JPS6122080B2 - - Google Patents
Info
- Publication number
- JPS6122080B2 JPS6122080B2 JP4270081A JP4270081A JPS6122080B2 JP S6122080 B2 JPS6122080 B2 JP S6122080B2 JP 4270081 A JP4270081 A JP 4270081A JP 4270081 A JP4270081 A JP 4270081A JP S6122080 B2 JPS6122080 B2 JP S6122080B2
- Authority
- JP
- Japan
- Prior art keywords
- cooking
- waste liquid
- steam
- parts
- anthraquinone
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- 238000000034 method Methods 0.000 claims description 47
- 238000010411 cooking Methods 0.000 claims description 45
- 239000007788 liquid Substances 0.000 claims description 37
- 239000002699 waste material Substances 0.000 claims description 34
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 claims description 29
- 238000011084 recovery Methods 0.000 claims description 19
- -1 anthraquinone compound Chemical class 0.000 claims description 17
- 239000000126 substance Substances 0.000 claims description 17
- ZVALGBPJYGUWIS-UHFFFAOYSA-N 1,4-dihydroanthracene-9,10-dione Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1CC=CC2 ZVALGBPJYGUWIS-UHFFFAOYSA-N 0.000 claims description 6
- 238000004537 pulping Methods 0.000 claims description 6
- 239000012752 auxiliary agent Substances 0.000 claims description 4
- XPCZSIPRUSOJFO-UHFFFAOYSA-N 1,4,4a,9a-tetrahydroanthracene-9,10-dione Chemical compound O=C1C2=CC=CC=C2C(=O)C2C1CC=CC2 XPCZSIPRUSOJFO-UHFFFAOYSA-N 0.000 claims description 3
- 239000012978 lignocellulosic material Substances 0.000 claims description 3
- 238000000926 separation method Methods 0.000 claims description 3
- 150000001340 alkali metals Chemical class 0.000 claims description 2
- RJGDLRCDCYRQOQ-UHFFFAOYSA-N anthrone Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3CC2=C1 RJGDLRCDCYRQOQ-UHFFFAOYSA-N 0.000 claims description 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 claims description 2
- 230000003247 decreasing effect Effects 0.000 claims description 2
- 239000007800 oxidant agent Substances 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical class [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 claims description 2
- 150000003568 thioethers Chemical class 0.000 claims description 2
- 229910000272 alkali metal oxide Inorganic materials 0.000 claims 1
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 claims 1
- 150000004056 anthraquinones Chemical class 0.000 description 14
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 238000001816 cooling Methods 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 5
- 239000011121 hardwood Substances 0.000 description 4
- 239000002655 kraft paper Substances 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 230000008020 evaporation Effects 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 235000011121 sodium hydroxide Nutrition 0.000 description 3
- PCFMUWBCZZUMRX-UHFFFAOYSA-N 9,10-Dihydroxyanthracene Chemical compound C1=CC=C2C(O)=C(C=CC=C3)C3=C(O)C2=C1 PCFMUWBCZZUMRX-UHFFFAOYSA-N 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 159000000000 sodium salts Chemical class 0.000 description 2
- 235000010265 sodium sulphite Nutrition 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- BHMLFPOTZYRDKA-IRXDYDNUSA-N (2s)-2-[(s)-(2-iodophenoxy)-phenylmethyl]morpholine Chemical compound IC1=CC=CC=C1O[C@@H](C=1C=CC=CC=1)[C@H]1OCCNC1 BHMLFPOTZYRDKA-IRXDYDNUSA-N 0.000 description 1
- YTWHNPHXSILERV-UHFFFAOYSA-N 1,2-dihydroanthracene-9,10-dione Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C=CCC2 YTWHNPHXSILERV-UHFFFAOYSA-N 0.000 description 1
- 241000009355 Antron Species 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 229920006322 acrylamide copolymer Polymers 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000000779 depleting effect Effects 0.000 description 1
- 235000019621 digestibility Nutrition 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 235000014666 liquid concentrate Nutrition 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000011514 reflex Effects 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 239000011122 softwood Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000005486 sulfidation Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Landscapes
- Paper (AREA)
Description
【発明の詳細な説明】
本発明はリグノセルロース物質を少なくとも１
種のアリカリ金属及び／又はアルカリ土類金属塩
（水酸化物、硫化物、炭酸化物、亜硫酸塩等）を
含有する薬液で蒸解パイプ化する方法において、
薬液中に添加される蒸解促進助剤（以下単に蒸解
助剤と略記する）を蒸解後の廃液から回収する方
法に関し、特に蒸解廃液からアントラキノン系化
合物を回収する方法に関するものである。DETAILED DESCRIPTION OF THE INVENTION The present invention provides at least one lignocellulosic material.
In a method of forming a cooking pipe with a chemical solution containing alkali metal and/or alkaline earth metal salts (hydroxides, sulfides, carbonates, sulfites, etc.),
The present invention relates to a method for recovering a cooking aid added to a chemical solution (hereinafter simply referred to as a cooking aid) from a cooking waste liquid, and in particular, to a method for recovering anthraquinone compounds from a cooking waste liquid.
近年、クラフトパルプ化法、ソーダパルプ化
法、亜硫酸塩パルブ化法等のケミカル及びセミケ
ミカルパルプ化法において、蒸解の促進及びパル
プ収率の向上を計る蒸解助剤としてアントラキノ
ン系化合物が効果的であることが確認されつつあ
り、既に一部実用化されており関連する特許出願
も例えば、東ドイツ特許第98549号、特公昭55−
1398号、特公昭53−13002号、特開昭52−37803
号、特開昭52−155202号、特開昭53−74101号、
特開昭55−142785号、特公昭53−45404号、……
…等々多数におよんでいる。 In recent years, anthraquinone compounds have been found to be effective as cooking aids to accelerate cooking and improve pulp yield in chemical and semi-chemical pulping methods such as kraft pulping, soda pulping, and sulfite pulping. It is being confirmed that there is, and some of it has already been put into practical use, and related patent applications, such as East German Patent No. 98549 and Japanese Patent Publication No.
No. 1398, Special Publication No. 53-13002, Japanese Patent Publication No. 52-37803
No., JP-A-52-155202, JP-A-53-74101,
Japanese Patent Publication No. 55-142785, Special Publication No. 53-45404,...
...and many more.
これらアントラキノン系化合物は一般にリグノ
セルロース100重量部に対して0.01重量部乃至数
重量部といつた割合になるよう蒸解薬液中に添加
して用いられているが、蒸解促進及びバルブ収率
の改善効果という点では添加割合が多い程良好な
改善効果が得られる。しかしながら、アントラキ
ノン系化合物は石炭、石油など有限な化石資源を
出発原料とし、複雑な合成段階を経て製造される
薬品であり、従来、その大部分は合成染料の中間
体として利用されており、パルプ製造用の助剤と
しては相当に高価な薬品である。従つて経済的な
制約から比較的低い添加率で、低い作用効果のも
とに実用されているのが現状である。さらに、将
来的には化石資源の入手難の深刻化とも相俟つて
一層高価な薬品となることは明白である。 These anthraquinone compounds are generally added to cooking chemicals at a ratio of 0.01 part to several parts by weight per 100 parts by weight of lignocellulose, but they have the effect of promoting cooking and improving bulb yield. In this respect, the higher the addition ratio, the better the improvement effect can be obtained. However, anthraquinone compounds are chemicals that are manufactured through complex synthesis steps using limited fossil resources such as coal and petroleum as starting materials. It is a fairly expensive chemical as a manufacturing aid. Therefore, due to economic constraints, it is currently put into practical use at a relatively low addition rate and with low effects. Furthermore, it is clear that in the future, along with the worsening difficulty in obtaining fossil resources, chemicals will become even more expensive.
かかる現状に鑑み、本発明者等はこのように高
価な蒸解助剤を回収し再利用する方法について鋭
意研究を重ねた結果、本発明を達成するに至つ
た。 In view of the current situation, the inventors of the present invention have conducted extensive research into methods of recovering and reusing such expensive cooking aids, and as a result, have achieved the present invention.
アントラキノン系化合物を回収する方法につい
ては、特開昭54−101901号に濃縮した後のパルプ
廃液を固化させる過程で生じる150〜400℃という
高温域での発生ガスを捕集して回収する方法が提
案されている。しかし、この方法では確に助剤の
回収率においては優れているものの、上記の如く
パルプ廃液を濃縮したのちさらに固化させるとい
う通常用いられていない特殊な工程を導入する必
要があるため設備上は言うにおよばず操業面でも
煩雑な作業を余儀なくされる。さらに、一般にク
ラフト法、ソーダ法、亜硫酸塩法或はこれらに類
したパルプ化法においては、蒸解後のパルプ廃液
中に含まれる無機薬品を回収するとともに、可燃
性の有機物を燃焼させ燃焼エネルギーとして回収
するべくパルプ廃液を濃縮した後燃焼させる回収
工程が設けられているが、上記の如く新たに固化
工程を導入すると機械設備の効率からしてこの回
収工程の効率が著しく低下してしまうため、特に
エネルギー資源枯渇という時代のすうせいからみ
て大きなマイナス要因を付随する回収法と言わざ
るを得ない。 Regarding the method of recovering anthraquinone compounds, Japanese Patent Application Laid-Open No. 101901/1983 describes a method of collecting and recovering gas generated in the high temperature range of 150 to 400°C that is generated in the process of solidifying pulp waste liquid after concentration. Proposed. However, although this method is certainly superior in terms of the recovery rate of the auxiliary agent, it requires the introduction of a special process that is not normally used, such as concentrating the pulp waste liquid and then solidifying it as described above. Needless to say, this also necessitates complicated operations. Furthermore, in general, in the kraft method, soda method, sulfite method, or similar pulping methods, inorganic chemicals contained in the pulp waste liquid after cooking are recovered, and flammable organic matter is burned to generate combustion energy. A recovery process is provided in which the pulp waste liquid is concentrated and then combusted for recovery, but if a new solidification process is introduced as described above, the efficiency of this recovery process will be significantly reduced in terms of the efficiency of the mechanical equipment. Particularly in view of the current situation of depleting energy resources, it must be said that this is a recovery method that comes with major negative factors.
而して、本発明の目的は蒸解助剤の回収率にお
いては上記の回収法に劣るものの、現状の設備範
囲内で実施が可能であり、しかも何らエネルギー
的な損失を伴うことなく蒸解助剤を回収し得る新
規な方法を提供することである。 Therefore, although the recovery rate of the cooking aid is inferior to the above-mentioned recovery method, the purpose of the present invention is to be able to recover the cooking aid without any energy loss, and which can be implemented within the scope of the current equipment. The object of the present invention is to provide a new method that can recover .
本発明の上記の如き目的は、アントラキノン系
化合物を蒸解助剤として含有する蒸解薬液を用い
るリグノセルロース物質のパルス化法において、
生成する蒸解廃液の濃縮工程で発生する気相部を
捕集し、含有されるアントラキノン系化合物を分
離回収することによつて達成される。 The above object of the present invention is to provide a method for pulsing lignocellulosic materials using a cooking chemical containing an anthraquinone compound as a cooking aid.
This is achieved by collecting the gas phase generated during the concentration process of the produced cooking waste and separating and recovering the anthraquinone compounds contained therein.
従来、蒸解後のパルプ廃液を濃縮する過程にお
いて発生する水蒸気は、その熱量を有効に使用さ
れた後、最終的には凝縮水（ドレン）とされ一部
は工程水として再使用されるものの大部分は排水
として放出されてしまう。ところが本発明者等は
アントラキノン系化合物を含む薬液を用いて蒸解
した後に得られるパルプ廃液の濃縮に際してはア
ントラキノン系化合物及びその誘導体が蒸発濃縮
時に容易に水蒸気とともに留出し気相部に移行す
ることを見出した。この留出物は実際には蒸発条
件、蒸気凝集条件、ドレン冷却条件等を適宜選択
することによつて高純度の固体或は結晶として分
離することが可能であるが、一般的な条件下での
析出は稀であり、温水中に溶解又は極めて微細な
結晶として懸濁しているため従来は全く気付かれ
ることなく排水としてすてられていたものであ
る。 Conventionally, the water vapor generated in the process of concentrating pulp waste liquid after cooking is effectively used for its calorific value, and is eventually turned into condensed water (drain), although some of it is reused as process water. A portion is discharged as wastewater. However, the present inventors have discovered that when concentrating pulp waste liquid obtained after cooking using a chemical solution containing anthraquinone compounds, anthraquinone compounds and their derivatives are easily distilled together with water vapor and transferred to the gas phase during evaporation and concentration. I found it. In reality, this distillate can be separated as a high-purity solid or crystal by appropriately selecting evaporation conditions, vapor condensation conditions, drain cooling conditions, etc., but under general conditions. Precipitation is rare, and because it is dissolved or suspended in the form of extremely fine crystals in hot water, conventionally it was discarded as wastewater without being noticed at all.
本発明者等の分析によれば、意外にも蒸解廃液
の濃縮工程で得られる上記のドレン中には多量の
蒸解助剤が含まれていることが明らかとなつた。
ドレン中に含まれる蒸解助剤の含有量は勿論パル
プ廃液中に含まれる助剤の含有量、即ち蒸解時に
蒸解薬液中に添加される助剤の量によつて変化す
るが、例えば１・４・4a・9a−テトラヒドロアン
トラキノンをリグノセルロース100重量部に対し
0.02〜0.1重量部使用した場合には10〜100ppmも
含有されており、これは全助剤使用量の約15〜40
重量％にも相当するものである。このドレン中に
含まれる蒸解助剤を分離捕集する方法としては(1)
蒸気をフラツシユタンク等にフラツシユさせて蒸
気に圧力変化、温度変化等のシヨツクを与えてや
る方法。(2)蒸気を冷却器で急冷する方法。(3)蒸気
から十分に熱回収し温度の低下したドレンを静置
する方法等により助剤を析出させてからフイルタ
ーによる過あるいは遠心分離により分離する方
法、さらにはドレンに有機或は無機の凝集沈澱剤
を添加し助剤の微粒子をフロツク化させた後上記
の分離処理を行う方法等各種の方法が挙げられ
る。かかる分離捕集方法によつてドレン中に含ま
れる蒸解助剤の約80重量％を回収することが出来
るが、留出してくる蒸解助剤の結晶の生成を助長
するべく前もつて結晶のタネを蒸気系内或はドレ
ンタンク中に導入すると回収効率が一層高められ
る。 According to the analysis conducted by the present inventors, it was unexpectedly revealed that the above-mentioned drain obtained in the process of concentrating cooking waste liquid contained a large amount of cooking aid.
The content of the cooking aid contained in the drain naturally varies depending on the content of the cooking aid contained in the pulp waste liquid, that is, the amount of the cooking aid added to the cooking chemical during cooking, but for example, 1.4・4a・9a-tetrahydroanthraquinone per 100 parts by weight of lignocellulose
When 0.02 to 0.1 part by weight is used, it contains 10 to 100 ppm, which is approximately 15 to 40 ppm of the total amount of auxiliary used.
It also corresponds to weight %. The method for separating and collecting the cooking aid contained in this drain is (1)
A method of flashing steam into a flash tank or the like to apply shocks such as pressure changes and temperature changes to the steam. (2) A method of rapidly cooling steam using a cooler. (3) A method in which the auxiliary agent is precipitated by a method such as sufficiently recovering heat from the steam and leaving the condensate whose temperature has decreased, and then separating it by filtration with a filter or centrifugation, or a method in which organic or inorganic agglomerates are collected in the condensate. Various methods may be used, including a method in which a precipitant is added to flocculate the fine particles of the auxiliary agent, and then the above-mentioned separation treatment is carried out. Approximately 80% by weight of the cooking aid contained in the drain can be recovered by this separation and collection method. If it is introduced into the steam system or drain tank, the recovery efficiency can be further increased.
本発明の方法により回収するのに適した蒸解助
剤としては、原理的には蒸解廃液の濃縮に際し水
蒸気蒸留され冷却後に固体として折出するもので
あれば如何なる物質でもよいが、前述の如く特に
アントラキノン系化合物の回収に適している。 In principle, the cooking aid suitable for recovery by the method of the present invention may be any substance as long as it is steam distilled during the concentration of the cooking waste liquid and precipitated as a solid after cooling. Suitable for recovering anthraquinone compounds.
とりわけ１・４・4a・9a−テトラヒドロアント
ラキノン、アントラキノン、アントロン、１・４
−ジヒドロアントラキノン、９・10−ジヒドロキ
シアントラセン及びこれらの塩の如きアントラキ
ノン系化合物の回収に適しており、これらのアン
トラキノン系化合物は主にドレン中からアントラ
キノンとして回収されるがその他１・４−ジヒド
ロアントラキノン及びアントロンとしても１部回
収される。なお、蒸解廃液を空気、酸素等の酸化
剤と接触させることにより酸化した後に濃縮する
とアントラキノン系化合物の回収効率が一層高め
られる為、かかる処理は本発明の方法における好
ましい実施態様である。 Especially 1,4,4a,9a-tetrahydroanthraquinone, anthraquinone, anthrone, 1,4
- Suitable for recovering anthraquinone compounds such as dihydroanthraquinone, 9,10-dihydroxyanthracene, and their salts; these anthraquinone compounds are mainly recovered from drains as anthraquinone, but other 1,4-dihydroanthraquinone And one copy was also collected as Antron. Note that if the cooking waste liquid is oxidized by contacting it with an oxidizing agent such as air or oxygen and then concentrated, the recovery efficiency of anthraquinone compounds can be further increased, so such treatment is a preferred embodiment of the method of the present invention.
上述の如く、本発明の方法によれば従来法のよ
うに例えば濃縮廃液を高温で固化するといつた特
殊な工程は全く必要なく、通常用いられている設
備により、しかも通常の蒸発濃縮温度である50〜
140℃といつた温度条件、さらには通常の圧力条
件下で蒸解廃液を濃縮する過程において発生する
蒸気中から蒸解助剤が極めて容易に回収されるも
のである。勿論リグノセルロースの種類、蒸解方
法さらには蒸解薬液の種類によつて本発明の方法
は特に限定されるものではなく、蒸解廃液中に前
述の如き蒸解助剤が含有されている限り本発明の
方法を有効に適用し得るものである。 As mentioned above, according to the method of the present invention, unlike conventional methods, there is no need for special steps such as solidifying the concentrated waste liquid at high temperatures, and it can be carried out using commonly used equipment and at normal evaporation and concentration temperatures. 50～
The cooking aid can be very easily recovered from the steam generated during the process of concentrating cooking waste under temperature conditions of 140°C and under normal pressure conditions. Of course, the method of the present invention is not particularly limited by the type of lignocellulose, the cooking method, or the type of cooking chemical, and the method of the present invention is applicable as long as the cooking aid as described above is contained in the cooking waste liquid. can be applied effectively.
以下に実施例を挙げて本発明をより具体的に説
明するが、勿論これらに限定されるものではな
い。なお、特に断らない限り例中の部および％は
それぞれ重量部および重量％を示す。 The present invention will be described in more detail with reference to Examples below, but it is of course not limited thereto. In addition, unless otherwise specified, parts and % in the examples indicate parts by weight and % by weight, respectively.
実施例 １
広葉樹チツプ100部に硫化度30％のクラフト蒸
解液をNa2O換算の活性アルカリ量として20部、
１・４・4a・9a−テトラヒドロアントラキノンの
ナトリウム塩を0.03部加え、オートクレーブ中で
液比3.5、温度175℃で100分間処理した。処理後
の未晒パルプを圧縮脱水し、パルプ廃液を全量採
取した。次いで未晒パルプにさらに100部の清水
を加え再度圧縮脱水し、この廃液も上記廃液に加
え最終的なパルプ廃液とした。廃液の量は400部
であり濃度は16％であつた。この廃液を100〜140
℃で濃度55％まで濃縮し、その際留出した蒸気を
30℃まで冷却しドレン280部を得た。ドレンを
過したところ0.006部のアントラキノンが回収さ
れた。回収率は20％であつた。Example 1 100 parts of hardwood chips and 20 parts of Kraft cooking liquor with a sulfidity of 30% as an active alkali amount calculated as Na 2 O.
0.03 part of sodium salt of 1,4,4a,9a-tetrahydroanthraquinone was added, and the mixture was treated in an autoclave at a liquid ratio of 3.5 and a temperature of 175°C for 100 minutes. The unbleached pulp after treatment was compressed and dehydrated, and the entire pulp waste liquid was collected. Next, an additional 100 parts of clean water was added to the unbleached pulp, and the pulp was compressed and dehydrated again, and this waste liquid was also added to the above-mentioned waste liquid to form the final pulp waste liquid. The amount of waste liquid was 400 parts and the concentration was 16%. 100~140% of this waste liquid
Concentrate at ℃ to a concentration of 55%, and distill the vapor at that time.
It was cooled to 30°C to obtain 280 parts of condensate. When drained, 0.006 parts of anthraquinone was recovered. The recovery rate was 20%.
実施例 ２
広葉樹チツプ100部に硫化度８％の低硫化度ク
ラフト蒸解度をNa2O換算の活性アルカリ量とし
て18部、アントラキノンを0.1部加え、液比3.5、
温度175℃で100分間オートクレーブ中で処理し
た。以下実施例１と同様にして16.5％濃度のパル
プ廃液390部を得た。このパルプ廃液中に10/m
ｉｎの流量で３分間空気を吹き込んで廃液を酸化し
た後、80〜140℃で58％濃度まで濃縮した。その
際留出した蒸気は前もつて0.001部のアントラキ
ノンを付着させた冷却管に連続して導入された。
濃縮完了後にドレンを遠心分離して得られたアン
トラキノンと上記冷却管内壁に析出付着したアン
トラキノンを合わせ0.035部のアントラキノンが
回収された。前もつて冷却管に付着させたアント
ラキノンの量を差し引いて得られる回収率は34％
であつた。Example 2 To 100 parts of hardwood chips, 18 parts of low sulfidation kraft digestibility with a sulfidity of 8% as an active alkali amount calculated as Na 2 O, and 0.1 part of anthraquinone were added, and the liquid ratio was 3.5.
Processed in an autoclave at a temperature of 175°C for 100 minutes. Thereafter, 390 parts of pulp waste liquid having a concentration of 16.5% was obtained in the same manner as in Example 1. 10/m in this pulp waste liquid
The waste liquid was oxidized by blowing air for 3 minutes at a flow rate of 100.degree. C., and then concentrated to a concentration of 58% at 80-140.degree. The vapor distilled at this time was continuously introduced into a cooling tube to which 0.001 part of anthraquinone was previously deposited.
After the concentration was completed, the anthraquinone obtained by centrifuging the drain and the anthraquinone deposited on the inner wall of the cooling tube were combined to recover 0.035 parts of anthraquinone. The recovery rate obtained by subtracting the amount of anthraquinone deposited on the cooling tube is 34%.
It was hot.
実施例 ３
広葉樹チツプ100部にソーダ蒸解液を苛性ソー
ダのNa2O換算で16部加え、さらに９・10−ジヒ
ドロキシアントラセンのナトリウム塩0.08部を加
えた。オートクレーブ中で液比3.5、温度160℃で
80分間処理した後、実施例１と同様の操作をして
濃度14.5％のパルプ廃液400部を得た。このパル
プ廃液を100〜137℃で56％濃度まで濃縮し、その
際留出したドレン290部にソーダ蒸解液を苛性ソ
ーダのNa2O換算で４部加えることによりアント
ラキノンの析出を促進させた後、ポリアクリル酸
−アクリルアミド共重合物を0.002部加え、過
したところ0.029部のアントラキノンが得られ
た。回収率は36％であつた。Example 3 To 100 parts of hardwood chips were added 16 parts of soda cooking liquor (calculated as Na 2 O of caustic soda), and further added 0.08 part of sodium salt of 9,10-dihydroxyanthracene. In an autoclave at a liquid ratio of 3.5 and a temperature of 160°C.
After treatment for 80 minutes, the same operation as in Example 1 was performed to obtain 400 parts of pulp waste liquid with a concentration of 14.5%. This pulp waste liquid was concentrated to a concentration of 56% at 100 to 137°C, and 4 parts of soda cooking liquor (calculated as Na 2 O of caustic soda) was added to 290 parts of the distilled condensate to promote the precipitation of anthraquinone. 0.002 part of polyacrylic acid-acrylamide copolymer was added and filtered, yielding 0.029 part of anthraquinone. The recovery rate was 36%.
実施例 ４
針葉樹チツプ100部に亜硫酸ソード16部苛性ソ
ーダ４部、１・４−ジヒドロアントラキノン0.2
部を加え、オートクレーブ中で液比3.5温度165℃
で４時間処理した。以下実施例１と同様にして
15.5％濃度のパルプ廃液を400部採取した。この
廃液に10/minの流量で３分間空気を吹き込ん
だ後90〜140℃で55％濃度まで濃縮した。その際
留出した蒸気から287部のドレンが得られ、これ
を過したところ0.084部のアントラキノンが得
られた。回収率は42％であつた。Example 4 100 parts of softwood chips, 16 parts of sodium sulfite, 4 parts of caustic soda, 0.2 parts of 1,4-dihydroanthraquinone
liquid ratio 3.5 in an autoclave at a temperature of 165℃
It was treated for 4 hours. In the same manner as in Example 1,
400 parts of pulp waste liquid with a concentration of 15.5% was collected. Air was blown into this waste liquid at a flow rate of 10/min for 3 minutes, and then concentrated to a concentration of 55% at 90-140°C. At that time, 287 parts of condensate was obtained from the distilled vapor, and when this was passed, 0.084 part of anthraquinone was obtained. The recovery rate was 42%.
実施例 ５
広葉樹チツプ100部に亜硫酸ソーダ10部、炭酸
ソーダ３部、アントラキノン0.5部を加えオート
クレーブ中で液比４、温度180℃で20分間処理
し、次いで12インチのテストレフアイナーで解繊
した。以下実施例１と同様にして濃度9.2％のパ
ルプ廃液を340部採取した。このパルプ廃液を50
〜120℃で45％濃度まで濃縮し、その際留出した
蒸気から270部のドレンを得た。ドレンを遠心分
離したところ0.254部のアントラキノンが回収さ
れた。回収率は51％であつた。Example 5 100 parts of hardwood chips were mixed with 10 parts of sodium sulfite, 3 parts of soda carbonate, and 0.5 parts of anthraquinone, treated in an autoclave at a liquid ratio of 4 and a temperature of 180°C for 20 minutes, and then defibrated using a 12-inch test reflex iner. . Thereafter, in the same manner as in Example 1, 340 parts of pulp waste liquid having a concentration of 9.2% was collected. 50% of this pulp waste liquid
It was concentrated to a concentration of 45% at ~120° C., and 270 parts of condensate were obtained from the distilled vapor. When the drain was centrifuged, 0.254 parts of anthraquinone was recovered. The recovery rate was 51%.
Claims (1)
有する蒸解薬液を用いるリグノセルロース物質の
パルプ化法において、生成する蒸解廃液の濃縮工
程で蒸解廃液から発生する蒸気又はそのドレンを
補集し、フラツシユさせて蒸気に圧力変化、温度
変化を与えるか、蒸気又はそのドレンを冷却器で
冷却するか或いは蒸気又はそのドレンから熱回収
し温度の低下したドレンを静置する、のいずれか
の方法により該助剤を析出させ固液分離により回
収する方法。 ２ 蒸解薬液がアルカリ金属及び／又はアルカリ
土類金属の水酸化物、硫化物、炭酸化物、亜硫酸
塩の少なくとも１種を含有する薬液である請求の
範囲第１項記載の回収方法。 ３ 蒸解廃液を酸化剤により酸化した後濃縮する
請求の範囲第１項記載の回収方法。 ４ アントラキノン系化合物が１・４・4a・9a−
テトラヒドロアントラキノン、アトラキノン、ア
ントロン、１・４−ジヒドロアントラキノン、
９・10−ヒドロキシアントラセン及びこれらの塩
から選ばれる少なくとも１種である請求の範囲第
１項記載の回収方法。[Scope of Claims] 1. In a method for pulping lignocellulosic materials using a cooking chemical solution containing an anthraquinone compound as a cooking aid, steam generated from the cooking waste liquid or its drainage is collected in the process of concentrating the cooking waste liquid. Then, either the steam is flashed to give pressure and temperature changes to the steam, the steam or its condensate is cooled with a cooler, or the heat is recovered from the steam or its condensate and the condensate whose temperature has decreased is left standing. A method in which the auxiliary agent is precipitated by a method and recovered by solid-liquid separation. 2. The recovery method according to claim 1, wherein the cooking chemical is a chemical containing at least one of alkali metal and/or alkaline earth metal hydroxides, sulfides, carbonates, and sulfites. 3. The recovery method according to claim 1, wherein the cooking waste liquid is oxidized with an oxidizing agent and then concentrated. 4 Anthraquinone compounds are 1, 4, 4a, 9a-
Tetrahydroanthraquinone, atraquinone, anthrone, 1,4-dihydroanthraquinone,
The recovery method according to claim 1, wherein the recovery method is at least one selected from 9,10-hydroxyanthracene and salts thereof.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4270081A JPS57191389A (en) | 1981-03-23 | 1981-03-23 | Recovery of digesting aid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4270081A JPS57191389A (en) | 1981-03-23 | 1981-03-23 | Recovery of digesting aid |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS57191389A JPS57191389A (en) | 1982-11-25 |
| JPS6122080B2 true JPS6122080B2 (en) | 1986-05-30 |
Family
ID=12643323
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4270081A Granted JPS57191389A (en) | 1981-03-23 | 1981-03-23 | Recovery of digesting aid |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS57191389A (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0791206B2 (en) * | 1987-01-12 | 1995-10-04 | 川崎化成工業株式会社 | Process for producing 1,4-dihydro-9,10-dihydroxyanthracene disodium salt octahydrate |
| JP2002536563A (en) * | 1999-02-15 | 2002-10-29 | キラム アクチボラゲット | Method for oxygen pulping lignocellulosic material and recovering pulping chemicals |
| AR122640A1 (en) | 2020-06-17 | 2022-09-28 | Suzano Sa | METHOD TO TREAT A CONDENSATE IN A PULP MANUFACTURING PROCESS |
-
1981
- 1981-03-23 JP JP4270081A patent/JPS57191389A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS57191389A (en) | 1982-11-25 |
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