JPH1087551A - Purification method of methacrylic acid - Google Patents
Purification method of methacrylic acidInfo
- Publication number
- JPH1087551A JPH1087551A JP24349496A JP24349496A JPH1087551A JP H1087551 A JPH1087551 A JP H1087551A JP 24349496 A JP24349496 A JP 24349496A JP 24349496 A JP24349496 A JP 24349496A JP H1087551 A JPH1087551 A JP H1087551A
- Authority
- JP
- Japan
- Prior art keywords
- methacrylic acid
- containing compound
- group
- treatment
- acid
- 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.)
- Granted
Links
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 title claims abstract description 100
- 238000000034 method Methods 0.000 title claims abstract description 25
- 238000000746 purification Methods 0.000 title claims abstract description 6
- 150000001875 compounds Chemical class 0.000 claims abstract description 62
- 125000003396 thiol group Chemical group [H]S* 0.000 claims abstract description 24
- 125000000542 sulfonic acid group Chemical group 0.000 claims abstract description 15
- 239000000126 substance Substances 0.000 claims abstract description 13
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 12
- 230000003197 catalytic effect Effects 0.000 claims abstract description 10
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 claims abstract description 7
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims abstract description 6
- 239000000463 material Substances 0.000 claims description 15
- 238000011084 recovery Methods 0.000 abstract description 24
- 238000011282 treatment Methods 0.000 description 37
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 16
- 125000003277 amino group Chemical group 0.000 description 15
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 10
- 239000003112 inhibitor Substances 0.000 description 10
- 238000006116 polymerization reaction Methods 0.000 description 10
- DHBXNPKRAUYBTH-UHFFFAOYSA-N 1,1-ethanedithiol Chemical compound CC(S)S DHBXNPKRAUYBTH-UHFFFAOYSA-N 0.000 description 9
- 238000004821 distillation Methods 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- 238000001577 simple distillation Methods 0.000 description 9
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical class C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 7
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 7
- 230000002378 acidificating effect Effects 0.000 description 7
- 229920001429 chelating resin Polymers 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 239000003456 ion exchange resin Substances 0.000 description 7
- 229920003303 ion-exchange polymer Polymers 0.000 description 7
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 6
- AMIMRNSIRUDHCM-UHFFFAOYSA-N Isopropylaldehyde Chemical compound CC(C)C=O AMIMRNSIRUDHCM-UHFFFAOYSA-N 0.000 description 6
- 238000000605 extraction Methods 0.000 description 6
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 6
- KQNPFQTWMSNSAP-UHFFFAOYSA-N isobutyric acid Chemical compound CC(C)C(O)=O KQNPFQTWMSNSAP-UHFFFAOYSA-N 0.000 description 6
- WJFKNYWRSNBZNX-UHFFFAOYSA-N 10H-phenothiazine Chemical compound C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-UHFFFAOYSA-N 0.000 description 5
- 150000001412 amines Chemical class 0.000 description 5
- 238000004040 coloring Methods 0.000 description 5
- NOUUUQMKVOUUNR-UHFFFAOYSA-N n,n'-diphenylethane-1,2-diamine Chemical compound C=1C=CC=CC=1NCCNC1=CC=CC=C1 NOUUUQMKVOUUNR-UHFFFAOYSA-N 0.000 description 5
- 230000003647 oxidation Effects 0.000 description 5
- 229950000688 phenothiazine Drugs 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 4
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 4
- 239000007858 starting material Substances 0.000 description 4
- STNJBCKSHOAVAJ-UHFFFAOYSA-N Methacrolein Chemical compound CC(=C)C=O STNJBCKSHOAVAJ-UHFFFAOYSA-N 0.000 description 3
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 3
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 3
- 238000011437 continuous method Methods 0.000 description 3
- UAOMVDZJSHZZME-UHFFFAOYSA-N diisopropylamine Chemical compound CC(C)NC(C)C UAOMVDZJSHZZME-UHFFFAOYSA-N 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 239000001282 iso-butane Substances 0.000 description 3
- RMVRSNDYEFQCLF-UHFFFAOYSA-N thiophenol Chemical compound SC1=CC=CC=C1 RMVRSNDYEFQCLF-UHFFFAOYSA-N 0.000 description 3
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 3
- HCZMHWVFVZAHCR-UHFFFAOYSA-N 2-[2-(2-sulfanylethoxy)ethoxy]ethanethiol Chemical compound SCCOCCOCCS HCZMHWVFVZAHCR-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 2
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 2
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 2
- OJGMBLNIHDZDGS-UHFFFAOYSA-N N-Ethylaniline Chemical compound CCNC1=CC=CC=C1 OJGMBLNIHDZDGS-UHFFFAOYSA-N 0.000 description 2
- 229920000297 Rayon Polymers 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- WGQKYBSKWIADBV-UHFFFAOYSA-N benzylamine Chemical compound NCC1=CC=CC=C1 WGQKYBSKWIADBV-UHFFFAOYSA-N 0.000 description 2
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 2
- WQAQPCDUOCURKW-UHFFFAOYSA-N butanethiol Chemical compound CCCCS WQAQPCDUOCURKW-UHFFFAOYSA-N 0.000 description 2
- VHRGRCVQAFMJIZ-UHFFFAOYSA-N cadaverine Chemical compound NCCCCCN VHRGRCVQAFMJIZ-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical compound C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 description 2
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethanethiol Chemical compound CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 description 2
- LIWAQLJGPBVORC-UHFFFAOYSA-N ethylmethylamine Chemical compound CCNC LIWAQLJGPBVORC-UHFFFAOYSA-N 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- -1 inorganic acid salts Chemical class 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- DPBLXKKOBLCELK-UHFFFAOYSA-N pentan-1-amine Chemical compound CCCCCN DPBLXKKOBLCELK-UHFFFAOYSA-N 0.000 description 2
- KIDHWZJUCRJVML-UHFFFAOYSA-N putrescine Chemical compound NCCCCN KIDHWZJUCRJVML-UHFFFAOYSA-N 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- XFNJVJPLKCPIBV-UHFFFAOYSA-N trimethylenediamine Chemical compound NCCCN XFNJVJPLKCPIBV-UHFFFAOYSA-N 0.000 description 2
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 description 2
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 description 1
- ZQXIMYREBUZLPM-UHFFFAOYSA-N 1-aminoethanethiol Chemical compound CC(N)S ZQXIMYREBUZLPM-UHFFFAOYSA-N 0.000 description 1
- BMVXCPBXGZKUPN-UHFFFAOYSA-N 1-hexanamine Chemical compound CCCCCCN BMVXCPBXGZKUPN-UHFFFAOYSA-N 0.000 description 1
- FETFXNFGOYOOSP-UHFFFAOYSA-N 1-sulfanylpropan-2-ol Chemical compound CC(O)CS FETFXNFGOYOOSP-UHFFFAOYSA-N 0.000 description 1
- PGIGZWJIJSINOD-UHFFFAOYSA-N 12h-benzo[a]phenothiazine Chemical compound C1=CC=CC2=C3NC4=CC=CC=C4SC3=CC=C21 PGIGZWJIJSINOD-UHFFFAOYSA-N 0.000 description 1
- CNDCQWGRLNGNNO-UHFFFAOYSA-N 2-(2-sulfanylethoxy)ethanethiol Chemical compound SCCOCCS CNDCQWGRLNGNNO-UHFFFAOYSA-N 0.000 description 1
- RPKCLSMBVQLWIN-UHFFFAOYSA-N 2-n-methylbenzene-1,2-diamine Chemical compound CNC1=CC=CC=C1N RPKCLSMBVQLWIN-UHFFFAOYSA-N 0.000 description 1
- WGTASENVNYJZBK-UHFFFAOYSA-N 3,4,5-trimethoxyamphetamine Chemical compound COC1=CC(CC(C)N)=CC(OC)=C1OC WGTASENVNYJZBK-UHFFFAOYSA-N 0.000 description 1
- 241001550224 Apha Species 0.000 description 1
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 1
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 1
- 229940092714 benzenesulfonic acid Drugs 0.000 description 1
- UENWRTRMUIOCKN-UHFFFAOYSA-N benzyl thiol Chemical compound SCC1=CC=CC=C1 UENWRTRMUIOCKN-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- SMTOKHQOVJRXLK-UHFFFAOYSA-N butane-1,4-dithiol Chemical compound SCCCCS SMTOKHQOVJRXLK-UHFFFAOYSA-N 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- QEBJRRFIWCWPMA-UHFFFAOYSA-N diethyl-bis(sulfanyl)-$l^{4}-sulfane Chemical compound CCS(S)(S)CC QEBJRRFIWCWPMA-UHFFFAOYSA-N 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- 229940043279 diisopropylamine Drugs 0.000 description 1
- WEHWNAOGRSTTBQ-UHFFFAOYSA-N dipropylamine Chemical compound CCCNCCC WEHWNAOGRSTTBQ-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000003916 ethylene diamine group Chemical group 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229940098779 methanesulfonic acid Drugs 0.000 description 1
- KZCOBXFFBQJQHH-UHFFFAOYSA-N octane-1-thiol Chemical compound CCCCCCCCS KZCOBXFFBQJQHH-UHFFFAOYSA-N 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- BHAAPTBBJKJZER-UHFFFAOYSA-N p-anisidine Chemical compound COC1=CC=C(N)C=C1 BHAAPTBBJKJZER-UHFFFAOYSA-N 0.000 description 1
- 125000005489 p-toluenesulfonic acid group Chemical group 0.000 description 1
- 229940100684 pentylamine Drugs 0.000 description 1
- SUVIGLJNEAMWEG-UHFFFAOYSA-N propane-1-thiol Chemical compound CCCS SUVIGLJNEAMWEG-UHFFFAOYSA-N 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 description 1
- 150000004992 toluidines Chemical class 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
(57)【要約】
【課題】 気相接触酸化反応で得られるメタクリル酸含
有物から高い回収率で着色の少ない高品質のメタクリル
酸を得ることができる精製法を提供する。
【解決手段】 メタクリル酸含有物を第１級および／ま
たは第２級のアミノ基含有化合物とメルカプト基含有化
合物、もしくは、第１級および／または第２級のアミノ
基含有化合物、メルカプト基含有化合物およびスルホン
酸基含有化合物で処理する。PROBLEM TO BE SOLVED: To provide a purification method capable of obtaining high-quality methacrylic acid with little coloration at a high recovery rate from a methacrylic acid-containing substance obtained by a gas phase catalytic oxidation reaction. SOLUTION: A methacrylic acid-containing substance is converted into a primary and / or secondary amino group-containing compound and a mercapto group-containing compound, or a primary and / or secondary amino group-containing compound, a mercapto group-containing compound. And a sulfonic acid group-containing compound.
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、イソブタン、イソ
ブチレン、第３級ブチルアルコール、メチル第３級ブチ
ルエーテル、メタクロレイン、イソブチルアルデヒド、
イソ酪酸等を気相接触酸化反応して得られるメタクリル
酸の新規な精製法に関する。TECHNICAL FIELD The present invention relates to isobutane, isobutylene, tertiary butyl alcohol, methyl tertiary butyl ether, methacrolein, isobutyraldehyde,
The present invention relates to a novel method for purifying methacrylic acid obtained by subjecting isobutyric acid or the like to a gas phase catalytic oxidation reaction.
【０００２】[0002]
【従来の技術】イソブタン、イソブチレン、第３級ブチ
ルアルコール、メチル第３級ブチルエーテル、メタクロ
レイン、イソブチルアルデヒド、イソ酪酸等を気相接触
酸化反応して得られるメタクリル酸含有物は、抽出や蒸
留等の通常の精製手段により比較的純度の高い製品とす
ることができるが、この方法では依然として着色の要因
となる微量の不純物が残存するため、本来透明であるは
ずの製品が着色するという問題があった。このような着
色要因物質のなかには、メタクリル酸と沸点の近いもの
があり、通常の蒸留操作では不純物の除去が困難であっ
たり、精製工程が複雑化してコストが高くなる等の問題
があった。2. Description of the Related Art A methacrylic acid-containing substance obtained by subjecting isobutane, isobutylene, tertiary butyl alcohol, methyl tertiary butyl ether, methacrolein, isobutyraldehyde, isobutyric acid and the like to a gas phase oxidation reaction is subjected to extraction, distillation, etc. Although a product having relatively high purity can be obtained by the conventional purification means, there is still a problem that a trace of impurities that cause coloring remains, so that a product that should be transparent is colored. Was. Some of such coloring factors have a boiling point close to that of methacrylic acid, and there have been problems such as difficulty in removing impurities by a normal distillation operation and an increase in cost due to complicated purification steps.
【０００３】このような着色要因物質を取り除くための
メタクリル酸の精製法として、例えば、重亜硫酸塩を使
用する方法（特公昭６２−４５２１８号公報）、酸性触
媒およびメルカプト基を有する化合物を使用する方法
（特開昭６０−６６３５号公報）、アミン類を使用する
方法（特公平３−３６４６号公報）等が、従来より提案
されている。As a method for purifying methacrylic acid to remove such coloring factors, for example, a method using bisulfite (Japanese Patent Publication No. 62-45218), an acid catalyst and a compound having a mercapto group are used. A method (JP-A-60-6635), a method using amines (JP-B-3-3646), and the like have been conventionally proposed.
【０００４】[0004]
【発明が解決しようとする課題】しかしながら、重亜硫
酸塩を使用する方法は効果が少ないため実用的でない。
酸性触媒およびメルカプト基を有する化合物を使用する
方法は、効果はあるものの工業的に満足のいくものでは
なかった。また、アミン類を単独で添加する方法は、不
純物を除去するために比較的多くのアミン類を添加する
必要があり、その結果、アミン類がメタクリル酸と反応
するためメタクリル酸の回収率が低下するという問題が
あった。However, the method using bisulfite is not practical because it has little effect.
Although the method using an acidic catalyst and a compound having a mercapto group has been effective, it has not been industrially satisfactory. In addition, in the method of adding amines alone, it is necessary to add a relatively large amount of amines in order to remove impurities, and as a result, the amines react with methacrylic acid, thereby reducing the recovery rate of methacrylic acid. There was a problem of doing.
【０００５】本発明は、気相接触酸化反応で得られるメ
タクリル酸含有物から着色の少ない高品質のメタクリル
酸を高い回収率で得ることができる精製法を提供するこ
とを目的としている。An object of the present invention is to provide a purification method capable of obtaining high-quality methacrylic acid with little coloring from a methacrylic acid-containing substance obtained by a gas phase catalytic oxidation reaction at a high recovery rate.
【０００６】[0006]
【課題を解決するための手段】本発明は、気相接触酸化
反応で得られるメタクリル酸含有物を第１級および／ま
たは第２級のアミノ基含有化合物とメルカプト基含有化
合物、もしくは、第１級および／または第２級のアミノ
基含有化合物、メルカプト基含有化合物およびスルホン
酸基含有化合物で処理することを特徴とするメタクリル
酸の精製法である。According to the present invention, a methacrylic acid-containing compound obtained by a gas phase catalytic oxidation reaction is reacted with a primary and / or secondary amino group-containing compound and a mercapto group-containing compound or a first compound. A method for purifying methacrylic acid, comprising treating with a secondary and / or secondary amino group-containing compound, a mercapto group-containing compound and a sulfonic acid group-containing compound.
【０００７】[0007]
【発明の実施の形態】本発明に用いられるメタクリル酸
含有物とは、イソブタン、イソブチレン、第３級ブチル
アルコール、メチル第３級ブチルエーテル、メタクロレ
イン、イソブチルアルデヒド、イソ酪酸等を気相接触酸
化した時に得られるメタクリル酸を含有する水溶液を、
抽出および蒸留等の分離操作により、メタクリル酸の含
有率を約５０重量％以上に高めたものをいうが、これに
限定されるものではない。BEST MODE FOR CARRYING OUT THE INVENTION The methacrylic acid-containing material used in the present invention is obtained by subjecting isobutane, isobutylene, tertiary butyl alcohol, methyl tertiary butyl ether, methacrolein, isobutyraldehyde, isobutyric acid and the like to gas phase contact oxidation. An aqueous solution containing methacrylic acid obtained sometimes is
It refers to one in which the content of methacrylic acid has been increased to about 50% by weight or more by separation operations such as extraction and distillation, but is not limited thereto.
【０００８】第１級および／または第２級のアミノ基含
有化合物（以下、アミノ基含有化合物という）として
は、脂肪族、芳香族アミンのいずれでもよく、１分子中
に複数個のアミノ基を有するアミン類、アンモニア、ヒ
ドラジンおよびその誘導体、さらにはヒドロキシルアミ
ンおよびその無機酸塩等の化合物も含まれる。アミノ基
含有化合物としては、例えば、プロピルアミン、ブチル
アミン、ペンチルアミン、ヘキシルアミン、ジエチルア
ミン、ジ−ｎ−プロピルアミン、ジイソプロピルアミ
ン、メチルエチルアミン、エチレンジアミン、トリメチ
レンジアミン、テトラメチレンジアミン、ペンタメチレ
ンジアミン、Ｎ，Ｎ’−ジフェニルエチレンジアミン、
エタノールアミン、ヘキサメチレンジアミン、ジエチレ
ントリアミン、テトラエチレンペンタミン、アニリン、
トルイジン、Ｎ−エチルアニリン、Ｎ−プロピルアミ
ン、ジフェニルアミン、フェニレンジアミン、Ｎ−メチ
ルフェニレンジアミン、ベンジルアミン、フェネチルア
ミン、アニシジン等が挙げられる。また、アミノ基含有
化合物の添加量はメタクリル酸含有物１００重量部に対
して０．００１〜１重量部、特に０．００５〜０．５重
量部の範囲が好ましい。The primary and / or secondary amino group-containing compound (hereinafter, referred to as an amino group-containing compound) may be any of aliphatic and aromatic amines, and may have a plurality of amino groups in one molecule. Compounds such as amines, ammonia, hydrazine and derivatives thereof, and hydroxylamine and inorganic acid salts thereof are also included. Examples of the amino group-containing compound include, for example, propylamine, butylamine, pentylamine, hexylamine, diethylamine, di-n-propylamine, diisopropylamine, methylethylamine, ethylenediamine, trimethylenediamine, tetramethylenediamine, pentamethylenediamine, N , N'-diphenylethylenediamine,
Ethanolamine, hexamethylenediamine, diethylenetriamine, tetraethylenepentamine, aniline,
Toluidine, N-ethylaniline, N-propylamine, diphenylamine, phenylenediamine, N-methylphenylenediamine, benzylamine, phenethylamine, anisidine and the like. The amount of the amino group-containing compound to be added is preferably in the range of 0.001 to 1 part by weight, more preferably 0.005 to 0.5 part by weight, based on 100 parts by weight of the methacrylic acid-containing substance.
【０００９】メルカプト基含有化合物としては、脂肪
族、芳香族いずれでもよく、分子中に１個以上のメルカ
プト基を有する化合物であればよい。このような化合物
としては、例えば、メチルメルカプタン、エチルメルカ
プタン、２−メルカプトエタノール、ｎ−プロピルメル
カプタン、１−メルカプト−２−プロパノール、ｎ−ブ
チルメルカプタン、ｎ−オクチルメルカプタン、１，２
−エタンジチオール、１，４−ブタンジチオール、２−
アミノエタンチオール、ジメルカプトジエチルスルフィ
ド、ジ（２−メルカプトエチル）エーテル、トリグリコ
ールジメルカプタン、フェニルメルカプタン、ベンジル
メルカプタン、ナフチルメルカプタン等が挙げられる。
また、メルカプト基含有化合物の添加量はメタクリル酸
含有物１００重量部に対して０．００１〜１重量部、特
に０．０１〜０．５重量部の範囲が好ましい。The mercapto group-containing compound may be aliphatic or aromatic, and may be any compound having at least one mercapto group in the molecule. Examples of such compounds include methyl mercaptan, ethyl mercaptan, 2-mercaptoethanol, n-propyl mercaptan, 1-mercapto-2-propanol, n-butyl mercaptan, n-octyl mercaptan,
-Ethanedithiol, 1,4-butanedithiol, 2-
Examples thereof include aminoethanethiol, dimercaptodiethylsulfide, di (2-mercaptoethyl) ether, triglycoldimercaptan, phenylmercaptan, benzylmercaptan, and naphthylmercaptan.
The addition amount of the mercapto group-containing compound is preferably in the range of 0.001 to 1 part by weight, particularly preferably 0.01 to 0.5 part by weight, per 100 parts by weight of the methacrylic acid-containing substance.
【００１０】スルホン酸基含有化合物としては、スルホ
ン酸基を有する無機または有機化合物を意味し、例え
ば、硫酸、ベンゼンスルホン酸、ｐ−トルエンスルホン
酸、メタンスルホン酸、スルホン酸基を交換基として有
する強酸性イオン交換樹脂等が挙げられる。スルホン酸
基含有化合物による処理は、回分式および連続式のいず
れの方法を用いてもよい。その際の使用量は、回分式で
はメタクリル酸含有物１００重量部に対して０．１〜５
０重量部、特に１〜３０重量部の範囲が好ましい。連続
式においては、メタクリル酸含有物の流通量はスルホン
酸基含有化合物に対して空間速度で０．０１〜１０ｈｒ
-1、特に０．０５〜５ｈｒ-1の範囲が好ましい。[0010] The sulfonic acid group-containing compound means an inorganic or organic compound having a sulfonic acid group, for example, sulfuric acid, benzenesulfonic acid, p-toluenesulfonic acid, methanesulfonic acid, or a sulfonic acid group as an exchange group. Strong acid ion exchange resins and the like can be mentioned. The treatment with the sulfonic acid group-containing compound may be performed by either a batch method or a continuous method. In this case, the amount used is 0.1 to 5 parts by weight per 100 parts by weight of the methacrylic acid-containing material in the batch system.
0 parts by weight, particularly preferably in the range of 1 to 30 parts by weight. In the continuous method, the flow rate of the methacrylic acid-containing material is 0.01 to 10 hours at a space velocity with respect to the sulfonic acid group-containing compound.
-1 , particularly preferably in the range of 0.05 to 5 hr -1 .
【００１１】本発明の方法において、アミノ基含有化合
物による処理を行った後にメルカプト基含有化合物によ
って処理、もしくは、メルカプト基含有化合物によって
処理を行った後にアミノ基含有化合物による処理を行う
のが好ましいが、アミノ基含有化合物とメルカプト基含
有化合物をメタクリル酸含有物へ同時に添加して処理を
行ってもよい。In the method of the present invention, it is preferable that the treatment with the amino group-containing compound is performed after the treatment with the amino group-containing compound, or the treatment with the amino group-containing compound is performed after the treatment with the mercapto group-containing compound. Alternatively, the treatment may be performed by simultaneously adding an amino group-containing compound and a mercapto group-containing compound to a methacrylic acid-containing substance.
【００１２】また、スルホン酸基含有化合物により処理
する場合は、アミノ基含有化合物による処理を行った後
に、メルカプト基含有化合物およびスルホン酸基含有化
合物によって処理、もしくは、メルカプト基含有化合物
およびスルホン酸基含有化合物による処理を行った後
に、アミノ基含有化合物による処理を行うのが好ましい
が、アミノ基含有化合物、メルカプト基含有化合物およ
びスルホン酸基含有化合物をメタクリル酸含有物へ同時
に添加して処理を行ってもよい。In the case of treatment with a sulfonic acid group-containing compound, treatment with an amino group-containing compound is followed by treatment with a mercapto group-containing compound and a sulfonic acid group-containing compound, or a treatment with a mercapto group-containing compound and a sulfonic acid group. After the treatment with the containing compound, the treatment with the amino group-containing compound is preferably performed, but the treatment is performed by simultaneously adding the amino group-containing compound, the mercapto group-containing compound and the sulfonic acid group-containing compound to the methacrylic acid-containing material. You may.
【００１３】アミノ基含有化合物による処理の方法とし
ては、例えば、メタクリル酸含有物にアミノ基含有化合
物を添加して所定の温度に加熱した後、好ましくは混合
物を攪拌しながら、一定時間保持する方法が用いられ
る。処理温度は５０〜１５０℃、特に８０〜１３０℃の
範囲が好ましい。処理時間は５分〜５時間、特に１５分
〜３時間の範囲が好ましい。As a method of treatment with an amino group-containing compound, for example, a method of adding an amino group-containing compound to a methacrylic acid-containing substance, heating the mixture to a predetermined temperature, and preferably holding the mixture for a predetermined time while stirring the mixture. Is used. The processing temperature is preferably in the range of 50 to 150C, particularly preferably 80 to 130C. The processing time is preferably in the range of 5 minutes to 5 hours, particularly preferably in the range of 15 minutes to 3 hours.
【００１４】メルカプト基含有化合物による処理の方法
としては、例えばメタクリル酸含有物にメルカプト基含
有化合物を添加して所定の温度に加熱した後、好ましく
は混合物を攪拌しながら、一定時間保持する方法が用い
られる。処理温度は５０〜１５０℃、特に８０〜１３０
℃の範囲が好ましい。処理時間は５分〜５時間、特に１
５分〜３時間の範囲が好ましい。As a method of treatment with a mercapto group-containing compound, for example, a method of adding a mercapto group-containing compound to a methacrylic acid-containing substance, heating the mixture to a predetermined temperature, and preferably holding the mixture for a predetermined time while stirring the mixture. Used. The processing temperature is 50-150 ° C, especially 80-130.
C. is preferred. Processing time is 5 minutes to 5 hours, especially 1
A range from 5 minutes to 3 hours is preferred.
【００１５】メルカプト基含有化合物およびスルホン酸
基含有化合物による処理は、回分式および連続式のいず
れの方法でも行えるが、好適な処理方式としては、例え
ば、スルホン化陽イオン交換樹脂等の固体触媒を固定床
に充填して、メルカプト基含有化合物を添加したメタク
リル酸含有物を連続的に流通処理する連続式が挙げられ
る。処理温度は２０〜１５０℃、特に４０〜１３０℃の
範囲が好ましい。処理時間は５分〜５時間、特に１５分
〜３時間の範囲が好ましい。The treatment with the mercapto group-containing compound and the sulfonic acid group-containing compound can be carried out by either a batch system or a continuous system. A preferred treatment system is, for example, a solid catalyst such as a sulfonated cation exchange resin. A continuous method in which a methacrylic acid-containing substance to which a mercapto group-containing compound is added by continuously filling a fixed bed and continuously flowing is used. The processing temperature is preferably in the range of 20 to 150C, particularly preferably in the range of 40 to 130C. The processing time is preferably in the range of 5 minutes to 5 hours, particularly preferably in the range of 15 minutes to 3 hours.
【００１６】アミノ基含有化合物による処理を行った
後、メルカプト基含有化合物および／またはスルホン酸
基含有化合物による処理を行う場合、または、メルカプ
ト基含有化合物および／またはスルホン酸基含有化合物
による処理を行った後、アミノ基含有化合物による処理
を行う場合、連続して処理を行ってもよいが、これらの
処理の間で蒸留等の操作を行ってもよい。When a treatment with a compound containing a mercapto group and / or a compound containing a sulfonic acid group is carried out after a treatment with a compound containing an amino group, or a treatment with a compound containing a mercapto group and / or a compound containing a sulfonic acid group is carried out. After that, when the treatment with the amino group-containing compound is performed, the treatment may be performed continuously, or an operation such as distillation may be performed between these treatments.
【００１７】最終的に、処理液は蒸留等の通常の分離操
作によって、メタクリル酸から未反応の処理剤、処理剤
と着色要因物質との反応物等を分離するが、この際、例
えば、フェノチアジン、ベンゾフェノチアジン等の重合
禁止剤を添加しておくことが好ましい。Finally, the processing liquid is separated from the methacrylic acid by a normal separation operation such as distillation to remove the unreacted processing agent, the reaction product of the processing agent and the coloring factor substance, and in this case, for example, phenothiazine It is preferable to add a polymerization inhibitor such as benzophenothiazine.
【００１８】[0018]
【実施例】以下、本発明の実施例および比較例を示す。
下記実施例および比較例中のメタクリル酸の純度は重量
百分率を意味する。また、メタクリル酸の回収率は、 回収率（％）＝Ｂ／Ａ×１００ により定義され、式中のＡおよびＢは、 Ａ：仕込みのメタクリル酸含有物中のメタクリル酸の重
量 Ｂ：処理後の精製メタクリル酸中のメタクリル酸の重量 を意味する。EXAMPLES Examples and comparative examples of the present invention will be described below.
The purity of methacrylic acid in the following Examples and Comparative Examples means percent by weight. The recovery rate of methacrylic acid is defined by a recovery rate (%) = B / A × 100, where A and B are: A: weight of methacrylic acid in methacrylic acid-containing material charged B: after treatment Means the weight of methacrylic acid in the purified methacrylic acid.
【００１９】［実施例１］イソブチレンを出発原料とし
て気相接触酸化によって得られたメタクリル酸を抽出お
よび蒸留によって精製し、純度９９．２％、色数がＡＰ
ＨＡ６３のメタクリル酸含有物を得た。このメタクリル
酸含有物１００ｇに重合禁止剤としてフェノチアジン
０．０５ｇを添加し、それにエチレンジアミン０．０５
ｇを添加して１００℃で２時間処理したものを１０mmHg
の減圧下で単蒸留した。得られたメタクリル酸に重合禁
止剤としてハイドロキノン０．０２ｇを添加し、これに
エタンジチオール０．３０ｇを添加して１００℃で２時
間処理したものを１０mmHgの減圧下で単蒸留して精製メ
タクリル酸を得た。このときのメタクリル酸の回収率は
９７％で、精製メタクリル酸の色数はＡＰＨＡ５であっ
た。Example 1 Methacrylic acid obtained by gas-phase catalytic oxidation using isobutylene as a starting material was purified by extraction and distillation to a purity of 99.2% and a color number of AP.
A methacrylic acid-containing material of HA63 was obtained. To 100 g of the methacrylic acid-containing material, 0.05 g of phenothiazine was added as a polymerization inhibitor, and 0.05 g of ethylenediamine was added thereto.
g at 10 ° C and treated at 100 ° C for 2 hours.
Under reduced pressure. To the obtained methacrylic acid was added 0.02 g of hydroquinone as a polymerization inhibitor, and 0.30 g of ethanedithiol was added thereto. The mixture was treated at 100 ° C. for 2 hours, and purified by simple distillation under reduced pressure of 10 mmHg. I got At this time, the recovery of methacrylic acid was 97%, and the color number of the purified methacrylic acid was APHA5.
【００２０】［実施例２］実施例１でエチレンジアミン
０．０５ｇの代わりに、Ｎ，Ｎ’−ジフェニルエチレン
ジアミン０．１０ｇを使用した以外は実施例１と同じ条
件で処理を行った。このときのメタクリル酸の回収率は
９７％で、精製メタクリル酸の色数はＡＰＨＡ６であっ
た。Example 2 A treatment was performed under the same conditions as in Example 1 except that 0.10 g of N, N'-diphenylethylenediamine was used instead of 0.05 g of ethylenediamine. At this time, the recovery of methacrylic acid was 97%, and the color number of purified methacrylic acid was APHA6.
【００２１】［実施例３］実施例１でエチレンジアミン
０．０５ｇの代わりに、ヒドラジン０．０３ｇおよび
Ｎ，Ｎ’−ジフェニルエチレンジアミン０．０５ｇを使
用した以外は実施例１と同じ条件で処理を行った。この
ときのメタクリル酸の回収率は９６．８％で、精製メタ
クリル酸の色数はＡＰＨＡ５であった。Example 3 A treatment was carried out under the same conditions as in Example 1 except that 0.03 g of hydrazine and 0.05 g of N, N'-diphenylethylenediamine were used instead of 0.05 g of ethylenediamine. Was. At this time, the recovery of methacrylic acid was 96.8%, and the color number of purified methacrylic acid was APHA5.
【００２２】［実施例４］イソブチレンを出発原料とし
て気相接触酸化によって得られたメタクリル酸を抽出お
よび蒸留によって精製し、純度９９．２％、色数がＡＰ
ＨＡ６３のメタクリル酸含有物を得た。このメタクリル
酸含有物１００ｇに重合禁止剤としてフェノチアジン
０．０５ｇを添加し、それにエタンジチオール０．３０
ｇを添加して１００℃で２時間処理したものを１０mmHg
の減圧下で単蒸留した。得られたメタクリル酸に重合禁
止剤としてハイドロキノン０．０２ｇを添加し、これに
エチレンジアミン０．０５ｇを添加して１００℃で２時
間処理したものを１０mmHgの減圧下で単蒸留して精製メ
タクリル酸を得た。このときのメタクリル酸の回収率は
９７％で、精製メタクリル酸の色数はＡＰＨＡ５であっ
た。Example 4 Methacrylic acid obtained by gas-phase catalytic oxidation using isobutylene as a starting material was purified by extraction and distillation to a purity of 99.2% and a color number of AP.
A methacrylic acid-containing material of HA63 was obtained. To 100 g of the methacrylic acid-containing material, 0.05 g of phenothiazine was added as a polymerization inhibitor, and 0.3 g of ethanedithiol was added thereto.
g at 10 ° C and treated at 100 ° C for 2 hours.
Under reduced pressure. To the obtained methacrylic acid, 0.02 g of hydroquinone was added as a polymerization inhibitor, and 0.05 g of ethylenediamine was added thereto, and the mixture was treated at 100 ° C. for 2 hours. The purified methacrylic acid was subjected to simple distillation under reduced pressure of 10 mmHg to obtain purified methacrylic acid. Obtained. At this time, the recovery of methacrylic acid was 97%, and the color number of the purified methacrylic acid was APHA5.
【００２３】［実施例５］イソブチレンを出発原料とし
て気相接触酸化によって得られたメタクリル酸を抽出お
よび蒸留によって精製し、純度９９．２％、色数がＡＰ
ＨＡ６３のメタクリル酸含有物を得た。このメタクリル
酸含有物１００ｇに重合禁止剤としてフェノチアジン
０．０５ｇを添加し、それにエチレンジアミン０．０５
ｇを添加して１００℃で２時間処理したものを１０mmHg
の減圧下で単蒸留した。得られたメタクリル酸に重合禁
止剤としてハイドロキノン０．０２ｇを添加し、これに
エタンジチオール０．１３ｇおよび強酸性イオン交換樹
脂アンバーリスト１５Ｅ（ロームアンドハース社製）
２．５ｇを添加して１００℃で１時間処理したものを１
０mmHgの減圧下で単蒸留して精製メタクリル酸を得た。
このときのメタクリル酸の回収率は９７％で、精製メタ
クリル酸の色数はＡＰＨＡ３であった。Example 5 Methacrylic acid obtained by gas-phase catalytic oxidation using isobutylene as a starting material was purified by extraction and distillation to a purity of 99.2% and a color number of AP.
A methacrylic acid-containing material of HA63 was obtained. To 100 g of the methacrylic acid-containing material, 0.05 g of phenothiazine was added as a polymerization inhibitor, and 0.05 g of ethylenediamine was added thereto.
g at 10 ° C and treated at 100 ° C for 2 hours.
Under reduced pressure. To the obtained methacrylic acid was added 0.02 g of hydroquinone as a polymerization inhibitor, and 0.13 g of ethanedithiol and Amberlyst 15E, a strongly acidic ion exchange resin (manufactured by Rohm and Haas Co.) were added thereto.
After adding 2.5 g and treating at 100 ° C. for 1 hour, 1
Simple distillation was performed under reduced pressure of 0 mmHg to obtain purified methacrylic acid.
At this time, the recovery of methacrylic acid was 97%, and the color number of the purified methacrylic acid was APHA3.
【００２４】［実施例６］実施例５でエチレンジアミン
０．０５ｇの代わりに、Ｎ，Ｎ’−ジフェニルエチレン
ジアミン０．１０ｇを使用した以外は実施例５と同じ条
件で処理を行った。このときのメタクリル酸の回収率は
９７％で、精製メタクリル酸の色数はＡＰＨＡ４であっ
た。Example 6 A treatment was performed under the same conditions as in Example 5 except that 0.10 g of N, N'-diphenylethylenediamine was used instead of 0.05 g of ethylenediamine. At this time, the recovery of methacrylic acid was 97%, and the color number of the purified methacrylic acid was APHA4.
【００２５】［実施例７］実施例５でエチレンジアミン
０．０５ｇの代わりに、ヒドラジン０．０３ｇおよび
Ｎ，Ｎ’−ジフェニルエチレンジアミン０．０５ｇを使
用した以外は実施例５と同じ条件で処理を行った。この
ときのメタクリル酸の回収率は９６．８％で、精製メタ
クリル酸の色数はＡＰＨＡ５であった。Example 7 The procedure of Example 5 was repeated, except that 0.05 g of ethylenediamine was replaced by 0.03 g of hydrazine and 0.05 g of N, N'-diphenylethylenediamine. Was. At this time, the recovery of methacrylic acid was 96.8%, and the color number of purified methacrylic acid was APHA5.
【００２６】［実施例８］イソブチレンを出発原料とし
て気相接触酸化によって得られたメタクリル酸を抽出お
よび蒸留によって精製し、純度９９．２％、色数がＡＰ
ＨＡ６３のメタクリル酸含有物を得た。このメタクリル
酸含有物１００ｇに重合禁止剤としてフェノチアジン
０．０５ｇを添加し、それにエタンジチオール０．１３
ｇおよび強酸性イオン交換樹脂アンバーリスト１５Ｅ
（ロームアンドハース社製）２．５ｇを添加して１００
℃で１時間処理したものを１０mmHgの減圧下で単蒸留し
た。得られたメタクリル酸に重合禁止剤としてハイドロ
キノン０．０２ｇを添加し、それにエチレンジアミン
０．０５ｇを添加して１００℃で２時間処理したものを
１０mmHgの減圧下で単蒸留して精製メタクリル酸を得
た。このときのメタクリル酸の回収率は９７％で、精製
メタクリル酸の色数はＡＰＨＡ３であった。Example 8 Methacrylic acid obtained by gas-phase catalytic oxidation using isobutylene as a starting material was purified by extraction and distillation to a purity of 99.2% and a color number of AP.
A methacrylic acid-containing material of HA63 was obtained. To 100 g of the methacrylic acid-containing material, 0.05 g of phenothiazine was added as a polymerization inhibitor, and 0.13 of ethanedithiol was added thereto.
g and strongly acidic ion exchange resin Amberlyst 15E
(Rohm and Haas) 2.5 g and add 100
The product treated at 1 ° C. for 1 hour was subjected to simple distillation under reduced pressure of 10 mmHg. To the obtained methacrylic acid, 0.02 g of hydroquinone as a polymerization inhibitor was added, and 0.05 g of ethylenediamine was added thereto, and the mixture was treated at 100 ° C. for 2 hours, and subjected to simple distillation under reduced pressure of 10 mmHg to obtain purified methacrylic acid. Was. At this time, the recovery of methacrylic acid was 97%, and the color number of the purified methacrylic acid was APHA3.
【００２７】［実施例９］実施例５でエチレンジアミン
０．０５ｇの代わりに、アニリン０．１０ｇを使用した
以外は実施例５と同じ条件で処理を行った。このときの
メタクリル酸の回収率は９７％で、精製メタクリル酸の
色数はＡＰＨＡ５であった。Example 9 A treatment was performed under the same conditions as in Example 5, except that 0.10 g of aniline was used instead of 0.05 g of ethylenediamine. At this time, the recovery of methacrylic acid was 97%, and the color number of the purified methacrylic acid was APHA5.
【００２８】［実施例１０］実施例５でエチレンジアミ
ン０．０５ｇの代わりに、エタノールアミン０．１０ｇ
を使用した以外は実施例５と同じ条件で処理を行った。
このときのメタクリル酸の回収率は９７％で、精製メタ
クリル酸の色数はＡＰＨＡ５であった。Example 10 Instead of 0.05 g of ethylenediamine in Example 5, 0.10 g of ethanolamine was used.
The processing was carried out under the same conditions as in Example 5 except that was used.
At this time, the recovery of methacrylic acid was 97%, and the color number of the purified methacrylic acid was APHA5.
【００２９】［実施例１１〜１７］実施例５でエタンジ
チオール０．１３ｇの代わりに、表１の各種メルカプト
基含有化合物を使用した以外は実施例５と同じ条件で処
理を行った。その結果を表１に示す。なお、表中の添加
量はメルカプト基含有化合物の添加量を示す。Examples 11 to 17 The procedure of Example 5 was repeated, except that various mercapto group-containing compounds shown in Table 1 were used instead of 0.13 g of ethanedithiol. Table 1 shows the results. In addition, the addition amount in a table | surface shows the addition amount of a mercapto group containing compound.
【００３０】[0030]
【表１】 [Table 1]
【００３１】［実施例１８］実施例５で強酸性イオン交
換樹脂アンバーリスト１５Ｅ（ロームアンドハース社
製）２．５ｇの代わりに、硫酸１．５ｇを使用した以外
は実施例５と同じ条件で処理を行った。このときのメタ
クリル酸の回収率は９６．８％で、精製メタクリル酸の
色数はＡＰＨＡ６であった。Example 18 The procedure of Example 5 was repeated, except that 1.5 g of sulfuric acid was used instead of 2.5 g of the strongly acidic ion exchange resin Amberlyst 15E (manufactured by Rohm and Haas). Processing was performed. At this time, the recovery of methacrylic acid was 96.8%, and the color number of purified methacrylic acid was APHA6.
【００３２】［実施例１９］実施例５で強酸性イオン交
換樹脂アンバーリスト１５Ｅ（ロームアンドハース社
製）２．５ｇの代わりに、ｐ−トルエンスルホン酸１．
５ｇを使用した以外は実施例５と同じ条件で処理を行っ
た。このときのメタクリル酸の回収率は９６．９％で、
精製メタクリル酸の色数はＡＰＨＡ６であった。Example 19 In Example 5, p-toluenesulfonic acid was replaced with 2.5 g of the strongly acidic ion exchange resin Amberlyst 15E (manufactured by Rohm and Haas).
Processing was performed under the same conditions as in Example 5 except that 5 g was used. The recovery of methacrylic acid at this time was 96.9%,
The color number of the purified methacrylic acid was APHA6.
【００３３】［実施例２０］実施例５において、エチレ
ンジアミン処理済みのメタクリル酸含有物にトリグリコ
ールジメルカプタン０．１３ｇを添加したものを、８０
℃の恒温下にあるアンバーリスト１５Ｅ５ｇを充填した
ガラス製Ｕ字管に、空間速度０．２ｈｒ-1で通過させて
連続的に処理した。次いで処理液１００ｇを１０mmHgの
減圧下で単蒸留して精製メタクリル酸を得た。このとき
のメタクリル酸の回収率は９７％で、精製メタクリル酸
の色数はＡＰＨＡ４であった。Example 20 The procedure of Example 5 was repeated except that 0.13 g of triglycol dimercaptan was added to the methacrylic acid-containing material treated with ethylenediamine.
A glass U-shaped tube filled with 15 g of Amberlyst 15E at a constant temperature of ° C. was passed through at a space velocity of 0.2 hr -1 for continuous treatment. Subsequently, 100 g of the treatment liquid was subjected to simple distillation under reduced pressure of 10 mmHg to obtain purified methacrylic acid. At this time, the recovery of methacrylic acid was 97%, and the color number of the purified methacrylic acid was APHA4.
【００３４】［比較例１］実施例１において、エタンジ
チオールによる処理を行わず、エチレンジアミンの使用
量を０．８ｇにして処理を行った。このときのメタクリ
ル酸の回収率は８５％と非常に低く、精製メタクリル酸
の色数はＡＰＨＡ１０と高い値であった。[Comparative Example 1] In Example 1, the treatment was carried out without using ethanedithiol and using 0.8 g of ethylenediamine. At this time, the recovery of methacrylic acid was as very low as 85%, and the color number of purified methacrylic acid was as high as APHA10.
【００３５】［比較例２］実施例１において、エチレン
ジアミンによる処理を行わず、エタンジチオールの使用
量は０．３０ｇのままで処理を行った。このときのメタ
クリル酸の回収率は９２％と低く、精製メタクリル酸の
色数はＡＰＨＡ１２と高い値であった。[Comparative Example 2] In Example 1, the treatment with ethylenediamine was not carried out, and the treatment was carried out with the amount of ethanedithiol used remaining at 0.30 g. At this time, the recovery of methacrylic acid was as low as 92%, and the color number of purified methacrylic acid was as high as APHA12.
【００３６】［比較例３］実施例５において、エチレン
ジアミンおよびエタンジチオールによる処理を行わず、
強酸性イオン交換樹脂アンバーリスト１５Ｅ（ロームア
ンドハース社製）２．５ｇだけを添加して１００℃で１
時間処理したものを１０mmHgの減圧下で単蒸留して精製
メタクリル酸を得た。このときのメタクリル酸の回収率
は９７％で良好であったが、精製メタクリル酸の色数は
ＡＰＨＡ２８と非常に高い値であった。[Comparative Example 3] In Example 5, no treatment with ethylenediamine and ethanedithiol was performed.
Add only 2.5 g of strongly acidic ion exchange resin Amberlyst 15E (manufactured by Rohm and Haas) and add 1 g at 100 ° C.
The treated product was subjected to simple distillation under reduced pressure of 10 mmHg to obtain purified methacrylic acid. At this time, the recovery rate of methacrylic acid was 97%, which was good, but the color number of purified methacrylic acid was APHA28, which was a very high value.
【００３７】［比較例４］実施例５において、エチレン
ジアミンの使用量を０．８ｇにして処理したものを１０
mmHgの減圧下で単蒸留した。得られたメタクリル酸に重
合禁止剤としてハイドロキノン０．０２ｇを添加し、そ
れに強酸性イオン交換樹脂アンバーリスト１５Ｅ（ロー
ムアンドハース社製）２．５ｇを添加して１００℃で１
時間処理したものを１０mmHgの減圧下で単蒸留して精製
メタクリル酸を得た。すなわち、エタンジチオールによ
る処理を行わなかった。このときのメタクリル酸の回収
率は８５％と低く、精製メタクリル酸の色数はＡＰＨＡ
１０と高い値であった。[Comparative Example 4] The same process as in Example 5 except that the amount of ethylenediamine used was 0.8 g,
Simple distillation was performed under reduced pressure of mmHg. To the obtained methacrylic acid, 0.02 g of hydroquinone was added as a polymerization inhibitor, and 2.5 g of strongly acidic ion exchange resin Amberlyst 15E (manufactured by Rohm and Haas Co.) was added thereto.
The treated product was subjected to simple distillation under reduced pressure of 10 mmHg to obtain purified methacrylic acid. That is, the treatment with ethanedithiol was not performed. At this time, the recovery of methacrylic acid was as low as 85%, and the color number of purified methacrylic acid was APHA.
It was a high value of 10.
【００３８】［比較例５］実施例５において、エチレン
ジアミンによる処理を行わず、それ以外は実施例５と同
じ条件で処理を行った。このときのメタクリル酸の回収
率は９６％と比較的良好であったが、精製メタクリル酸
の色数はＡＰＨＡ１０と高い値であった。[Comparative Example 5] In Example 5, the treatment was carried out under the same conditions as in Example 5, except that the treatment with ethylenediamine was not carried out. At this time, the recovery of methacrylic acid was relatively good at 96%, but the number of colors of the purified methacrylic acid was as high as APHA10.
【００３９】[0039]
【発明の効果】本発明によれば、気相接触酸化反応で得
られるメタクリル酸含有物から高い回収率で着色の少な
い高品質のメタクリル酸を得ることができる。According to the present invention, it is possible to obtain high-quality methacrylic acid with little coloration at a high recovery rate from a methacrylic acid-containing substance obtained by a gas phase catalytic oxidation reaction.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 宮脇 佳宏 広島県大竹市御幸町20番１号 三菱レイヨ ン株式会社大竹事業所内 (72)発明者 小林 義明 広島県大竹市御幸町20番１号 三菱レイヨ ン株式会社大竹事業所内 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Yoshihiro Miyawaki 20-1, Miyukicho, Otake City, Hiroshima Prefecture Inside Mitsubishi Rayon Co., Ltd. Otake Office (72) Inventor Yoshiaki Kobayashi 20-1, Miyukicho, Otake City, Hiroshima Prefecture Mitsubishi Rayon Co., Ltd.
Claims (2)
含有物を第１級および／または第２級のアミノ基含有化
合物とメルカプト基含有化合物で処理することを特徴と
するメタクリル酸の精製法。A method for purifying methacrylic acid, comprising treating a methacrylic acid-containing substance obtained by a gas phase catalytic oxidation reaction with a primary and / or secondary amino group-containing compound and a mercapto group-containing compound. .
は第２級のアミノ基含有化合物、メルカプト基含有化合
物およびスルホン酸基含有化合物で処理することを特徴
とする請求項１記載のメタクリル酸の精製法。2. The methacrylic acid according to claim 1, wherein the methacrylic acid-containing material is treated with a primary and / or secondary amino group-containing compound, a mercapto group-containing compound and a sulfonic acid group-containing compound. Purification method.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP24349496A JP3222068B2 (en) | 1996-09-13 | 1996-09-13 | Purification method of methacrylic acid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP24349496A JP3222068B2 (en) | 1996-09-13 | 1996-09-13 | Purification method of methacrylic acid |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH1087551A true JPH1087551A (en) | 1998-04-07 |
| JP3222068B2 JP3222068B2 (en) | 2001-10-22 |
Family
ID=17104732
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP24349496A Expired - Lifetime JP3222068B2 (en) | 1996-09-13 | 1996-09-13 | Purification method of methacrylic acid |
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| Country | Link |
|---|---|
| JP (1) | JP3222068B2 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2003059862A1 (en) * | 2002-01-15 | 2003-07-24 | Mitsubishi Chemical Corporation | Process for producing high-purity (meth)acrylic acid |
| WO2005051883A1 (en) * | 2003-11-28 | 2005-06-09 | Mitsubishi Chemical Corporation | Method of purifying (meth)acrylic acid |
| JP2005179352A (en) * | 2003-11-28 | 2005-07-07 | Mitsubishi Chemicals Corp | (Meth) acrylic acid purification method |
| JP2015515963A (en) * | 2012-05-03 | 2015-06-04 | エボニック インダストリーズ アクチエンゲゼルシャフトＥｖｏｎｉｋ Ｉｎｄｕｓｔｒｉｅｓ ＡＧ | Method for producing high purity, non-yellowing (meth) acrylic acid |
-
1996
- 1996-09-13 JP JP24349496A patent/JP3222068B2/en not_active Expired - Lifetime
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2003059862A1 (en) * | 2002-01-15 | 2003-07-24 | Mitsubishi Chemical Corporation | Process for producing high-purity (meth)acrylic acid |
| WO2005051883A1 (en) * | 2003-11-28 | 2005-06-09 | Mitsubishi Chemical Corporation | Method of purifying (meth)acrylic acid |
| JP2005179352A (en) * | 2003-11-28 | 2005-07-07 | Mitsubishi Chemicals Corp | (Meth) acrylic acid purification method |
| JP2015515963A (en) * | 2012-05-03 | 2015-06-04 | エボニック インダストリーズ アクチエンゲゼルシャフトＥｖｏｎｉｋ Ｉｎｄｕｓｔｒｉｅｓ ＡＧ | Method for producing high purity, non-yellowing (meth) acrylic acid |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3222068B2 (en) | 2001-10-22 |
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