JP2009167554A - Method for producing pulp - Google Patents
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- JP2009167554A JP2009167554A JP2008006334A JP2008006334A JP2009167554A JP 2009167554 A JP2009167554 A JP 2009167554A JP 2008006334 A JP2008006334 A JP 2008006334A JP 2008006334 A JP2008006334 A JP 2008006334A JP 2009167554 A JP2009167554 A JP 2009167554A
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- 238000004519 manufacturing process Methods 0.000 title claims abstract description 25
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 96
- 238000000034 method Methods 0.000 claims abstract description 58
- 229920005610 lignin Polymers 0.000 claims abstract description 57
- 238000010411 cooking Methods 0.000 claims abstract description 34
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 26
- 239000000243 solution Substances 0.000 claims abstract description 19
- 239000007864 aqueous solution Substances 0.000 claims abstract description 16
- 230000001590 oxidative effect Effects 0.000 claims abstract description 4
- 239000002023 wood Substances 0.000 claims description 56
- 230000008569 process Effects 0.000 claims description 42
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 32
- 229910001868 water Inorganic materials 0.000 claims description 32
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 30
- 238000007254 oxidation reaction Methods 0.000 claims description 28
- 230000003647 oxidation Effects 0.000 claims description 26
- 238000005406 washing Methods 0.000 claims description 12
- 239000003513 alkali Substances 0.000 claims description 11
- 238000004140 cleaning Methods 0.000 claims description 11
- 238000010438 heat treatment Methods 0.000 claims description 7
- 230000029087 digestion Effects 0.000 claims description 5
- 238000000926 separation method Methods 0.000 claims description 5
- 238000005520 cutting process Methods 0.000 claims description 3
- 238000002791 soaking Methods 0.000 claims 1
- 239000002655 kraft paper Substances 0.000 abstract description 8
- 229910052979 sodium sulfide Inorganic materials 0.000 abstract description 8
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 abstract description 8
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 12
- 239000000126 substance Substances 0.000 description 10
- 239000000463 material Substances 0.000 description 9
- 238000010276 construction Methods 0.000 description 8
- 239000001301 oxygen Substances 0.000 description 8
- 229910052760 oxygen Inorganic materials 0.000 description 8
- 239000002994 raw material Substances 0.000 description 8
- 238000004064 recycling Methods 0.000 description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 7
- 238000004061 bleaching Methods 0.000 description 6
- 239000001569 carbon dioxide Substances 0.000 description 6
- 229910002092 carbon dioxide Inorganic materials 0.000 description 6
- 239000001913 cellulose Substances 0.000 description 5
- 229920002678 cellulose Polymers 0.000 description 5
- 239000000446 fuel Substances 0.000 description 5
- OSVXSBDYLRYLIG-UHFFFAOYSA-N dioxidochlorine(.) Chemical compound O=Cl=O OSVXSBDYLRYLIG-UHFFFAOYSA-N 0.000 description 4
- 239000000428 dust Substances 0.000 description 4
- 239000002699 waste material Substances 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
- QMMFVYPAHWMCMS-UHFFFAOYSA-N Dimethyl sulfide Chemical compound CSC QMMFVYPAHWMCMS-UHFFFAOYSA-N 0.000 description 3
- -1 HFCs Chemical compound 0.000 description 3
- 239000005708 Sodium hypochlorite Substances 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- 239000000123 paper Substances 0.000 description 3
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 3
- 239000004155 Chlorine dioxide Substances 0.000 description 2
- 229920002488 Hemicellulose Polymers 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 2
- GQPLMRYTRLFLPF-UHFFFAOYSA-N Nitrous Oxide Chemical compound [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 description 2
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 2
- 229920001131 Pulp (paper) Polymers 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 229920002522 Wood fibre Polymers 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 235000019398 chlorine dioxide Nutrition 0.000 description 2
- WQOXQRCZOLPYPM-UHFFFAOYSA-N dimethyl disulfide Chemical compound CSSC WQOXQRCZOLPYPM-UHFFFAOYSA-N 0.000 description 2
- 238000010828 elution Methods 0.000 description 2
- 238000005187 foaming Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 235000005985 organic acids Nutrition 0.000 description 2
- 238000010525 oxidative degradation reaction Methods 0.000 description 2
- 239000011120 plywood Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 238000007127 saponification reaction Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000002025 wood fiber Substances 0.000 description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 235000016496 Panda oleosa Nutrition 0.000 description 1
- 240000000220 Panda oleosa Species 0.000 description 1
- 229910018503 SF6 Inorganic materials 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000010426 asphalt Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 150000001720 carbohydrates Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 210000000078 claw Anatomy 0.000 description 1
- 239000002361 compost Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000037213 diet Effects 0.000 description 1
- 235000005911 diet Nutrition 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000001272 nitrous oxide Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 238000010129 solution processing Methods 0.000 description 1
- SFZCNBIFKDRMGX-UHFFFAOYSA-N sulfur hexafluoride Chemical compound FS(F)(F)(F)(F)F SFZCNBIFKDRMGX-UHFFFAOYSA-N 0.000 description 1
- 229960000909 sulfur hexafluoride Drugs 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 239000002916 wood waste Substances 0.000 description 1
Landscapes
- Paper (AREA)
Abstract
Description
本発明は、クラフト法との比較で、硫化ソーダ及び高温・高圧条件を用いずに高収率でパルプを製造し、リグニンを回収するようにしたパルプの製造方法に関する。 The present invention relates to a method for producing a pulp in which a pulp is produced in a high yield without using sodium sulfide and high-temperature / high-pressure conditions and lignin is recovered as compared with the kraft method.
更には、建築発生木材（木質建築の解体木屑・建築廃材、家具類）をパルプ原料として利用しようとするものである。 Furthermore, it is intended to use building-generated timber (demolition wood waste, building waste, furniture, etc. of wooden construction) as a pulp raw material.
建設リサイクル法（建設工事に係る資材の再資源化等に関する法律（平成１２年５月３１日法律第１０４号））の施行により、建設（解体）工事に伴って廃棄されるコンクリート塊、アスファルト・コンクリート塊、建設発生木材の分別リサイクルが求められている。 As a result of the enforcement of the Construction Recycling Law (Act on the Recycling of Materials Related to Construction Work (Act No. 104 of May 31, 2000)), concrete blocks, asphalt, There is a need for separate recycling of concrete lumps and construction wood.
また、気候変動枠組条約に基づき、１９９７年に京都議定書が議決されたが、地球温暖化の原因となる、温室効果ガスの一種である二酸化炭素、メタン、亜酸化窒素、HFCs、六フッ化硫黄について、先進国における削減率を１９９０年基準として各国別に定め、共同で約束期間内に目標を達成することになった。日本では、２００２年５月３１日に国会承認され、２００４年６月４日に国際連合に受諾書を寄託している。
目標として、２００８〜２０１２年の間に、日本マイナス６％、アメリカマイナス７％、ＥＵマイナス８％といった削減率を設定している。
In addition, the Kyoto Protocol was approved in 1997 based on the Framework Convention on Climate Change, but carbon dioxide, methane, nitrous oxide, HFCs, sulfur hexafluoride, which are types of greenhouse gases that cause global warming. As a result, the reduction rate in developed countries was determined for each country based on the 1990 standard, and the target was jointly achieved within the commitment period. In Japan, the Diet was approved on May 31, 2002, and a letter of acceptance was deposited with the United Nations on June 4, 2004.
As a target, reduction rates such as Japan minus 6%, America minus 7%, EU minus 8% are set between 2008 and 2012.
本発明は、このような社会の要請に応えようとするものである。 The present invention is intended to meet such social demands.
建設発生木材については、縮減（焼却）されるものも含めてリサイクル率の目標が９５％に設定されており、木材チップに粉砕して、パーティクル用ボード、製紙原料、堆肥、マルチング、サーマルリサイクル（燃料）、ケミカルリサイクル等にリサイクルされているが、不適正堆積（不法投棄）もあり、それが自然発火して火災が発生したこともある。
家屋に使用されている材料は木材が最も多いが、修製材をはじめ板材は直行に張り合わせたもの、塗料、接着剤を使用したもの等、資材としてリサイクルが困難なものが多く、リサイクルの過半はサーマルリサイクル（燃料）である。
建設発生木材は、関東圏だけでも９００万トン／年排出されているが、廃木材を縮減（焼却）、サーマルリサイクルではなく、製紙原料として用いれば、紙は２〜３回リサイクルされるので、木材を産出するのに必要な森林の２〜３倍の森林を温存することになり、酸素の供給、炭酸ガスの発生の抑制効果も２〜３倍となるのである。
For the wood generated from construction, the recycling rate target is set at 95%, including those that are reduced (incinerated), and pulverized into wood chips for particle board, papermaking raw material, compost, mulching, thermal recycling ( Fuel), chemical recycling, etc., but there is also improper accumulation (illegal dumping), which spontaneously ignited and sometimes caused a fire.
Wood is the most common material used in houses, but there are many materials that are difficult to recycle, such as straightened materials such as repair materials, and materials that use paints and adhesives. Thermal recycling (fuel).
Construction-generated wood is discharged 9 million tons / year in the Kanto area alone, but if waste wood is used as a raw material for papermaking instead of reducing (incineration) and thermal recycling, paper is recycled two or three times. This means that two to three times as many forests as necessary to produce timber will be preserved, and the effects of suppressing oxygen supply and carbon dioxide generation will be two to three times.
このように、建設発生木材は、製紙原料としてリサイクルすることが有利であるが、パルプの生産量の９５％を占めるクラフト法においては、良質の木材チップを製紙原料としており、建築発生木材のごく一部しか用いられていないのが現状である。 In this way, it is advantageous to recycle construction-generated wood as a papermaking raw material. However, in the kraft method, which accounts for 95% of pulp production, high-quality wood chips are used as papermaking raw materials, so Currently, only a part is used.
現在、世界でのパルプの９５％は、木質チップを主原料として、クラフト法にて生産されている。この生産方法は、天然素材、主として森林から伐採された木材を砕いた木質チップに、水、苛性ソーダ、硫化ソーダを一定割合にて加え、６〜７気圧の容器内で平均１６０℃の温度で３時間以上蒸解（煮沸）させ、連続的に木質に含まれるセルロースの結合機能を持つリグニンをこの溶液中に溶解させ、セルロースとヘミセルロースを単離させることによりセルロースの塊であるパルプを生成させている。得られたパルプは通称フレッシュパルプと呼称されている。この方法は現在最もコストパフォーマンスの良いパルプの製造方法である。 Currently, 95% of the world's pulp is produced by the craft method using wood chips as the main raw material. In this production method, water, caustic soda, and sodium sulfide are added at a fixed rate to wood chips obtained by pulverizing natural materials, mainly wood cut from forests, and a temperature of 160 ° C. is averaged at a temperature of 160 ° C. It is cooked (boiling) for more than an hour, and lignin having the cellulose binding function contained in the wood is continuously dissolved in this solution, and cellulose and hemicellulose are isolated to produce pulp that is a lump of cellulose. . The resulting pulp is commonly called fresh pulp. This method is currently the most cost effective pulp production method.
クラフト法の概要を図１に基づいて説明する。
チップは、ムラ炊きにならないように、また、均一な蒸解を行うため、チップの厚みと長さを一定範囲に揃えると共にチップのダストを除去される。
クラフト蒸解工程では、水、薬品（苛性ソーダ、硫化ソーダ）を一定割合にて加え、１６０℃、６気圧前後で３時間以上蒸解（煮沸）させ、リグニンを溶解させる。
続く洗浄工程では、薬品（苛性ソーダ、硫化ソーダ）で溶かし出されたリグニンや薬品（黒液）をパルプから分離した後、パルプを水で洗浄する。
脱リグニン工程では、パルプに残っているリグニンを酸素とアルカリで更に溶かし出す。
精選工程では、パルプに含まれるゴミなどの異物を分離して除去する。
漂白工程では、塩素、二酸化塩素、酸素、苛性ソーダ、次亜塩素酸ソーダ等の薬品を使ってパルプを漂白する。
そして、黒液は、濃縮されて、プロセス内で燃料として使用され、炭酸ソーダとして回収される。
The outline of the craft method will be described with reference to FIG.
In order to prevent the chips from becoming unevenly cooked and to perform uniform cooking, the thickness and length of the chips are kept within a certain range and dust on the chips is removed.
In the kraft cooking process, water and chemicals (caustic soda, sodium sulfide) are added at a constant rate and cooked (boiled) at 160 ° C. and around 6 atm for 3 hours or more to dissolve lignin.
In the subsequent washing step, lignin and chemicals (black liquor) dissolved by chemicals (caustic soda and sodium sulfide) are separated from the pulp, and then the pulp is washed with water.
In the delignification step, the lignin remaining in the pulp is further dissolved with oxygen and alkali.
In the selection process, foreign matters such as dust contained in the pulp are separated and removed.
In the bleaching process, the pulp is bleached using chemicals such as chlorine, chlorine dioxide, oxygen, caustic soda and sodium hypochlorite.
The black liquor is then concentrated, used as fuel in the process, and recovered as sodium carbonate.
更に、クラフト法関連の特許文献を挙げる。
クラフト法は、上質の紙が製造できる利点があるが、次のような問題点がある。
（１）天然素材である森林を伐採することにより得られる木質チップを利用しており、旺盛な需要をまかなうには、多くの森林破壊を惹起しており、環境問題に課題がある。
（２）木質からリグニンを短時間に溶出せしめるため、１６０℃、６気圧前後の蒸解に使用可能な圧力容器を必要とし、装置が大型化し高価であり、ランニングコストとエネルギー消費が大きい。
（３）高温高圧下でリグニンの溶解を行うので、ヘミセルロース、セルロースの一部が溶出し、収率が５０％程度と悪い。
（４）蒸解液に硫化ソーダが含まれるため、硫化水素、メチルメルカプタン、硫化ジメチル、二硫化ジメチルが発生し、悪臭公害に注意が必要である。
（５）良質な水を大量に使用するため、水源の確保と排水処理にコストがかかる。
（６）パルプの収率が５０％前後であるから、木材の５０％前後がリグニンとして黒液中に分離され、濃縮・焼却により多量の炭酸ガスが発生する。
（説明）リグニンもセルロースと同様に炭水化物であるから、リグニン中の炭素は、Ｃ（１２）／ＣＨ2Ｏ（３０）＝０．４の割合で含まれる。１トンのパルプの製造には１トンのリグニンが生ずるから、リグニンの焼却により０．４トンの炭素が二酸化炭素になる。
Ｃ：ＣＯ2＝１２：４４であるから１トンのリグニン（０．４トンの炭素）では、０．４×４４／１２＝１．４７トンの二酸化炭素が発生する。
（７）以上のように、この方式は、専ら良質の木質チップを用いて良質のパルプを製造するものであり、建設発生木材をパルプ化するものではないし、炭酸ガスが多量発生するものである。
The kraft method has the advantage of producing high-quality paper, but has the following problems.
(1) The use of wood chips obtained by cutting natural forests has led to many deforestation to meet vigorous demand, and there are problems with environmental issues.
(2) In order to elute lignin from wood in a short time, a pressure vessel that can be used for cooking at 160 ° C. and around 6 atm is required, the apparatus is large and expensive, and running cost and energy consumption are large.
(3) Since lignin is dissolved under high temperature and high pressure, hemicellulose and a part of cellulose are eluted, and the yield is poor at about 50%.
(4) Since sodium sulfide is contained in the cooking liquor, hydrogen sulfide, methyl mercaptan, dimethyl sulfide, and dimethyl disulfide are generated, and it is necessary to pay attention to bad odor pollution.
(5) Since high-quality water is used in large quantities, it costs money to secure water sources and to treat wastewater.
(6) Since the yield of the pulp is around 50%, around 50% of the wood is separated into the black liquor as lignin, and a large amount of carbon dioxide is generated by concentration and incineration.
(Explanation) Since lignin is a carbohydrate like cellulose, carbon in lignin is contained in a ratio of C (12) / CH 2 O (30) = 0.4. Since 1 ton of lignin is produced in the production of 1 ton of pulp, the incineration of lignin converts 0.4 ton of carbon to carbon dioxide.
Since C: CO 2 = 12: 44, 1 ton of lignin (0.4 ton of carbon) generates 0.4 × 44/12 = 1.47 ton of carbon dioxide.
(7) As described above, this method is to produce high-quality pulp exclusively using high-quality wood chips, not to pulp construction-generated wood, and to generate a large amount of carbon dioxide. .
本発明は、上記問題点に鑑み、建設発生木材をも用いず、圧力容器を必要とせず、収率が高く、硫化物のような公害源を用いず、水の使用量が少なく、リグニンを燃料に用いないパルプの製造方法を提供することにある。 In view of the above problems, the present invention does not use construction-generated wood, does not require a pressure vessel, has a high yield, does not use pollution sources such as sulfides, uses less water, and reduces lignin. An object of the present invention is to provide a method for producing pulp that is not used as fuel.
本発明は上記課題を解決する新規な発明であり、下記構成のパルプの製造方法である。
（１）木質チップを希苛性ソーダ水溶液に浸漬して親水化する親水化処理工程と、
次いで前記工程で得られた親水化処理済み木質チップに水又は温水を加えてアルカリ分を除去する第１洗浄処理工程と、
前記第一洗浄処理工程を施して得られた第１洗浄処理済み木質チップに希硝酸を加えて常温又は加温下において酸化処理して木質チップに含まれるリグニンを選択的に部分酸化する酸化処理工程と、
前記酸化処理工程で得られた酸化処理済み木質チップに水又は温水を加えて希硝酸分を除去する第２洗浄工程と、
前記第２洗浄工程で得られた第２洗浄処理済み木質チップに希苛性ソーダ水溶液を加え加温して前記木質チップを蒸解する蒸解処理工程と、
前記蒸解処理工程で得られた蒸解処理済み物を濾別して蒸解パルプとリグニンを含有する黒液とに分離する蒸解パルプ・黒液分離処理工程とからなることを特徴とするパルプの製造方法。
（２）木質チップ１重量部を、１〜１０重量％濃度の苛性ソーダ水溶液５〜２０重量部に１５〜４０℃で１０〜６０時間浸漬して親水化する親水化処理工程と、
次いで前記工程で得られた親水化処理済み木質チップに水又は温水を加えてアルカリ分を除去する第１洗浄処理工程と、
前記第１洗浄処理工程を施して得られた第１洗浄処理済み木質チップ１重量部に、１〜１０重量％濃度の硝酸水溶液３〜１５重量部を加えて、８０〜９８℃で４０〜１２０分間酸化処理して木質チップに含まれるリグニンを選択的に部分酸化する酸化処理工程と、
前記酸化処理工程で得られた酸化処理済み木質チップに水又は温水を加えて希硝酸分を除去する第２洗浄工程と、
前記第２洗浄工程で得られた第２洗浄処理済み木質チップ１重量部に、１〜２０重量％濃度の苛性ソーダ水溶液５〜２０重量部を加え常圧下又は加圧下において９５〜１００℃で３０〜１２０分間加熱して前記木質チップを蒸解する蒸解処理工程と、
前記蒸解処理工程で得られた蒸解処理済み物を濾別して蒸解パルプとリグニンを含有する黒液とに分離する蒸解パルプ・黒液分離処理工程とからなることを特徴とするパルプの製造方法。
This invention is a novel invention which solves the said subject, and is a manufacturing method of the pulp of the following structure.
(1) a hydrophilization treatment step of hydrophilizing a wooden chip by immersing it in a dilute caustic soda solution;
Next, a first cleaning treatment step of removing alkali by adding water or warm water to the hydrophilized wood chip obtained in the step,
Oxidation treatment in which dilute nitric acid is added to the first washed wood chip obtained by performing the first washing treatment step and oxidized at room temperature or under heating to selectively oxidize lignin contained in the wood chip. Process,
A second washing step of removing dilute nitric acid by adding water or warm water to the oxidized wood chip obtained in the oxidation treatment step;
A cooking process for cooking the wooden chips by adding a dilute caustic soda aqueous solution to the second washed processed wooden chips obtained in the second cleaning process;
A pulp production method comprising: a digested pulp / black liquor separation process for separating the digested product obtained in the digestion process and separating it into a digested pulp and a black liquor containing lignin.
(2) A hydrophilization treatment step in which 1 part by weight of a wood chip is hydrophilized by immersing it in 5 to 20 parts by weight of a caustic soda aqueous solution having a concentration of 1 to 10% by weight at 15 to 40 ° C. for 10 to 60 hours;
Next, a first cleaning treatment step of removing alkali by adding water or warm water to the hydrophilized wood chip obtained in the step,
3 to 15 parts by weight of an aqueous nitric acid solution having a concentration of 1 to 10% by weight is added to 1 part by weight of a first cleaned wood chip obtained by performing the first cleaning process step, and 40 to 120 at 80 to 98 ° C. An oxidation treatment step that selectively oxidizes lignin contained in the wood chip by oxidizing for a minute,
A second washing step of removing dilute nitric acid by adding water or warm water to the oxidized wood chip obtained in the oxidation treatment step;
5 to 20 parts by weight of a 1 to 20% by weight aqueous caustic soda solution is added to 1 part by weight of the second washed wood chip obtained in the second washing step, and 30 to 30 at 95 to 100 ° C. under normal pressure or under pressure. A cooking process for cooking the wood chips by heating for 120 minutes;
A pulp production method comprising: a digested pulp / black liquor separation process for separating the digested product obtained in the digestion process and separating it into a digested pulp and a black liquor containing lignin.
（３）親水化処理工程、酸化処理工程、又は蒸解処理工程のいずれか１又は２以上が低加圧下（例えば１〜２気圧）で実施されることを特徴とする前記（１）又は（２）に記載のパルプの製造方法。
（４）蒸解処理工程を、第１段階の蒸解処理工程と第２段階の蒸解処理工程に分割して実施し、第１段階の蒸解処理工程では第２段階の蒸解処理工程におけるよりも濃度の低い苛性ソーダ水溶液を使用することを特徴とする前記（１）〜（３）のいずれか１項に記載のパルプの製造方法。
（５）酸化処理工程を施した後、更に熱水を追加導入して硝酸の酸化反応速度を速めて、硝酸が全て費消されるようにすることを特徴とする前記（１）〜（４）のいずれか１項に記載のパルプの製造方法。
（６）木質チップが、森林を伐採することにより得られる木材、間伐材又は建設発生木材から選択される１種又は２種以上の木材であることを特徴とする前記（１）〜（５）のいずれか１項に記載のパルプの製造方法。
（７）リグニンを含有する黒液からリグニンを凝集させて分取することを特徴とする前記（１）〜（６）のいずれか１項にパルプの製造方法。
(3) The above (1) or (2), wherein any one or more of the hydrophilization treatment step, the oxidation treatment step, or the cooking treatment step is performed under low pressure (for example, 1 to 2 atm). ) Pulp manufacturing method.
(4) The cooking process is divided into a first stage cooking process and a second stage cooking process, and the first stage cooking process has a concentration higher than that in the second stage cooking process. The method for producing pulp according to any one of (1) to (3), wherein a low aqueous caustic soda solution is used.
(5) The above (1) to (4), wherein after the oxidation treatment step, additional hot water is further introduced to increase the oxidation reaction rate of nitric acid so that all nitric acid is consumed. The manufacturing method of the pulp of any one of these.
(6) Said (1)-(5), wherein the wood chip is one or more kinds of wood selected from wood obtained by cutting a forest, thinned wood, or construction generated wood The manufacturing method of the pulp of any one of these.
(7) The method for producing pulp according to any one of (1) to (6), wherein lignin is aggregated and fractionated from a black liquor containing lignin.
以上説明したとおり、本発明では、建設発生木材をも用い得、圧力容器を必要とせず、収率が高く、硫化物のような公害源を用いず、水の使用量が少なく、リグニンを燃料に用いないパルプの製造方法を提供することが可能となる効果は格別なものである。 As described above, in the present invention, construction-generated wood can be used, no pressure vessel is required, the yield is high, no pollution source such as sulfide is used, the amount of water used is small, and lignin is used as fuel. The effect that makes it possible to provide a method for producing a pulp that is not used in the process is exceptional.
クラフト法の蒸解工程では、高濃度の苛性ソーダ水溶液を用い硫化ソーダを添加しているが、高温・高圧のアルカリでリグニンを低分子化し、硫化ソーダでリグニンが再結合により高分子化するのを防止している。苛性ソーダ水溶液は、リグニンを溶解すると共に、有機酸の中和、樹脂分の鹸化に消費されるものである。
そこで、本発明では、蒸解工程以前に強い酸化剤である希硝酸水溶液を用いてリグニンを選択的に低分子化し、蒸解工程においては、希苛性ソーダ水溶液を採用して大気圧で沸騰点以下の穏かな条件下で蒸解を行い、リグニンのそれ以上の低分子化を避けつつリグニンを溶出し、黒液からのリグニンの凝縮・分離を容易にするものである。
In the kraft cooking process, sodium sulfide is added using a high-concentration caustic soda solution, but the lignin is depolymerized with high-temperature and high-pressure alkali to prevent lignin from being polymerized by recombination with sodium sulfide. is doing. The aqueous caustic soda solution dissolves lignin and is consumed for neutralization of organic acids and saponification of resin components.
Therefore, in the present invention, the lignin is selectively reduced in molecular weight using a dilute nitric acid aqueous solution that is a strong oxidizing agent before the cooking process, and in the cooking process, a dilute caustic soda aqueous solution is used to relax at a pressure below the boiling point at atmospheric pressure. Digestion is carried out under kana conditions, and lignin is eluted while avoiding further lowering of lignin, facilitating the condensation and separation of lignin from black liquor.
以下、図２の本発明のフローチャートの概略図に基づいて説明する。
チップとして、森林から伐採された木材を砕いた木質チップ類、建設発生木材（木質建築の解体木屑、建築廃材、廃合板類、ＣＣＡ材等）等を破砕して、夾雑物（金具、釘、セメント、張り合わせた物等）を分離したものを用いる。
チップの大きさは、原料により異なるが、薬液処理に適合する範囲（数ｍｍ〜十数ｍｍ）である。
親水化処理工程では、破砕されたチップを希苛性ソーダ水溶液（好ましくは１〜１０重量％濃度、より好ましくは１〜５重量％濃度）に常温（好ましくは１５〜４５℃）、大気圧下、数十時間（好ましくは１０〜５０時間）液浸する。
木質の繊維中にある内腔に低濃度の苛性ソーダ水溶液が浸透するので、木質繊維が水酸イオンの作用を受け、親水性になる。
希苛性ソーダ水溶液は、１〜１０重量％濃度がよく、１重量％未満では、所望の効果が得られないし、１０重量％を超えると後工程で希硝酸を適用するので、洗浄を充分にしなければならず洗浄工程に負荷がかかる。
また、親水化処理工程では、希苛性ソーダ水溶液で処理する前にチップを水に浸漬しておくと、なお一層親水化処理が容易になる。
Hereinafter, description will be made based on the schematic diagram of the flowchart of the present invention in FIG.
Chips such as wood chips that have been crushed from the forest, timber generated from construction (demolition of wood construction, waste wood, waste plywood, CCA materials, etc.) are crushed, and impurities (metal fittings, nails, Cement, pasted materials, etc.) are used.
The size of the chip varies depending on the raw material, but is in a range (several mm to several tens of mm) suitable for chemical solution processing.
In the hydrophilization treatment step, the crushed chip is diluted to a dilute caustic soda aqueous solution (preferably 1 to 10% by weight concentration, more preferably 1 to 5% by weight concentration) at room temperature (preferably 15 to 45 ° C.) and under atmospheric pressure. Immerse for 10 hours (preferably 10 to 50 hours).
Since the low concentration caustic soda aqueous solution penetrates into the lumen in the wood fiber, the wood fiber becomes hydrophilic under the action of the hydroxide ions.
The dilute caustic soda aqueous solution has a concentration of 1 to 10% by weight, and if it is less than 1% by weight, the desired effect cannot be obtained. If it exceeds 10% by weight, dilute nitric acid is applied in the subsequent step. That puts a load on the cleaning process.
In the hydrophilization treatment step, the hydrophilization treatment is further facilitated by immersing the chip in water before the treatment with the dilute caustic soda aqueous solution.
洗浄工程では、次工程の酸化処理のためにアルカリ分を充分除去するようにすれば良い。 In the washing step, the alkali content may be sufficiently removed for the oxidation treatment in the next step.
酸化処理工程では、親水化されたチップを希硝酸水溶液（好ましくは１〜１０重量％濃度）に浸漬し、リグニンを選択的に部分酸化して、酸化分解と低分子化を促す。
希硝酸は、主に次式のように反応し強い酸化作用を示す。
２ＨＮＯ3→２ＮＯ＋５［Ｏ］＋Ｈ2Ｏ
［Ｏ］は、酸素ラジカル（活性酸素）であり、反応性が高く、存在時間は極めて短い。
リグニンにあるＣ−Ｏ−Ｃ結合、Ｃ＝Ｃ結合、Ｃ＝Ｏ結合を分解し、酸化分解と低分子化を達成するものである。
希硝酸は、汚れが触媒的に作用し、加熱により、急速に反応が進行することがあるし、８０℃程度で急速に反応するから、酸化処理工程では、パルプ及び希硝酸を常温で導入し、その後９８℃前後まで加熱すると、酸化処理の全期間に渡り制御された酸化状態を維持することができる。
加熱あるいは撹拌のために、容器の底部から蒸気を吹き込むことが有効である。
この処理時間は、数十分であることが適切である。
［Ｏ］の副反応として、Ｏ2、ＮＯ2の生成があり、容器頂部から、ＮＯ、ＮＯ2を含有するガスが回収される。
ＮＯ及びＮＯ2は、窒素酸化物（ＮＯx）であるから、回収して硝酸の原料とすることが適切である。
硝酸の工業的製法として、オストワルト法が知られている。
２ＮＯ＋Ｏ2 → ２ＮＯ2
３ＮＯ2＋Ｈ2Ｏ→２ＨＮＯ3＋ＮＯ（ＮＯは戻す）
オストワルト法を採用して、この工程で発生するＮＯ、ＮＯ2を、硝酸として回収することができる。
In the oxidation treatment step, the hydrophilized chip is immersed in a dilute nitric acid aqueous solution (preferably 1 to 10% by weight concentration) to selectively oxidize lignin selectively to promote oxidative degradation and low molecular weight.
Dilute nitric acid reacts mainly as shown in the following formula and exhibits a strong oxidizing action.
2HNO 3 → 2NO + 5 [O] + H 2 O
[O] is an oxygen radical (active oxygen), has high reactivity, and has a very short existence time.
It decomposes the C—O—C bond, C═C bond, and C═O bond in lignin to achieve oxidative degradation and low molecular weight.
Diluted nitric acid acts as a catalyst for dirt, and may react rapidly when heated, and reacts rapidly at about 80 ° C. Therefore, in the oxidation process, pulp and dilute nitric acid are introduced at room temperature. Then, when heated to around 98 ° C., a controlled oxidation state can be maintained over the entire period of the oxidation treatment.
It is effective to blow steam from the bottom of the container for heating or stirring.
It is appropriate that this processing time is several tens of minutes.
As a side reaction of [O], there is generation of O 2 and NO 2 , and a gas containing NO and NO 2 is recovered from the top of the container.
Since NO and NO 2 are nitrogen oxides (NO x ), it is appropriate to collect them as raw materials for nitric acid.
The Ostwald process is known as an industrial process for producing nitric acid.
2NO + O 2 → 2NO 2
3NO 2 + H 2 O → 2HNO 3 + NO (NO is returned)
By employing the Ostwald method, NO and NO 2 generated in this step can be recovered as nitric acid.
酸化処理工程では、硝酸の分解反応を完全に終結させるために、酸化処理の終了時に更に熱水を投入し、加熱することが好ましい。この操作により、残存する硝酸分は、殆どが反応し、除去される。
酸化処理工程でのリグニンの溶出は少ない。
発生するＮＯ及びＮＯ2は、前工程のそれと共に回収される。
In the oxidation treatment step, in order to completely terminate the decomposition reaction of nitric acid, it is preferable that hot water is further added and heated at the end of the oxidation treatment. By this operation, most of the remaining nitric acid content reacts and is removed.
There is little elution of lignin in the oxidation process.
The generated NO and NO 2 are recovered together with that in the previous step.
次の洗浄工程では、溶出した少量のリグニンと薬液をチップから分離し、水で洗浄する。 In the next washing step, the eluted small amount of lignin and the chemical solution are separated from the chip and washed with water.
蒸解工程では、チップと希苛性ソーダ水溶液（好ましくは１〜２０重量％濃度）とを共に加熱（好ましくは９５〜１００℃で、３０〜１２０分間）することにより、リグニンを溶解させる。
苛性ソーダ水溶液はリグニンを溶解させると共に、有機酸の中和、樹脂分の鹸化に消費されるものである。
蒸解時間は、より好ましくは３０〜６０分である。
この工程で、含まれるリグニンはほとんど（９５％以上）溶解する。
希苛性ソーダ水溶液の濃度は、より好ましくは１〜１０重量％であり、１重量％未満では、リグニンの溶解が進まないし、１０重量％を超えると、リグニンの溶解には支障はないが、反応に寄与しないカセイソーダとして無駄に排出されるか、あるいは黒液中のリグニンの濃度が高くなりすぎて、黒液からのリグニンの凝集・分取に支障が生じる恐れがある。
In the cooking step, the lignin is dissolved by heating both the chip and the dilute caustic soda aqueous solution (preferably 1 to 20% by weight concentration) (preferably at 95 to 100 ° C. for 30 to 120 minutes).
The aqueous caustic soda solution dissolves lignin and is consumed for neutralization of organic acids and saponification of resin components.
The cooking time is more preferably 30 to 60 minutes.
In this step, most of the lignin contained is dissolved (95% or more).
The concentration of the dilute caustic soda solution is more preferably 1 to 10% by weight. If the concentration is less than 1% by weight, the dissolution of lignin does not proceed. If the concentration exceeds 10% by weight, there is no problem in dissolving the lignin. The caustic soda which does not contribute is discharged wastefully, or the concentration of lignin in the black liquor becomes too high, and there is a possibility that the aggregation and sorting of the lignin from the black liquor may be hindered.
続く洗浄工程では、蒸解したパルプと黒液とを分離し、パルプを水で洗浄して次工程に送る。
黒液は、数％以下の濃度のリグニンを含むが、低濃度であるため、凝集によりリグニンを容易に分取できる。
In the subsequent washing step, the digested pulp and black liquor are separated, and the pulp is washed with water and sent to the next step.
Black liquor contains lignin at a concentration of several percent or less, but because of its low concentration, lignin can be easily separated by aggregation.
以下、蒸解したパルプの公知の処理法が適用できる。
脱リグニン工程では、パルプに残っているリグニンを酸素とアルカリで更に溶かし出す。
精選工程では、パルプに含まれるゴミなどの異物を分離して除去する。
漂白工程では、塩素、二酸化塩素、酸素、苛性ソーダ、次亜塩素酸ソーダ等の薬品を使ってパルプを漂白する。
Hereafter, the well-known processing method of the digested pulp is applicable.
In the delignification step, the lignin remaining in the pulp is further dissolved with oxygen and alkali.
In the selection process, foreign matters such as dust contained in the pulp are separated and removed.
In the bleaching process, the pulp is bleached using chemicals such as chlorine, chlorine dioxide, oxygen, caustic soda and sodium hypochlorite.
また、本発明では、リグニンを分取して資源化しているし、また、排水の処理、薬品の回収にあたり、電解処理技術、水処理技術を適用し、有機物は凝集・分取して、資源化を図り、水、ナトリウム、塩素については、電解処理技術を適用して、リサイクルし得るものである。 Further, in the present invention, lignin is separated and turned into resources, and in wastewater treatment and chemical recovery, electrolytic treatment technology and water treatment technology are applied, and organic substances are agglomerated and separated to produce resources. Water, sodium, and chlorine can be recycled by applying electrolytic treatment technology.
次に実施例について説明するが、一例であり、本発明はこれに限定されるものではない。
図３の本発明のフローチャートに沿って説明する。
建設発生木材（合板）を回転爪を内臓する破砕機（図示せず）により粗破砕し、更に二次的に破砕して、５０ｍｍ以下の木質チップを分級した。更に３〜１５ｍｍになるように破砕・分級を繰り返して、木質チップを調製した。
親水化処理工程では、５重量％の希カセイソーダ水溶液に浸漬した。液温は常温で５０時間処理した。
以降に述べるプロセスでは、適切な工程間洗浄が必要であるが、以下は洗浄については省略した。
酸化処理槽は密閉可能な容器であるが、親水化処理したチップを５重量％濃度の希硝酸水溶液と共に常温で酸化処理槽に投入し、下方から蒸気を吹き込んで、徐々に加熱・撹拌し酸化処理を施した。処理槽内は４０分後に８０℃に達した。高温になるにつれて、発泡が激しくなるが、激しい時は、一時加熱を中止する。酸化処理層の上部から、ＮＯを含むガスを回収した。リグニンは選択的に部分酸化されるが、溶出量は少なかった。
更に、熱湯を加え、加熱して、酸化処理を続行したが、処理は９８℃に達したところで発泡が治まり、反応の終点に達した。
酸化処理して洗浄したチップを５重量％濃度の苛性ソーダ水溶液と共に蒸解槽に投入し、下方から蒸気を吹き込んで煮沸・撹拌した。処理時間は、９８℃に達してから１時間とした。
なお、被処理物の木質チップ１重量部に対して、親水化処理工程では苛性ソーダ水溶液１０重量部を、酸化処理工程では硝酸水溶液１０重量部を、蒸解処理工程では苛性ソーダ水溶液１０重量部
を各々加えて処理した。
Next, although an Example is described, it is an example and this invention is not limited to this.
This will be described along the flowchart of the present invention in FIG.
Construction-generated wood (plywood) was roughly crushed by a crusher (not shown) having a built-in rotary claw, and then secondarily crushed to classify wood chips of 50 mm or less. Furthermore, crushing and classification were repeated so as to be 3 to 15 mm to prepare a wood chip.
In the hydrophilization treatment step, it was immersed in a 5% by weight dilute caustic soda aqueous solution. The liquid temperature was treated at room temperature for 50 hours.
In the process described below, appropriate inter-step cleaning is necessary, but the following was omitted for cleaning.
Although the oxidation treatment tank is a sealable container, the hydrophilized chip is put into the oxidation treatment tank at room temperature together with a 5% by weight dilute nitric acid aqueous solution, and steam is blown from below, and gradually heated and stirred to oxidize. Treated. The inside of the treatment tank reached 80 ° C. after 40 minutes. As the temperature rises, the foaming becomes intense, but when it is intense, temporary heating is stopped. A gas containing NO was recovered from the upper part of the oxidation treatment layer. Lignin was selectively partially oxidized, but the amount of elution was small.
Furthermore, hot water was added and heated to continue the oxidation treatment, but when the treatment reached 98 ° C., the foaming stopped and the end point of the reaction was reached.
The chips cleaned by oxidation treatment were put into a cooking tank together with a 5% by weight aqueous caustic soda solution, and steam was blown from below to boil and stir. The treatment time was 1 hour after reaching 98 ° C.
In addition, 10 parts by weight of aqueous caustic soda solution is added in the hydrophilization process, 10 parts by weight of aqueous nitric acid solution in the oxidation process, and 10 parts by weight of aqueous caustic soda solution in the cooking process with respect to 1 part by weight of the wood chips to be treated. And processed.
処理後、蒸解したパルプと黒液を分離した。黒液からリグニンを凝集・分取したが、チップに含まれるリグニンの９５％以上が溶出されていた。
蒸解したパルプは洗浄後、パルプに残っているリグニンを酸素とアルカリで更に溶かし出し、漂白工程では、次亜塩素酸ソーダを使ってパルプを漂白したところ、クラフト法パルプと同等のものが得られた。精選工程では、パルプに含まれるゴミなどの異物を分離して除去した。
本実施例で得られたパルプを用いて製紙となし、その製紙の試験を行った。
その結果を表１及び表２に示す。
なお、本実施例における製紙は手漉きによって行ったものであるため坪量は低いが、表１及び表２の各数値から見て、その物性値、成分組成は、カナダＬ材のパルプによって得られた製紙と同等のものであることが解った。
After the treatment, the digested pulp and black liquor were separated. Lignin was aggregated and fractionated from the black liquor, but 95% or more of the lignin contained in the chip was eluted.
After the digested pulp is washed, the lignin remaining in the pulp is further dissolved with oxygen and alkali, and in the bleaching process, the pulp is bleached with sodium hypochlorite to obtain the equivalent of kraft pulp. It was. In the selection process, foreign matters such as dust contained in the pulp were separated and removed.
The pulp obtained in this example was used for papermaking, and the papermaking test was conducted.
The results are shown in Tables 1 and 2.
In addition, since the papermaking in this example is performed by hand-making, the basis weight is low, but as seen from the numerical values in Tables 1 and 2, the physical property values and the component composition are obtained from Canadian L-wood pulp. It was found to be equivalent to the paper making.
Claims (7)
次いで前記工程で得られた親水化処理済み木質チップに水又は温水を加えてアルカリ分を除去する第１洗浄処理工程と、
前記第一洗浄処理工程を施して得られた第１洗浄処理済み木質チップに希硝酸を加えて常温又は加温下において酸化処理して木質チップに含まれるリグニンを選択的に部分酸化する酸化処理工程と、
前記酸化処理工程で得られた酸化処理済み木質チップに水又は温水を加えて希硝酸分を除去する第２洗浄工程と、
前記第２洗浄工程で得られた第２洗浄処理済み木質チップに希苛性ソーダ水溶液を加え加温して前記木質チップを蒸解する蒸解処理工程と、
前記蒸解処理工程で得られた蒸解処理済み物を濾別して蒸解パルプとリグニンを含有する黒液とに分離する蒸解パルプ・黒液分離処理工程とからなることを特徴とするパルプの製造方法。 A hydrophilization treatment step of hydrophilizing the wood chips by immersing them in dilute caustic soda solution;
Next, a first cleaning treatment step of removing alkali by adding water or warm water to the hydrophilized wood chip obtained in the step,
Oxidation treatment in which dilute nitric acid is added to the first washed wood chip obtained by performing the first washing treatment step and oxidized at room temperature or under heating to selectively oxidize lignin contained in the wood chip. Process,
A second washing step of removing dilute nitric acid by adding water or warm water to the oxidized wood chip obtained in the oxidation treatment step;
A cooking process for cooking the wooden chips by adding a dilute caustic soda aqueous solution to the second washed processed wooden chips obtained in the second cleaning process;
A pulp production method comprising: a digested pulp / black liquor separation process for separating the digested product obtained in the digestion process and separating it into a digested pulp and a black liquor containing lignin.
次いで前記工程で得られた親水化処理済み木質チップに水又は温水を加えてアルカリ分を除去する第１洗浄処理工程と、
前記第１洗浄処理工程を施して得られた第１洗浄処理済み木質チップ１重量部に、１〜１０重量％濃度の硝酸水溶液３〜１５重量部を加えて、８０〜９８℃で４０〜１２０分間酸化処理して木質チップに含まれるリグニンを選択的に部分酸化する酸化処理工程と、
前記酸化処理工程で得られた酸化処理済み木質チップに水又は温水を加えて希硝酸分を除去する第２洗浄工程と、
前記第２洗浄工程で得られた第２洗浄処理済み木質チップ１重量部に、１〜２０重量％濃度の苛性ソーダ水溶液５〜２０重量部を加え常圧下又は加圧下において９５〜１００℃で３０〜１２０分間加熱して前記木質チップを蒸解する蒸解処理工程と、
前記蒸解処理工程で得られた蒸解処理済み物を濾別して蒸解パルプとリグニンを含有する黒液とに分離する蒸解パルプ・黒液分離処理工程とからなることを特徴とするパルプの製造方法。 A hydrophilization treatment step of hydrophilizing 1 part by weight of wood chips by soaking in 5 to 20 parts by weight of a 1 to 10% by weight aqueous caustic soda solution at 15 to 40 ° C. for 10 to 60 hours;
Next, a first cleaning treatment step of removing alkali by adding water or warm water to the hydrophilized wood chip obtained in the step,
3 to 15 parts by weight of an aqueous nitric acid solution having a concentration of 1 to 10% by weight is added to 1 part by weight of a first cleaned wood chip obtained by performing the first cleaning process step, and 40 to 120 at 80 to 98 ° C. An oxidation treatment step that selectively oxidizes lignin contained in the wood chip by oxidizing for a minute,
A second washing step of removing dilute nitric acid by adding water or warm water to the oxidized wood chip obtained in the oxidation treatment step;
5 to 20 parts by weight of a 1 to 20% by weight aqueous caustic soda solution is added to 1 part by weight of the second washed wood chip obtained in the second washing step, and 30 to 30 at 95 to 100 ° C. under normal pressure or under pressure. A cooking process for cooking the wood chips by heating for 120 minutes;
A pulp production method comprising: a digested pulp / black liquor separation process for separating the digested product obtained in the digestion process and separating it into a digested pulp and a black liquor containing lignin.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2014208803A (en) * | 2013-03-29 | 2014-11-06 | ロイス・ドットコム株式会社 | Lignin recovery method |
| JP2022189624A (en) * | 2021-06-11 | 2022-12-22 | 国立大学法人九州工業大学 | Method for producing alkali soluble cellulose material from vegetable biomass |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2014208803A (en) * | 2013-03-29 | 2014-11-06 | ロイス・ドットコム株式会社 | Lignin recovery method |
| JP2022189624A (en) * | 2021-06-11 | 2022-12-22 | 国立大学法人九州工業大学 | Method for producing alkali soluble cellulose material from vegetable biomass |
| JP7687613B2 (en) | 2021-06-11 | 2025-06-03 | 国立大学法人九州工業大学 | Method for producing alkali-soluble cellulosic materials from plant biomass |
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