JPH0427967B2 - - Google Patents
Info
- Publication number
- JPH0427967B2 JPH0427967B2 JP58093193A JP9319383A JPH0427967B2 JP H0427967 B2 JPH0427967 B2 JP H0427967B2 JP 58093193 A JP58093193 A JP 58093193A JP 9319383 A JP9319383 A JP 9319383A JP H0427967 B2 JPH0427967 B2 JP H0427967B2
- Authority
- JP
- Japan
- Prior art keywords
- formaldehyde
- catalyst
- alkali
- reaction
- copper
- 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 - Lifetime
Links
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 138
- 239000003054 catalyst Substances 0.000 claims description 39
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 31
- 239000010949 copper Substances 0.000 claims description 31
- 229910052802 copper Inorganic materials 0.000 claims description 29
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 27
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 24
- 239000003513 alkali Substances 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 21
- 239000007864 aqueous solution Substances 0.000 claims description 20
- 239000000243 solution Substances 0.000 claims description 16
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 10
- 239000001301 oxygen Substances 0.000 claims description 10
- 229910052760 oxygen Inorganic materials 0.000 claims description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 2
- 239000000920 calcium hydroxide Substances 0.000 claims description 2
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 2
- 150000004675 formic acid derivatives Chemical class 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 description 22
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 11
- 229910052751 metal Inorganic materials 0.000 description 10
- 239000002184 metal Substances 0.000 description 10
- 150000005846 sugar alcohols Polymers 0.000 description 8
- 238000001994 activation Methods 0.000 description 7
- 239000001257 hydrogen Substances 0.000 description 7
- 229910052739 hydrogen Inorganic materials 0.000 description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
- 238000000354 decomposition reaction Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 238000007086 side reaction Methods 0.000 description 6
- 230000004913 activation Effects 0.000 description 5
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical class [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 4
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 4
- 230000003213 activating effect Effects 0.000 description 3
- 238000004817 gas chromatography Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 2
- 239000005751 Copper oxide Substances 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 description 2
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 2
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 description 2
- 239000012670 alkaline solution Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 229910000431 copper oxide Inorganic materials 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 235000019253 formic acid Nutrition 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229920003002 synthetic resin Polymers 0.000 description 2
- 239000000057 synthetic resin Substances 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- 229910001369 Brass Inorganic materials 0.000 description 1
- JJLJMEJHUUYSSY-UHFFFAOYSA-L Copper hydroxide Chemical compound [OH-].[OH-].[Cu+2] JJLJMEJHUUYSSY-UHFFFAOYSA-L 0.000 description 1
- 239000005750 Copper hydroxide Substances 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-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
- 229920000877 Melamine resin Polymers 0.000 description 1
- 239000004640 Melamine resin Substances 0.000 description 1
- 229920001807 Urea-formaldehyde Polymers 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 239000010951 brass Substances 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 238000011437 continuous method Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910001956 copper hydroxide Inorganic materials 0.000 description 1
- 238000011549 displacement method Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Landscapes
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
本発明はホルムアルデヒドの除去方法に関す
る。更に詳しくは、特定の触媒の存在下ホルムア
ルデヒドの自己カニツアロ反応によりホルムアル
デヒドを除去する方法に関する。
ホルムアルデヒドは、化学工業において重要な
原料として大量に使用されている。例えば、ペン
タエリスリトール、トリメチロールプロパン、ト
リメチロールエタン、ネオペンチルグリコールな
どの多価アルコール、またフエノール樹脂、メラ
ミン樹脂、ユリア樹脂などの合成樹脂の原料とし
て用いられている。しかしながら、かかる多価ア
ルコール、合成樹脂の反応液、廃液中には未反応
ホルムアルデヒドが残存しており、種々の不利益
を生じる。すなわち、多価アルコールを製造する
際、反応終了液中の未反応ホルムアルデヒドをそ
のままにして多価アルコールを回収した場合、未
反応ホルムアルデヒドが着色物質に変化したり多
価アルコールと副反応を起こし多価アルコールの
品質や収率に悪影響を及ぼす。また、廃液中に未
反応ホルムアルデヒドが残存すると、廃液の
CODを高めそのまま放流することができない。
このため、ホルムアルデヒドを除去する必要があ
り、種々の方法が提案されている。それらの中
で、下式のようにホルムアルデヒドの自己カニツ
アロ反応を利用してホルムアルデヒドをアルカリ
でメタノールとギ酸アルアルカリ塩に分解する方
法がある。
2nHCHO＋Ｍ（OH）ｎ→nCH3OH
＋（HCOO）nM ……(1)
（式中、Ｍはアカリ金属又はアルカリ土類金属
を示す。ｎは１または２である。）
この際、活性化酸化銅触媒の存在下で分解する
方法（特開昭54−3002号）および活性化金属触媒
の存在下で分解する方法（チエコスロバキア特許
第169106号）がある。
活性化酸化銅触媒による方法は、未反応ホルム
アルデヒドをほぼ完全に除去できるが、触媒が微
粉化し易く、そのため触媒が処理液に一部同伴さ
れるのでろ過工程を必要とする上に、触媒の追加
も必要である。また、ある時点で触媒の劣化が起
こるので取替えが必要である。更に、分解反応の
初期において、ホルムアルデヒドの自己カニツア
ロ反応以外に酸化銅とホルムアルデヒドとから下
式の副反応が多量に起こり、水素を発生して危険
も伴なう。
2HCHO＋2CuO＋２／ｎ Ｍ（OH）ｎ
→２／ｎ（HCOO）nM＋Cu2O＋H2O＋H2
……(2)
（式中、Ｍおよびｎは前記に同じ。）
2HCHO＋Cu2O＋２／nM（OH）ｎ
→２／ｎ（HCOO）nM＋2Cu＋H2O＋H2
……(3)
（式中、Ｍおよびｎは前記に同じ。）
また、式(1)より明らかなように自己カニツアロ
反応がホルムアルデヒド２モルに対してアルカリ
１当量で反応が進行するのに対し、この副反応は
前記の式(2)，(3)からわかるようにホルムアルデヒ
ド１モルに対しアルカリ１当量の反応であるた
め、分解反応におけるアルカリ使用量も多く、且
つ生成メタノールをギ酸に分解してしまう。
活性化金属銅触媒による方法は、前記特許明細
書の実施例にある様に濃アルカリ下で酸素を供給
して活性化処理した金属銅触媒でないと効果を示
さない。従つて、濃アルカリ下で金属銅に酸素を
供給するので、触媒中に酸化銅或いは水酸銅が増
加し、前記の水素を生成する副反応が多量に起
り、危険である。また、活性化処理時において
も、銅の溶出が多い等の欠点がある。
本発明者等は以上の事実をふまえて欠点の少な
いホルムアルデヒドの除去方法を鋭意検討した結
果、金属銅をホルムアルデヒドを含有するアルカ
リ溶液で処理したのち、PH７〜12の溶液中で酸素
を供給して得た活性化金属銅が、従来に比べて水
素を生成する副反応を抑制しホルムアルデヒドの
自己カニツアロ反応に対し、選択性の高い触媒で
あることを見い出し、本発明を完成するに至つ
た。即ち、本発明はホルムアルデヒドを触媒の存
在下アルカリでメタノールとギ酸アルカリ塩に除
去するにあたり、触媒として、ホルムアルデヒド
を含有するアルカリ溶液で処理し次いで、PH７〜
12の水溶液中で酸素処理した金属銅を用いること
を特徴とするホルムアルデヒドの除去方法であ
る。本発明によればホルムアルデヒドの分解反応
は水素を生成する副反応が従来の触媒の活性化金
属銅および活性化酸化銅に比べて極く少量起こる
のみで、ほとんどがメタノールとギ酸アルカリ塩
を生成する自己カニツアロ反応である。また触媒
の持続力もきわめてすぐれており、更に触媒の活
性が低下した場合はPH７〜12の水溶液中で酸素を
供給するだけで簡単に再生することができる。従
つて、本発明の利点は、水素の生成が少ない、危
険性が少ない、アルカリの使用量が少ない、回収
メタノール量が多い、触媒の活性持続力がすぐれ
ている、活性化処理に多価アルコール反応液も使
用できるので経済的、触媒の再生が簡単、触媒の
溶出がない等である。
本発明の触媒原料となる金属銅の純度には特別
な条件はなく、純銅或いは種々の銅含有合金が使
用できる。触媒の形状は切削銅の様な細片、普通
の銅線、粉末或いは銅を種々の担体に被覆した形
で使用できる。金属銅の活性化方法は、金属銅を
0.3〜1.0％ホルムアルデヒドを含有する0.1〜0.3
％アルカリ水溶液に50〜70℃にて10〜24時間浸漬
乃至接触させ、次にPH７〜12の水溶液中で酸素を
20〜70℃にて10〜24時間供給する。酸素の純度は
特に限定はなく、経済的見地から空気を利用する
のが最も有利である。アルカリとしては水酸化ア
ルカリ金属や水酸化アルカリ土類金属が使用でき
る。この活性化方法に用いるホルムアルデヒド含
有アルカリ水溶液には特に制限はなく、少なくと
もホルムアルデヒドとアルカリとを含有するもの
であれば充分当該水溶液として供することができ
る。例えば、未反応ホルムアルデヒドとアルカリ
とを含有する多価アルコール反応液をそのまま金
属銅の活性化用ホルムアルデヒド含有アルカリ水
溶液として使用することができる。したがつて、
本発明の金属銅のホルムアルデヒド含有アルカリ
水溶液処理とは、本発明のホルムアルデヒド除去
の対象となるホルムアルデヒド含有液がアルカリ
をも含有しているときにはそのまま、またアルカ
リを含有していないときにはアルカリを加えた液
による未活性金属銅の処理をも含むものである。
なお、この際ホルムアルデヒド含有アルカリ水
溶液による処理を行なわず、PH７〜12の水溶液中
で酸素を供給しただけでは活性の高い触媒は得ら
れないか又は活性化処理に長時間を要する。本発
明の活性化方法を実施してはじめて金属銅が自己
カニツアロ反応に対し選択性の高い、活性持続力
のきわめてすぐれた触媒になる。
また、本発明は触媒の活性が低下した場合に
は、すでに触媒がホルムアルデヒド含有アルカリ
水溶液により処理されているので単にPH７〜12の
水溶液中で20〜70℃、４〜24時間酸素を供給する
ことにより簡単に再生できることも大きな特徴で
ある。従つて一度反応器に入れた触媒は簡単な再
生を繰に返すことにより半永久的に使用すること
ができる。
本発明においてホルムアルデヒドを分解させる
ために使用されるアルカリとしては水酸化アルカ
リ金属または水酸化アルカリ土類金属があげられ
る。その具体例としては、例えば水酸化カリウ
ム、水酸化ナトリウム、水酸化カルシウム等があ
げられる。本発明のホルムアルデヒドの除去方法
を実施するに際して、アルカリ量はホルムアルデ
ヒド１モルに対して0.5〜0.55当量程度でよい。
ホルムアルデヒドの分解反応は常温でも進行する
が50〜90℃の範囲で反応を進行させるのが好まし
い。反応は連続式、回分式のどちらでも可能であ
るが、連続式が有利である。触媒負荷量は反応温
度、触媒の表面積、ホルムアルデヒド濃度および
アルカリ濃度によつても異なるが、見掛け10〜20
メツシユの切削銅を使用した場合、５〜10／
cat.Hr程度である。
つぎに実施例をあげて本発明を説明する。
実施例 １
網ふるいでふるい分けした10〜20メツシユの切
削金属銅100mlを内径３mmのガラス反応器に充填
し、ホルムアルデヒド0.3％および水酸化ナトリ
ウム0.2％を含む水溶液を60℃に予熱後10c.c.／
minの速度で10時間反応器に通液し、次に蒸留水
で切削金属銅を洗浄した後、反応器の上部迄蒸留
水を入れPH7.6温度60℃の条件下、空気を底部よ
り24時間供給して金属銅の活性化処理を行なつ
た。
次にホルムアルデヒド0.4％および水酸化ナト
リウム0.28％を含む水溶液を60℃に予熱後、触媒
負荷量５／cat.Hrで連続的に反応器の底部
より導入し、処理後のホルムアルデヒド量、生成
メタノール量および生成水素量を定量分析し経時
変化を調べた。その結果を表−１に示す。
なお、ホルムアルデヒドは亜硫酸ソーダ法、メ
タノールは処理液をギ酸で中和後GC（ガスクロマ
トグラフイー）法、水素は水中置換法で採取後
GC法により定量分析した。
The present invention relates to a method for removing formaldehyde. More specifically, the present invention relates to a method for removing formaldehyde by autocannivalo reaction of formaldehyde in the presence of a specific catalyst. Formaldehyde is used in large quantities as an important raw material in the chemical industry. For example, it is used as a raw material for polyhydric alcohols such as pentaerythritol, trimethylolpropane, trimethylolethane, and neopentyl glycol, and synthetic resins such as phenolic resin, melamine resin, and urea resin. However, unreacted formaldehyde remains in the reaction liquid and waste liquid of polyhydric alcohols and synthetic resins, causing various disadvantages. In other words, when producing polyhydric alcohol, if the unreacted formaldehyde in the reaction finished liquid is left as it is and the polyhydric alcohol is recovered, the unreacted formaldehyde may change into a colored substance or cause a side reaction with the polyhydric alcohol, resulting in polyhydric alcohol. Adversely affects alcohol quality and yield. Additionally, if unreacted formaldehyde remains in the waste liquid,
It increases the COD and cannot be released as is.
For this reason, it is necessary to remove formaldehyde, and various methods have been proposed. Among them, there is a method of decomposing formaldehyde into methanol and an alkali formate salt with an alkali by utilizing the autocanizaro reaction of formaldehyde as shown in the following formula. 2nHCHO + M(OH)n→nCH 3 OH + (HCOO)nM ...(1) (In the formula, M represents an alkali metal or an alkaline earth metal. n is 1 or 2.) At this time, activated oxidation There is a method of decomposition in the presence of a copper catalyst (JP-A-54-3002) and a method of decomposition in the presence of an activated metal catalyst (Ciekoslovakia Patent No. 169106). The method using an activated copper oxide catalyst can almost completely remove unreacted formaldehyde, but the catalyst tends to become finely powdered, so some of the catalyst is entrained in the treatment solution, requiring a filtration step and requiring the addition of a catalyst. is also necessary. Also, at some point the catalyst deteriorates and needs to be replaced. Furthermore, in the early stage of the decomposition reaction, in addition to the self-cannitzaro reaction of formaldehyde, a large amount of side reactions of the following formula occur between copper oxide and formaldehyde, generating hydrogen, which is also dangerous. 2HCHO+2CuO+2/n M(OH)n →2/n(HCOO)nM+Cu 2 O+H 2 O+H 2
...(2) (In the formula, M and n are the same as above.) 2HCHO + Cu 2 O + 2/nM (OH)n → 2/n (HCOO) nM + 2Cu + H 2 O + H 2
...(3) (In the formula, M and n are the same as above.) Also, as is clear from formula (1), while the autocannitzaro reaction proceeds with 1 equivalent of alkali per 2 moles of formaldehyde, As can be seen from the above equations (2) and (3), this side reaction is a reaction of 1 equivalent of alkali per 1 mole of formaldehyde, so the amount of alkali used in the decomposition reaction is large, and the methanol produced is decomposed into formic acid. I end up. The method using an activated metallic copper catalyst is not effective unless the metallic copper catalyst is activated by supplying oxygen in a concentrated alkali environment as described in the examples of the above-mentioned patent specification. Therefore, since oxygen is supplied to metallic copper under concentrated alkali, copper oxide or copper hydroxide increases in the catalyst, and a large amount of the above-mentioned hydrogen-producing side reaction occurs, which is dangerous. Furthermore, there are also drawbacks such as a large amount of copper being eluted during the activation process. In view of the above facts, the inventors of the present invention have intensively investigated a method for removing formaldehyde that has few drawbacks. After treating copper metal with an alkaline solution containing formaldehyde, the inventors have conducted a process of treating copper metal with an alkaline solution containing formaldehyde, and then supplying oxygen in a solution with a pH of 7 to 12. The present inventors have discovered that the obtained activated metallic copper is a highly selective catalyst for the autocannitzaro reaction of formaldehyde, suppressing side reactions that produce hydrogen compared to conventional methods, and has completed the present invention. That is, in the present invention, formaldehyde is removed into methanol and alkali formate using an alkali in the presence of a catalyst.
This is a formaldehyde removal method characterized by using metallic copper treated with oxygen in an aqueous solution of No. 12. According to the present invention, in the decomposition reaction of formaldehyde, only a small amount of the side reaction that generates hydrogen occurs compared to the activated metal copper and activated copper oxide of conventional catalysts, and most of the reaction generates methanol and alkali formate. This is an autocanizaro reaction. Furthermore, the catalyst has excellent sustainability, and if the activity of the catalyst decreases, it can be easily regenerated by simply supplying oxygen in an aqueous solution with a pH of 7 to 12. Therefore, the advantages of the present invention are that less hydrogen is produced, less danger is involved, less amount of alkali is used, more methanol is recovered, the catalyst has excellent sustainability of activity, and polyhydric alcohol is not used in the activation process. It is economical because a reaction solution can also be used, catalyst regeneration is easy, and there is no catalyst elution. There are no special requirements for the purity of metallic copper, which is the raw material for the catalyst of the present invention, and pure copper or various copper-containing alloys can be used. The catalyst can be used in the form of strips such as cut copper, ordinary copper wire, powder, or copper coated on various carriers. The method for activating metallic copper is
0.1-0.3 containing 0.3-1.0% formaldehyde
% alkaline aqueous solution at 50 to 70℃ for 10 to 24 hours, and then exposed to oxygen in an aqueous solution with a pH of 7 to 12.
Supply at 20-70°C for 10-24 hours. The purity of oxygen is not particularly limited, and from an economic standpoint, it is most advantageous to use air. As the alkali, an alkali metal hydroxide or an alkaline earth metal hydroxide can be used. The formaldehyde-containing alkaline aqueous solution used in this activation method is not particularly limited, and any aqueous solution containing at least formaldehyde and an alkali can be used as the aqueous solution. For example, a polyhydric alcohol reaction solution containing unreacted formaldehyde and an alkali can be used as it is as a formaldehyde-containing alkaline aqueous solution for activating metallic copper. Therefore,
The formaldehyde-containing alkaline aqueous solution treatment of metallic copper of the present invention means that when the formaldehyde-containing solution to be removed according to the present invention also contains an alkali, it is used as it is, or when it does not contain an alkali, it is treated with an alkali-added solution. It also includes the treatment of unactivated metallic copper by. At this time, if the treatment with the formaldehyde-containing alkaline aqueous solution is not carried out and oxygen is merely supplied in the aqueous solution having a pH of 7 to 12, a highly active catalyst cannot be obtained or the activation treatment requires a long time. Only when the activation method of the present invention is carried out can metal copper become a catalyst with high selectivity for the autocannitzaro reaction and extremely excellent durability of activity. In addition, in the present invention, when the activity of the catalyst decreases, since the catalyst has already been treated with an alkaline aqueous solution containing formaldehyde, it is possible to simply supply oxygen for 4 to 24 hours at 20 to 70°C in an aqueous solution with a pH of 7 to 12. Another great feature is that it can be played easily. Therefore, the catalyst once placed in the reactor can be used semi-permanently by repeating simple regeneration. The alkali used to decompose formaldehyde in the present invention includes alkali metal hydroxides and alkaline earth metal hydroxides. Specific examples include potassium hydroxide, sodium hydroxide, calcium hydroxide, and the like. When carrying out the formaldehyde removal method of the present invention, the amount of alkali may be about 0.5 to 0.55 equivalents per mole of formaldehyde.
Although the formaldehyde decomposition reaction proceeds even at room temperature, it is preferable to allow the reaction to proceed in the range of 50 to 90°C. The reaction can be carried out either continuously or batchwise, but the continuous method is advantageous. The amount of catalyst loaded varies depending on the reaction temperature, surface area of the catalyst, formaldehyde concentration, and alkali concentration, but the apparent
When using mesh cutting copper, 5 to 10/
About cat.Hr. Next, the present invention will be explained with reference to Examples. Example 1 A glass reactor with an inner diameter of 3 mm was filled with 100 ml of cut copper metal having 10 to 20 meshes sieved through a mesh sieve, and an aqueous solution containing 0.3% formaldehyde and 0.2% sodium hydroxide was preheated to 60°C and then heated to 10 c.c. /
The liquid was passed through the reactor for 10 hours at a rate of The metallic copper was activated by supplying a certain amount of time. Next, after preheating an aqueous solution containing 0.4% formaldehyde and 0.28% sodium hydroxide to 60°C, it was continuously introduced from the bottom of the reactor at a catalyst loading of 5/cat.Hr, and the amount of formaldehyde and methanol produced after treatment. The amount of hydrogen produced was quantitatively analyzed and changes over time were investigated. The results are shown in Table-1. Formaldehyde was collected using the sodium sulfite method, methanol was collected using the GC (gas chromatography) method after neutralizing the treated solution with formic acid, and hydrogen was collected using the water displacement method.
Quantitative analysis was performed by GC method.
【表】
実施例 ２
10〜20メツシユの切削金属銅２を内径40mmの
ジヤケツト付ステンレス製反応器に充填し、ホル
ムアルデヒド1.0％および水酸化ナトリウム0.1％
を含む水溶液を60℃に予熱後12／Hrの速度で
15時間通液し、以後、実施例１と同様にして金属
銅の活性化処理を行なつた。次にホルムアルデヒ
ドに対し0.55倍当量の水酸化ナトリウムを添加し
た0.4％の未反応ホルムアルデヒドを含むペンタ
エリスリトール反応液を70℃に予熱後、触媒負荷
量６／cat.Hrで反応器に導入し、未反応ホ
ルムアルデヒドの除去処理を行なつた。その結果
を表−２に示す。[Table] Example 2 10 to 20 meshes of cut copper metal 2 were packed into a stainless steel reactor with an inner diameter of 40 mm and a jacket, and 1.0% formaldehyde and 0.1% sodium hydroxide were added.
At a rate of 12/Hr after preheating an aqueous solution containing
The solution was passed for 15 hours, and thereafter, the activation treatment of metallic copper was performed in the same manner as in Example 1. Next, a pentaerythritol reaction solution containing 0.4% unreacted formaldehyde to which 0.55 equivalents of sodium hydroxide was added to formaldehyde was preheated to 70°C, and then introduced into the reactor at a catalyst loading of 6/cat.Hr. Reaction formaldehyde removal treatment was performed. The results are shown in Table-2.
【表】
実施例 ３
実施例２と同じ反応器で実施例２と同様に活性
化処理して得られた触媒を用いて0.3％の未反応
ホルムアルデヒドを含むトリメチロールプロパン
反応液を温度条件を60℃にした以外は実施例２と
同様にして処理した。その結果を表−３に示す。
なお、触媒の活性持続力を調べるため、処理液
中のホルムアルデヒド量が0.03％以上になる迄つ
づけた。[Table] Example 3 Using a catalyst obtained by activation treatment in the same manner as in Example 2 in the same reactor as in Example 2, a trimethylolpropane reaction solution containing 0.3% unreacted formaldehyde was heated under temperature conditions of 60°C. The treatment was carried out in the same manner as in Example 2, except that the temperature was changed to .degree. The results are shown in Table-3. In addition, in order to examine the activity sustainability of the catalyst, the treatment was continued until the amount of formaldehyde in the treatment solution reached 0.03% or more.
【表】
実施例 ４
実施例３の活性の低下した触媒をPH10のトリメ
チロールプロパン反応液中で20℃、10時間空気を
供給して触媒の再生を行なつた。
この再生した触媒を用いて、0.3％の未反応ホ
ルムアルデヒドを含むトリメチロールプロパン反
応液を実施例３と同様に処理した。その結果を表
−４に示す。[Table] Example 4 The catalyst of Example 3 with reduced activity was regenerated by supplying air at 20° C. for 10 hours in a trimethylolpropane reaction solution of pH 10. Using this regenerated catalyst, a trimethylolpropane reaction solution containing 0.3% unreacted formaldehyde was treated in the same manner as in Example 3. The results are shown in Table 4.
【表】
実施例 ５
1.2％の未反応ホルムアルデヒドを含むネオペ
ンチルグリコール反応液を実施例３と同じ活性化
金属銅で実施例３と同様にして未反応ホルムアル
デヒドの除去処理を行なつた。その結果を表−５
に示す。[Table] Example 5 A neopentyl glycol reaction solution containing 1.2% of unreacted formaldehyde was treated to remove unreacted formaldehyde in the same manner as in Example 3 using the same activated metal copper as in Example 3. Table 5 shows the results.
Shown below.
【表】
実施例 ６
10〜20メツシユの切削黄銅100mlを実施例１と
同様な活性化処理して得られた触媒を用いて、ホ
ルムアルデヒド0.4％およびナトリウム0.3％をむ
水溶液を実施例１と同様にして処理を行なつた。
その結果を表−６に示す。[Table] Example 6 An aqueous solution containing 0.4% formaldehyde and 0.3% sodium was prepared in the same manner as in Example 1 using a catalyst obtained by activating 100 ml of cut brass with 10 to 20 meshes in the same manner as in Example 1. The process was carried out as follows.
The results are shown in Table-6.
【表】
比較例 １
10〜20メツシユの切削金属銅100mlを５％水酸
化ナトリウム水溶液に加え６時間空気を供給して
得られた触媒を用いて、ホルムアルデヒド0.4％
および水酸化ナトリウム0.3％を含む水溶液を実
施例１と同様にして処理を行なつた。その結果を
表−７に示す。[Table] Comparative Example 1 Using a catalyst obtained by adding 100 ml of cut metal copper of 10 to 20 meshes to a 5% aqueous sodium hydroxide solution and supplying air for 6 hours, 0.4% formaldehyde was added.
An aqueous solution containing 0.3% of sodium hydroxide was treated in the same manner as in Example 1. The results are shown in Table-7.
【表】
比較例 ２
10〜20メツシユの切削金属銅100mlを蒸留水に
加え60℃、７日間、空気を供給して得られた触媒
を用いて、ホルムアルデヒド0.4％および水酸化
ナトリウム0.3％を含む水溶液を実施例１と同様
にして処理を行なつた。処理開始直後のホルムア
ルデヒドの残量は0.24％（転化率40％）であつ
た。[Table] Comparative Example 2 A catalyst containing 0.4% formaldehyde and 0.3% sodium hydroxide was prepared by adding 100ml of cut metal copper of 10 to 20 meshes to distilled water and supplying air at 60°C for 7 days. The aqueous solution was treated in the same manner as in Example 1. The remaining amount of formaldehyde immediately after the start of treatment was 0.24% (conversion rate 40%).
Claims (1)
でメタノールとギ酸アルカリ塩に分解除去するに
あたり、該触媒としてホルムアルデヒドを含有す
るアルカリ水溶液で処理し次いでPH７〜12の溶液
中で酸素処理した金属銅を用いることを特徴とす
るホルムアルデヒドの除去方法。 ２ アルカリが水酸化カリウム、水酸化ナトリウ
ムまたは水酸化カルシウムである特許請求の範囲
第１項記載の方法。[Scope of Claims] 1. When formaldehyde is decomposed and removed with an alkali in the presence of a catalyst into methanol and an alkali formate salt, the method is treated with an alkaline aqueous solution containing formaldehyde as the catalyst, and then treated with oxygen in a solution with a pH of 7 to 12. A method for removing formaldehyde characterized by using metallic copper. 2. The method according to claim 1, wherein the alkali is potassium hydroxide, sodium hydroxide or calcium hydroxide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58093193A JPS59216839A (en) | 1983-05-26 | 1983-05-26 | Removal of formaldehyde |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58093193A JPS59216839A (en) | 1983-05-26 | 1983-05-26 | Removal of formaldehyde |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS59216839A JPS59216839A (en) | 1984-12-06 |
| JPH0427967B2 true JPH0427967B2 (en) | 1992-05-13 |
Family
ID=14075740
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP58093193A Granted JPS59216839A (en) | 1983-05-26 | 1983-05-26 | Removal of formaldehyde |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS59216839A (en) |
Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5145213B2 (en) * | 2005-04-15 | 2013-02-13 | ユニヴァーシティー オブ サザン カリフォルニア | Efficient and selective conversion of carbon dioxide to methanol, dimethyl ether and derivatives |
| CA2604574C (en) | 2005-04-15 | 2013-11-19 | University Of Southern California | Selective oxidative conversion of methane to methanol, dimethyl ether and derived products |
| US7378561B2 (en) | 2006-08-10 | 2008-05-27 | University Of Southern California | Method for producing methanol, dimethyl ether, derived synthetic hydrocarbons and their products from carbon dioxide and water (moisture) of the air as sole source material |
| US7795175B2 (en) | 2006-08-10 | 2010-09-14 | University Of Southern California | Nano-structure supported solid regenerative polyamine and polyamine polyol absorbents for the separation of carbon dioxide from gas mixtures including the air |
| US8163066B2 (en) | 2007-05-21 | 2012-04-24 | Peter Eisenberger | Carbon dioxide capture/regeneration structures and techniques |
| US9028592B2 (en) | 2010-04-30 | 2015-05-12 | Peter Eisenberger | System and method for carbon dioxide capture and sequestration from relatively high concentration CO2 mixtures |
| WO2011137398A1 (en) | 2010-04-30 | 2011-11-03 | Peter Eisenberger | System and method for carbon dioxide capture and sequestration |
| US11059024B2 (en) | 2012-10-25 | 2021-07-13 | Georgia Tech Research Corporation | Supported poly(allyl)amine and derivatives for CO2 capture from flue gas or ultra-dilute gas streams such as ambient air or admixtures thereof |
| SG11201604934QA (en) | 2013-12-31 | 2016-07-28 | Eisenberger Peter And Chichilnisky Graciela Jointly | Rotating multi-monolith bed movement system for removing co2 from the atmosphere |
| KR101918652B1 (en) * | 2016-12-29 | 2018-11-14 | 주식회사 마디 | Activated carbon for removal of formaldehyde gas and the method thereof |
| EP4532081A4 (en) | 2022-05-27 | 2025-09-17 | Zero Carbon Systems Inc | HIGH-THROUGH DIRECT AIR COLLECTION SYSTEM FOR MOVING PLATES |
-
1983
- 1983-05-26 JP JP58093193A patent/JPS59216839A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS59216839A (en) | 1984-12-06 |
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