活力单位(u)的总数,再根据漆酶活性计算出漆酶的用量;滑石粉用量为木素磺酸钠粉质量的0.8%;最后按重量份比确定水的用量,由于本例中漆酶为漆酶液,因此水的用量应包括漆酶液的重量,而且水应最后按145重量份的比例范围内酌定加入。漆酶活性测定可采用ABTS——分光光度计法,用的底物为2,2′-连氮-双-(3-乙基苯并噻唑-6-磺酸)简称ABTS,一个酶活单位(u)指一定反应条件下,每分钟(min)催化1μmol ABTS转化为产物所需的酶量。b. The measurement of laccase binder raw materials: the dosage of laccase is 40 enzyme activity units (u) per gram (g) of dry sodium lignosulfonate powder, and the dosage of talcum powder is sodium lignosulfonate powder 0.8% by mass, 20 parts by weight of sodium lignosulfonate and 145 parts by weight of water. When preparing laccase adhesive, first use the amount of sodium lignosulfonate as the base, and calculate the total number of enzyme activity units (u) according to its absolute dry mass of 40u/g, and then calculate the laccase activity according to the laccase activity. The consumption of talcum powder is 0.8% of sodium lignosulfonate powder quality; Finally, the consumption of water is determined by weight ratio, because laccase is laccase liquid in this example, so the consumption of water should include the weight of laccase liquid , and water should finally be added as appropriate in a proportion of 145 parts by weight. Laccase activity can be determined by ABTS—spectrophotometer method, the substrate used is 2,2′-azino-bis-(3-ethylbenzothiazole-6-sulfonic acid) referred to as ABTS, an enzyme activity unit (u) refers to the amount of enzyme required to catalyze the conversion of 1 μmol ABTS to the product per minute (min) under certain reaction conditions.

c、漆酶粘合剂的制备:按照上述配比称取各原料,先将滑石粉与漆酶液混合,搅拌均匀成糊状物,再将该糊状物与木素磺酸钠混合并搅拌均匀,最后加入水搅拌匀均即可。c. Preparation of laccase adhesive: take each raw material according to the above ratio, first mix talc powder with laccase liquid, stir to form a paste, then mix the paste with sodium lignosulfonate and mix Stir well, and finally add water and mix well.

d、漆酶粘合剂与木纤维的混合:利用步骤c得到的粘合剂,在搅拌机中对木纤维边喷射边搅拌,粘合剂用量按其固体含量占木纤维绝干质量的9%比例计算。D, the mixing of laccase binder and wood fiber: utilize the binder that step c obtains, stir while spraying to wood fiber limit in mixer, binder consumption accounts for 9% of wood fiber absolute dry mass by its solid content Proportional calculations.

e、漆酶处理纤维板的压制:将步骤d得到纤维板料用常规的工序即经铺装、预压、热压、后处理即成,预压线压力1.5kN/cm,热压温度170℃,热压压力2.0MPa,预压时间15s,热压时间30s/mm。e. Compression of laccase-treated fiberboard: the fiberboard obtained in step d is prepared by conventional procedures, namely paving, pre-pressing, hot-pressing, and post-treatment. The pre-pressing line pressure is 1.5kN/cm, and the hot-pressing temperature is 170°C. The hot pressing pressure is 2.0MPa, the pre-pressing time is 15s, and the hot pressing time is 30s/mm.

上述各实施例中所述漆酶还可以选用诺维信(中国)投资有限公司生产的干燥漆酶粉,由于其本身不含水,因此其用量不计入水的用量中。The laccase described in the above embodiments can also be dry laccase powder produced by Novozymes (China) Investment Co., Ltd., since it does not contain water, its dosage is not included in the water dosage.

为了进一步提高漆酶的活化效果,可以在前述五个实施例制备粘合剂的原料中加入磷酸氢二钠—柠檬酸缓冲液,其用量须保证能够调节反应体系的pH值至3.5-4.5,并且该缓冲液的液量应计入水的用量中。In order to further improve the activation effect of laccase, disodium hydrogen phosphate-citric acid buffer can be added to the raw materials for preparing the adhesive in the aforementioned five embodiments, and the amount must ensure that the pH value of the reaction system can be adjusted to 3.5-4.5. And the amount of this buffer should be included in the amount of water used.

本发明将滑石粉用于漆酶活化木素磺酸盐的反应体系,在其它处理条件相同的情况下,其活性氧类(ROS)自由基浓度比未加滑石粉的反应体系高1-5倍。下面列出不同酶用量和加与不加滑石粉处理木材产生的ROS水平列表1:In the present invention, talcum powder is used in the reaction system of laccase to activate lignosulfonate. Under the same conditions, the concentration of reactive oxygen species (ROS) free radicals is 1-5 times higher than that of the reaction system without talc powder. times. The following is a list of ROS levels produced by different enzyme dosages and wood treated with and without talc1:

(表1)(Table 1)

由表1可见,不同酶用量对ROS自由基浓度有显著影响,当酶用量为40u每克绝干木素磺酸盐质量时,ROS自由基浓度达到峰值,在滑石粉的加入量为木素磺酸盐绝干质量0.8%时,ROS自由基浓度比不加滑石粉的高1-5倍。正因为如此,制备粘合剂时,即使不用缓冲液调节反应体系的pH值,不加温、不预留反应时间,虽有酶的作用不十分充分之虑,但用该粘合剂生产的人造板强度依然能达到相应的国标要求,这是难以预料到的。It can be seen from Table 1 that different enzyme dosages have a significant impact on the concentration of ROS free radicals. When the dosage of enzymes is 40u per gram of absolute dry lignosulfonate, the concentration of ROS free radicals reaches a peak value. When the absolute dry mass of sulfonate is 0.8%, the concentration of ROS free radicals is 1-5 times higher than that without talc. Because of this, even if the pH value of the reaction system is not adjusted with a buffer solution, the temperature is not increased, and the reaction time is not reserved when preparing the adhesive, although the action of the enzyme may not be sufficient, the adhesive produced The strength of wood-based panels can still meet the corresponding national standard requirements, which is hard to predict.

Claims (3)

1. laccase activation lignosulphonates are manufactured a method for fiberboard, it is characterized in that step is as follows:
A, timber or its processing residue material is separated into wood-fibred and is dried, control moisture content is 3-5%;
B, talcum powder mixed with laccase and mix thoroughly, then adding lignosulphonates mixing and stirring, finally adding water and stir and obtain laccase adhesive;
C, the adhesive that utilizes step b to obtain stir injection limit, wood-fibred limit in mixer, and the 8-13% ratio that binder dosage accounts for wood-fibred over dry quality in its solids content is calculated;
D, the fiber plate that step c is obtained are mated formation, precompressed, hot pressing, post processing, precompressed linear pressure 1.5-2.5kN/cm, hot pressing temperature 170-200 ℃, hot pressing pressure 2.0-3.5MPa, squeeze time 10-30 s, hot pressing time 30-60s/mm;
Each raw material proportioning of preparing described adhesive in step b is,
The lignosulphonates of 20-25 weight portion;
In every grammes per square metre lignosulphonates over dry powder, add the laccase of 40-55 enzyme activity unit;
The talcum powder of lignosulphonates opaque amount 0.5%-1%;
The water of 145-200 weight portion;
Described laccase is dry laccase powder or laccase liquid, and wherein the weight of laccase liquid counts in the consumption of water.
2. laccase activation lignosulphonates according to claim 1 are manufactured the method for fiberboard, it is characterized in that: described talcous granularity is 1000-3000 order.
3. laccase activation lignosulphonates according to claim 1 and 2 are manufactured the method for fiberboard, it is characterized in that: described lignosulphonates are ammonium lignin sulfonate or sodium lignosulfonate.
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