JPH02279655A - Production of acrylic ester - Google Patents
Production of acrylic esterInfo
- Publication number
- JPH02279655A JPH02279655A JP10016889A JP10016889A JPH02279655A JP H02279655 A JPH02279655 A JP H02279655A JP 10016889 A JP10016889 A JP 10016889A JP 10016889 A JP10016889 A JP 10016889A JP H02279655 A JPH02279655 A JP H02279655A
- Authority
- JP
- Japan
- Prior art keywords
- acrylic acid
- alcohol
- separation column
- liquid
- reactor
- 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
- -1 acrylic ester Chemical class 0.000 title claims description 16
- 238000004519 manufacturing process Methods 0.000 title claims description 10
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 88
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims abstract description 86
- 238000006243 chemical reaction Methods 0.000 claims abstract description 43
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000003054 catalyst Substances 0.000 claims abstract description 20
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000003729 cation exchange resin Substances 0.000 claims abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 230000002378 acidificating effect Effects 0.000 claims abstract description 10
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 10
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 claims abstract description 7
- 125000002723 alicyclic group Chemical group 0.000 claims abstract description 7
- 238000005886 esterification reaction Methods 0.000 claims description 47
- 239000007788 liquid Substances 0.000 claims description 44
- 238000000926 separation method Methods 0.000 claims description 37
- 230000032050 esterification Effects 0.000 claims description 23
- 150000002148 esters Chemical class 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 5
- 239000012530 fluid Substances 0.000 claims description 4
- 125000005396 acrylic acid ester group Chemical group 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- 239000011347 resin Substances 0.000 abstract description 14
- 229920005989 resin Polymers 0.000 abstract description 14
- 239000000463 material Substances 0.000 abstract description 3
- 229920002125 Sokalan® Polymers 0.000 abstract description 2
- 239000000126 substance Substances 0.000 abstract description 2
- JHPBZFOKBAGZBL-UHFFFAOYSA-N (3-hydroxy-2,2,4-trimethylpentyl) 2-methylprop-2-enoate Chemical compound CC(C)C(O)C(C)(C)COC(=O)C(C)=C JHPBZFOKBAGZBL-UHFFFAOYSA-N 0.000 abstract 1
- 230000001105 regulatory effect Effects 0.000 abstract 1
- 239000000203 mixture Substances 0.000 description 17
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 238000006116 polymerization reaction Methods 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- 150000007513 acids Chemical class 0.000 description 5
- 238000009835 boiling Methods 0.000 description 5
- 239000003112 inhibitor Substances 0.000 description 5
- 229910052500 inorganic mineral Inorganic materials 0.000 description 5
- 239000011707 mineral Substances 0.000 description 5
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 239000008346 aqueous phase Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- LAQYHRQFABOIFD-UHFFFAOYSA-N 2-methoxyhydroquinone Chemical compound COC1=CC(O)=CC=C1O LAQYHRQFABOIFD-UHFFFAOYSA-N 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 229910001882 dioxygen Inorganic materials 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 description 1
- WJFKNYWRSNBZNX-UHFFFAOYSA-N 10H-phenothiazine Chemical compound C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-UHFFFAOYSA-N 0.000 description 1
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 1
- 235000006732 Torreya nucifera Nutrition 0.000 description 1
- 244000111306 Torreya nucifera Species 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000006757 chemical reactions by type Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 229950000688 phenothiazine Drugs 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野］
本発明はアクリル酸エステルの製造方法に関する。更に
詳しく述べると、アクリル酸と、炭素数１〜４の低級脂
肪族アルコールまたは脂環式アルコールとをエステル化
反応させることからなるアクリル酸エステルの製造方法
に関する。DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a method for producing acrylic esters. More specifically, the present invention relates to a method for producing an acrylic ester, which comprises esterifying acrylic acid and a lower aliphatic alcohol or alicyclic alcohol having 1 to 4 carbon atoms.
［従来の技術］
従来、アクリル酸エステルを連続的に製造するに際して
、アクリル酸とアルコールとを反応器にて硫酸、リン酸
等の鉱酸や強酸性陽イオン交換樹脂のエステル化触媒を
用いて反応させ、アクリル酸分離塔にて反応生成物を蒸
留して未反応のアクリル酸を主成分とする高沸点分と生
成アクリル酸エステル、未反応アルコールおよび生成水
を主成分とする低沸点分とに分離し、更に、前者からは
アクリル酸を適宜精製処理して反応原料とともに循環再
使用する一方、後者からはアクリル酸エステルを分離・
精製するとともに未反応アルコールを回収して反応器へ
循環する操作が行なわれている（特公昭６３−２０４１
５号、特開昭５８−１５９４４２号各公報）０
硫酸、リン酸等の鉱酸をエステル化触媒として用いる方
法（特開昭５８−２６８４３号）では、触媒を連続的に
反応器に投入するため触媒の経時劣化がなく反応系内の
状態を一定に保つ利点があるが、腐食性の高い鉱酸を用
いるので耐食性の機器材質を選定せざるをえず、機器が
高価になると同時に、廃液中に含まれる鉱酸を無害化す
る廃液処理も繁雑となる欠点を有する。[Prior art] Conventionally, when producing acrylic acid esters continuously, acrylic acid and alcohol are mixed in a reactor using mineral acids such as sulfuric acid or phosphoric acid or an esterification catalyst such as a strongly acidic cation exchange resin. The reaction product is distilled in an acrylic acid separation column to separate a high boiling point component mainly consisting of unreacted acrylic acid and a low boiling point component mainly consisting of the produced acrylic ester, unreacted alcohol and produced water. Furthermore, the acrylic acid from the former is appropriately purified and reused together with the reaction raw materials, while the acrylic ester is separated and reused from the latter.
In addition to purification, unreacted alcohol is recovered and recycled to the reactor (Special Publication No. 63-2041).
5, JP-A No. 58-159442) 0 In the method using mineral acids such as sulfuric acid and phosphoric acid as an esterification catalyst (JP-A No. 58-26843), the catalyst is continuously introduced into a reactor. This has the advantage of keeping the conditions within the reaction system constant without deteriorating the catalyst over time.However, since highly corrosive mineral acids are used, corrosion-resistant equipment materials must be selected, which makes the equipment expensive and waste liquid It also has the disadvantage that the waste liquid treatment to render the mineral acids contained therein harmless is complicated.
一方、強酸性陽イオン交換樹脂をエステル化触媒として
用いる方法（特公昭６３−２０４１５号、特開昭５８−
１５９４４２号各公報）０硫上述の鉱酸をエステル化触
［として用いる方法のような欠点は起こらない。しかし
、エステル化触媒として反応器に充填きれた強酸性陽イ
オン交換樹脂は長期にわたって交換きれることがなく、
連続運転に伴って経時的に樹脂の劣化が起こる。また、
エステル化反応後、反応生成物はアクリル酸分離塔にて
蒸留するが、該アクリル酸分離塔においては、高温にな
ると重合物の生成が顕著になったり急激な重合の危険が
生じるので許容できる塔底温度の上限を規定してこの規
定温度以下に納まるように完全にアクリル酸を分離せず
にアクリル酸エステルを含んだ状態で塔底液を抜き出し
、適宜精製処理して反応原料とともに循環再使用するこ
とが行なわれている。On the other hand, a method using a strongly acidic cation exchange resin as an esterification catalyst (Japanese Patent Publication No. 63-20415, Japanese Unexamined Patent Application Publication No. 1988-58-
No. 159442) The drawbacks of the above-mentioned methods using mineral acids as esterification catalysts do not occur. However, the strongly acidic cation exchange resin filled into the reactor as an esterification catalyst cannot be replaced for a long time.
Continuous operation causes resin deterioration over time. Also,
After the esterification reaction, the reaction product is distilled in an acrylic acid separation column. However, in the acrylic acid separation column, at high temperatures, the formation of polymers becomes noticeable and there is a risk of rapid polymerization, so the column is not suitable for use. The upper limit of the bottom temperature is specified, and the bottom liquid is extracted while containing the acrylic ester without completely separating the acrylic acid so that the upper limit of the bottom temperature remains below this specified temperature.The bottom liquid is then purified as appropriate and recycled together with the reaction raw materials for reuse. things are being done.
ところが、転化率の低下によって、アクリル酸エステル
収量を確保するためにはアクリル酸分離塔の塔底液中の
アクリル酸エステルの組成を低下させねばならず、アク
リル酸分離塔塔底温度が上昇してくる。その結果、重合
物の生成が増えて収率低下し、ついには規定した温度に
到達したところで運転を停止して触媒交換が行なわれる
。更には、アクリル酸分離塔の塔底液は反応器に循環さ
れるので塔底液組成が変化するのに伴って反応器入口で
の液組成も変化し、樹脂が！１１ｉｆ’Ｊまたは収縮を
起こし場合によっては割れが起こったりし、このことも
また樹脂寿命を短くする要因となっている。However, due to the decrease in conversion rate, the composition of acrylic ester in the bottom liquid of the acrylic acid separation tower must be lowered in order to ensure the acrylic ester yield, and the temperature at the bottom of the acrylic acid separation tower increases. It's coming. As a result, the production of polymers increases and the yield decreases, and when the specified temperature is finally reached, the operation is stopped and the catalyst is replaced. Furthermore, since the bottom liquid of the acrylic acid separation tower is circulated to the reactor, as the bottom liquid composition changes, the liquid composition at the reactor inlet also changes, and the resin! 11if'J or shrinkage may occur, and in some cases cracking may occur, which is also a factor in shortening the life of the resin.
［発明が解決しようとする課題］
本発明の目的はこのような従来法の欠点を改善すること
にある。即ち安価な機器材質を用い、廃液処理費用を削
減し、長期間の連続運転が可能になるように樹脂寿命を
維持するアクリル酸エステルの製造方法を提供すること
にある。[Problems to be Solved by the Invention] An object of the present invention is to improve the drawbacks of such conventional methods. That is, the object of the present invention is to provide a method for producing acrylic acid ester that uses inexpensive equipment materials, reduces waste liquid treatment costs, and maintains the resin life so as to enable long-term continuous operation.
［課題を解決するための手段］
本発明者等は鋭意検討の結果、アクリル酸と炭素数１〜
４の低級脂肪族アルコールまたは脂環式アルコールを強
酸性陽イオン交換樹脂を触媒としてエステル化反応させ
る際に、アクリル酸の転化率が常に一定になる様に反応
温度を調節しながらエステル化反応させることによっオ
、アクリル酸分離塔を安定した状態で運転でき、エステ
ル化反応語に循環する循環液の組成が安定し、反応器の
入口液組成も安定し、前記本発明の目的を達成できるこ
とを見出した。即ち本発明はアクリル酸と、炭素数１〜
４の低級脂肪族アルコールまたは脂環式アルコールとを
エステル化反応器に供給し、該反応器にて強酸性陽イオ
ン交換樹脂を触媒としてアクリル酸の転化率が常に一定
になる様に反応温度を調節しながらエステル化反応させ
、得られた反応生成物をアクリル酸分離塔に導いて、ア
クリル酸分離塔の塔頂からアクリル酸エステル、水およ
び未反応アルコールを留去させる一方、アクリル酸分離
塔の塔底から実質的に全量のアクリル酸を含む液を抜き
だして循環液としてエステル化反応器に循環させること
を特徴とするアクリル酸エステルの製造方法である。以
下に本発明を更に詳しく説明する。[Means for Solving the Problems] As a result of intensive studies, the present inventors found that acrylic acid and
When esterifying the lower aliphatic alcohol or alicyclic alcohol in step 4 using a strongly acidic cation exchange resin as a catalyst, the esterification reaction is carried out while adjusting the reaction temperature so that the conversion rate of acrylic acid is always constant. Particularly, the acrylic acid separation column can be operated in a stable state, the composition of the circulating liquid that circulates to the esterification reaction is stabilized, and the composition of the inlet liquid of the reactor is also stabilized, so that the above objects of the present invention can be achieved. I found out. That is, the present invention uses acrylic acid and
The lower aliphatic alcohol or alicyclic alcohol of No. 4 is supplied to an esterification reactor, and the reaction temperature is maintained in the reactor using a strongly acidic cation exchange resin as a catalyst so that the conversion rate of acrylic acid is always constant. The esterification reaction is carried out under control, and the resulting reaction product is led to an acrylic acid separation column, and the acrylic ester, water, and unreacted alcohol are distilled off from the top of the acrylic acid separation column. This is a method for producing an acrylic ester, characterized in that a liquid containing substantially the entire amount of acrylic acid is withdrawn from the bottom of the column and circulated as a circulating liquid to an esterification reactor. The present invention will be explained in more detail below.
本発明で使用するアクリル酸は粗製アクリル酸及び精製
アクリル酸のいずれも使用可能であり、エステル化反応
後、アクリル酸分離塔から回収される未反応アクリル酸
も循環再使用される。The acrylic acid used in the present invention can be either crude acrylic acid or purified acrylic acid, and unreacted acrylic acid recovered from the acrylic acid separation column after the esterification reaction is also recycled and reused.
炭素数１〜４の低級の脂肪族アルコールまたは脂環式ア
ルコールの具体例としてはメタノール。A specific example of the lower aliphatic alcohol or alicyclic alcohol having 1 to 4 carbon atoms is methanol.
エタノール、プロパツール、ブタノール等が挙げられ、
これらは直鎖状のものであっても分岐を有するものであ
っても良い。また、エステル化反応後、アクリル酸エス
テルを精製する過程で回収される未反応アルコールを循
環再使用してもよい。Examples include ethanol, propatool, butanol, etc.
These may be linear or branched. Further, after the esterification reaction, unreacted alcohol recovered during the process of purifying the acrylic ester may be recycled and reused.
本発明ではエステル化反応用の触媒として強酸性陽イオ
ン交換樹脂を用いる。多孔質またはゲルタイプの樹脂が
使用可能であるが多孔質タイプの樹脂が好適に用いられ
る。特に粗製アクリル酸を使用する場合には耐有機汚染
性に優れた多孔質タイプの樹脂を使用するのが好ましい
。多孔質の強酸性陽イオン交換樹脂としては架橋度２〜
１６％。In the present invention, a strongly acidic cation exchange resin is used as a catalyst for the esterification reaction. Although porous or gel type resins can be used, porous type resins are preferably used. Particularly when crude acrylic acid is used, it is preferable to use a porous type resin with excellent organic stain resistance. As a porous strongly acidic cation exchange resin, the degree of crosslinking is 2~
16%.
ポロシティ０． １〜１．０ｍｌ／ｇｏ 平均細孔径
１００〜６００人のものが好ましく使用でき、具体例と
してはＣ−２６Ｃ（デュオライト社製）。Porosity 0. 1 to 1.0 ml/go Those having an average pore diameter of 100 to 600 can be preferably used, and a specific example is C-26C (manufactured by Duolite).
ＰＫ−２０８，ＰＫ−２１６，ＰＫ−２２８（三菱化成
社製）、ＭＳＣ−１，８８（ダウ社製）。PK-208, PK-216, PK-228 (manufactured by Mitsubishi Chemical Corporation), MSC-1,88 (manufactured by Dow Corporation).
アンバーリスト−１６（ローム アンド ハース社製）
、５ＰＣ−１０８，３ＰＣ−１１２（バイエル社製）な
どが挙げられる。Amberlyst-16 (manufactured by Rohm and Haas)
, 5PC-108, 3PC-112 (manufactured by Bayer), and the like.
エステル化反応は反応器入口液、出口液の組成を分析す
るなどしてアクリル酸の転化率を監視し、該転化率が常
に一定になる様に反応温度を調節しながら行なわれる。The esterification reaction is carried out by monitoring the conversion rate of acrylic acid by analyzing the composition of the reactor inlet liquid and outlet liquid, and adjusting the reaction temperature so that the conversion rate is always constant.
好ましくは運転を開始して定常状態に達したときのアク
リル酸の転化率を基準として、±５％以内、より好まし
くは±３％以内の範囲に納まる転化率とする。また、高
い選択率を得るためにアクリル酸の転化率は１５〜５０
％の範囲であるのが好ましい。この場合、反応温度を調
節しても、転化率は一定であって選択率も高いために反
応器出口の液組成があまり変化せずに安定した運転条件
が保たれる。Preferably, the conversion rate is within ±5%, more preferably within ±3%, based on the conversion rate of acrylic acid when a steady state is reached after starting the operation. In addition, in order to obtain high selectivity, the conversion rate of acrylic acid is 15 to 50.
% range is preferred. In this case, even if the reaction temperature is adjusted, the conversion rate remains constant and the selectivity is high, so that the liquid composition at the reactor outlet does not change much and stable operating conditions are maintained.
運転開始から触媒を寿命として交換するまでの反応温度
範囲は目的とするエステル化反応によって異なるが、通
常５０〜１１０℃である。また、エステル化反応は液相
にて行なわへ 反応型式としては流動床、固定床いずれ
でもよく、複数の反応器を順次切り換えて触媒交換しつ
つ連続操業することも可能である。The reaction temperature range from the start of operation until the catalyst reaches the end of its service life and is replaced varies depending on the intended esterification reaction, but is usually 50 to 110°C. Furthermore, the esterification reaction is carried out in the liquid phase.The reaction type may be either a fluidized bed or a fixed bed, and it is also possible to operate continuously by sequentially switching between multiple reactors and replacing the catalyst.
エステル化反応においては、通常用いられているような
重合禁止剤を使用することができる。使用きれる重合禁
止剤としては例えばハイドロキノン、メトキシハイドロ
キノン、フェノチアジン。In the esterification reaction, commonly used polymerization inhibitors can be used. Examples of polymerization inhibitors that can be used include hydroquinone, methoxyhydroquinone, and phenothiazine.
ヒドロキシルアミン、フェニレンジアミンなどが挙げら
れる。なお、反応を分子状酸素の存在下で行うと重合禁
止剤の効果を更に高めることができる。Examples include hydroxylamine and phenylenediamine. Note that the effect of the polymerization inhibitor can be further enhanced if the reaction is carried out in the presence of molecular oxygen.
このようにして得られたエステル化反応生成物はアクリ
ル酸分離塔に導いて、アクリル酸分離塔の塔頂からアク
リル酸エステル、水および未反応アルコールを留去させ
る。一方、アクリル酸分離塔の塔底から実質的に全量の
アクリル酸を含む液を抜きだして循環液としてエステル
化反応器に循環させる。The esterification reaction product thus obtained is introduced into an acrylic acid separation column, and the acrylic ester, water, and unreacted alcohol are distilled off from the top of the acrylic acid separation column. On the other hand, a liquid containing substantially the entire amount of acrylic acid is extracted from the bottom of the acrylic acid separation column and is circulated to the esterification reactor as a circulating liquid.
アクリル酸分離塔においては、前述したとおや、塔底温
度が規定温度以下に納まるように完全にアクリル酸を分
離せずにアクリル酸エステルを含んだ状態で塔底液を抜
き出す。次いで、塔底液は循環液としてエステル化反応
器に循環するのであるが、エステル化反応を進めるうえ
では該循環液組成はアクリル酸エステルおよび水を減ら
しアクリル酸を増やす方が有利になる。従ってアクリル
酸分離塔から排出される塔底液は、目的とするエステル
、反応条件によっても異なるが、アクリル酸の濃度が５
０重量％以上、より好ましくは６０重量％以上、また水
の濃度が５重量％以下、より好ましくは２重量％以下で
あるのが望ましい。In the acrylic acid separation column, as mentioned above, the bottom liquid is extracted in a state containing acrylic ester without completely separating acrylic acid so that the bottom temperature is below a specified temperature. Next, the bottom liquid is circulated to the esterification reactor as a circulating liquid, and in order to proceed with the esterification reaction, it is advantageous to reduce the acrylic ester and water and increase the acrylic acid in the circulating liquid composition. Therefore, the bottom liquid discharged from the acrylic acid separation tower has an acrylic acid concentration of 5%, although it varies depending on the target ester and reaction conditions.
It is desirable that the concentration of water is 0% by weight or more, more preferably 60% by weight or more, and the concentration of water is 5% by weight or less, more preferably 2% by weight or less.
アクリル酸分離塔においてもエステル化反応に関して例
示したと同様の重合禁止剤を用いる。分子状酸素の存在
下で行うと重合禁止剤の効果を更に高めることができる
ことも同様である。The same polymerization inhibitor as exemplified for the esterification reaction is also used in the acrylic acid separation column. Similarly, the effect of the polymerization inhibitor can be further enhanced if it is carried out in the presence of molecular oxygen.
アクリル酸分離塔塔底液は循環液としてエステル化反応
器に循環されるが、その一部を薄層蒸発器に導いて重合
物などの高沸点不純物を除去するなど適宜精製処理した
後エステル化反応器に循環させるのが好ましい。エステ
ル化反応器に循環させる循環液量は多すぎても少なすぎ
てもエステル化反応に必要な樹脂量が増加するので好ま
しくない。循環液量は新規供給量に対して１〜５倍量が
適切である。The bottom liquid of the acrylic acid separation tower is circulated as a circulation liquid to the esterification reactor, but a part of it is led to a thin-layer evaporator to remove high-boiling point impurities such as polymers, and is then subjected to appropriate purification treatment before esterification. Preferably, it is recycled to the reactor. If the amount of circulating liquid circulated to the esterification reactor is too large or too small, the amount of resin required for the esterification reaction will increase, which is not preferable. The appropriate amount of circulating fluid is 1 to 5 times the new supply amount.
次に、本発明の好適な実施態様を例示する第１図に従フ
て更に詳しく説明する。Next, a preferred embodiment of the present invention will be explained in more detail with reference to FIG. 1, which illustrates the preferred embodiment.
ライン１よりアクリル酸、ライン２よりアルコ−ル、ラ
イン７より循環液を供給し、これら混合物を多孔質の強
酸性陽イオン交換樹脂を充填したエステル化反応器１０
１に供給する。エステル化反応器１０１において、反応
熱入口３および出口４の液を分析してアクリル酸の転化
率を監視し、該転化率が常に一定になる様に反応温度を
調節しながらエステル化反応を行う。Acrylic acid is supplied from line 1, alcohol is supplied from line 2, and circulating liquid is supplied from line 7, and these mixtures are fed into an esterification reactor 10 filled with a porous strongly acidic cation exchange resin.
Supply to 1. In the esterification reactor 101, the conversion rate of acrylic acid is monitored by analyzing the liquid at the reaction heat inlet 3 and outlet 4, and the esterification reaction is carried out while adjusting the reaction temperature so that the conversion rate is always constant. .
生成エステル、未反応アクリル酸、未反応アルコールお
よび生成水からなるエステル化反応生成物をエステル化
反応器１０１の出口４から抜き出し、アクリル酸分離塔
１０２に供給して蒸留する。An esterification reaction product consisting of the produced ester, unreacted acrylic acid, unreacted alcohol, and produced water is extracted from the outlet 4 of the esterification reactor 101, supplied to the acrylic acid separation column 102, and distilled.
アクリル酸分離塔１０２の塔底から実質的に全量の未反
応アクリル酸を含む液を抜き出し、循環液としてライン
７よりエステル化反応器１０１へ循環する。ここでアク
リル酸分離塔塔底液の一部を薄層蒸発器１０３に供給し
て重合物などの寓沸点不純物をライン６より糸外に除去
し、留出物を残りのアクリル酸分離塔塔底液とともに循
環する。A liquid containing substantially the entire amount of unreacted acrylic acid is extracted from the bottom of the acrylic acid separation column 102 and circulated to the esterification reactor 101 via line 7 as a circulating liquid. Here, a part of the bottom liquid of the acrylic acid separation column is supplied to the thin layer evaporator 103 to remove low boiling point impurities such as polymers from the line 6, and the distillate is transferred to the bottom of the acrylic acid separation column. It circulates with the liquid.
また、アクリル酸分離塔１０２の塔頂からは生成エステ
ル、未反応アルコールおよび生成水が留出し、受器１０
４にてエステル相と水相とに二相分離する。一部は還流
液としてアクリル酸分離塔１０２に循環する。ライン８
よりエステル相を抜き出し、図外の精製工程に送ってア
クリル酸エステル製品を得る。一方、ライン９より水相
を抜き出し、図外のアルコール回収工程または廃水処理
工程に送る。Further, produced ester, unreacted alcohol, and produced water are distilled from the top of the acrylic acid separation column 102, and the receiver 10
In step 4, two phases are separated into an ester phase and an aqueous phase. A portion is recycled to the acrylic acid separation column 102 as a reflux liquid. line 8
The ester phase is extracted and sent to a purification process not shown in the figure to obtain an acrylic ester product. On the other hand, the aqueous phase is extracted from line 9 and sent to an alcohol recovery process or a wastewater treatment process (not shown).
本発明においては、エステル化反応はアクリル酸の転化
率が常に一定になる様に行なわれるので、エステル化反
応生成物の組成は安定しており、アクリル酸分離塔１０
２の運転条件も安定して行なわれる。即ち、アクリル酸
分離塔１０２の操作温度は一定し、塔底から抜き出され
、反応器に循環される循環液の組成も一定している。In the present invention, the esterification reaction is carried out so that the conversion rate of acrylic acid is always constant, so the composition of the esterification reaction product is stable, and the acrylic acid separation column 10
The second operating condition is also stable. That is, the operating temperature of the acrylic acid separation column 102 is constant, and the composition of the circulating liquid extracted from the bottom of the column and circulated to the reactor is also constant.
［実施例］ 更に、本発明を以下の実施例によって詳しく説明する。[Example] Further, the present invention will be explained in detail by the following examples.
なお、各実施例は第１図の装置を用いて行ない、アクリ
ル酸の転化率は反応器入口液、出口液のアクリル酸濃度
を分析して下記式に従って計算した。Each Example was carried out using the apparatus shown in FIG. 1, and the conversion rate of acrylic acid was calculated according to the following formula by analyzing the acrylic acid concentration of the reactor inlet liquid and outlet liquid.
アクリル酸の転化率；
第１表
第１図の装置を用い、純度９９．７重量％のアクリル酸
およびメタノールを原料とし、エステル化反応器に多孔
質の陽イオン交換樹脂７．５２を充填してアクリル酸メ
チルの製造を行なった。運転開始時（運転を開始して定
常状態に達したとき）及び運転開始から７ケ月後の状況
は第１表に示したとおりであった。Conversion rate of acrylic acid; Using the apparatus shown in Table 1 and Figure 1, using acrylic acid and methanol with a purity of 99.7% by weight as raw materials, the esterification reactor was filled with porous cation exchange resin 7.52%. Methyl acrylate was produced. The conditions at the start of operation (when the steady state was reached after the start of operation) and seven months after the start of operation were as shown in Table 1.
運転中、反応器でのアクリル酸の転化率を一定に保つ為
に樹脂の経時劣化に伴い反応温度を徐々に上昇させた結
果、７ケ月間の連続運転後反応温度は６７℃となったが
この間の反応温度の上昇割合はほぼ一定であった。また
、運転中はアクリル酸の転化率、エステル化反応生成物
の組成、アクリル酸分離塔の塔底温度、循環液の組成な
どは安定していた。During operation, in order to maintain a constant conversion rate of acrylic acid in the reactor, the reaction temperature was gradually increased as the resin deteriorated over time, and as a result, the reaction temperature reached 67℃ after 7 months of continuous operation. During this period, the rate of increase in reaction temperature was almost constant. Furthermore, during operation, the conversion rate of acrylic acid, the composition of the esterification reaction product, the bottom temperature of the acrylic acid separation column, the composition of the circulating liquid, etc. were stable.
宜Ｗ
実施例１と同じ純度９９．７重量％のアクリル酸とブタ
ノールとを原料とし、エステル反応器に多孔質の陽イオ
ン交換樹脂２０Ｑを充填し、反応温度６５℃にて実施例
１に準じてアクリル酸ブチルの製造を開始した。Using acrylic acid and butanol with the same purity of 99.7% by weight as in Example 1 as raw materials, an ester reactor was filled with porous cation exchange resin 20Q, and the reaction temperature was 65°C according to Example 1. The production of butyl acrylate was started.
運転を開始して定常状態に達したとき、各流量はアクリ
ル酸（ライン１）１．３３ｋｇ／時、ブタ／ −）Ｉｔ
（ライン２） ２． ００ｋｇ／時、 ｌｌ［ｔｆ
ｆｌ （ライン？）６．６６ｋｇ／時、アクリル酸の転
化率は２８．５％、アクリル酸分離塔塔底温度は１００
℃であった０
７ケ月間連続運転する間にエステル化反応温度は６５℃
からほぼ一定の割合で上昇し、７６℃になった。しかし
、７ケ月間の連続運転中、アクリル酸の転化率、エステ
ル化反応生成物の組成、アクリル酸分離塔の塔底温度、
循環液の組成などは安定していた。When the operation started and steady state was reached, each flow rate was 1.33 kg/hour of acrylic acid (line 1), pig/-) It
(Line 2) 2. 00kg/hour, ll[tf
fl (line?) 6.66 kg/hour, acrylic acid conversion rate 28.5%, acrylic acid separation column bottom temperature 100
The esterification reaction temperature was 65℃ during continuous operation for 7 months.
The temperature rose at an almost constant rate from then on to 76°C. However, during continuous operation for seven months, the conversion rate of acrylic acid, the composition of the esterification reaction product, the bottom temperature of the acrylic acid separation column,
The composition of the circulating fluid was stable.
区数■ユ
運転中の反応温度を７６℃に保った他は実施例２と同様
にしてアクリル酸ブチルの製造を実施した。その結果、
樹脂の経時劣化が起こり、アクリル酸の転化率は徐々に
低下し、アクリル酸分離塔の塔底温度は徐々に上昇して
５ケ月間で連続運転を停止せざるをえなかった。運転を
開始して定常状態に達したと萱のアクリル酸の転化率は
３５゜０％であったのが運転停止時には１７．５％に低
下しており、実施例２に比べて樹脂寿命は明らかに短く
なっており、単位触媒量当りの総生産量も少なかった。Butyl acrylate was produced in the same manner as in Example 2, except that the reaction temperature during operation was maintained at 76°C. the result,
The resin deteriorated over time, the conversion rate of acrylic acid gradually decreased, and the temperature at the bottom of the acrylic acid separation column gradually increased, necessitating the suspension of continuous operation after 5 months. The conversion rate of acrylic acid in Kaya was 35.0% when the steady state was reached after the operation started, but it decreased to 17.5% when the operation was stopped, and compared to Example 2, the resin life was shortened. It was clearly shorter, and the total production per unit amount of catalyst was also smaller.
［発明の効果］
本発明によればアクリル酸の転化率が常に一定になる様
にエステル化反応させるので、アクリル酸分離塔の運転
条件も安定しており、アクリル酸分離塔での塔底温度上
昇による重合物の増加もなく、またアクリル酸分離塔塔
底液の組成も一定するので反応器の液組成も一定であり
、その結果樹脂の膨潤、収縮９割れなどの問題を防いで
樹脂寿命を長く維持することができ、前記本発明の目的
が達成される。本発明においては、反応器の温度が規定
の温度に達した時点をもって触媒の寿命とし、触媒交換
を行なう。本発明によれば、新たに充填された触媒が寿
命に到達したとして交換されるまでの単位触媒量当りの
総生産量は前記従来の方法に比べて多い値が得られる。[Effects of the Invention] According to the present invention, since the esterification reaction is carried out so that the conversion rate of acrylic acid is always constant, the operating conditions of the acrylic acid separation column are also stable, and the bottom temperature of the acrylic acid separation column is kept constant. There is no increase in polymerized products due to rising, and the composition of the bottom liquid of the acrylic acid separation column is also constant, so the liquid composition of the reactor is also constant.As a result, problems such as resin swelling and shrinkage cracking are prevented, and the resin life is extended. can be maintained for a long time, and the above object of the present invention is achieved. In the present invention, the life of the catalyst is reached when the temperature of the reactor reaches a specified temperature, and the catalyst is replaced. According to the present invention, the total production amount per unit amount of catalyst until the newly filled catalyst reaches the end of its life and is replaced can be increased compared to the conventional method.
第１図は本発明の好適な実施態様を例示するフローシー
ト図を表わす。
１０１・・・エステル化反応器
１０２・・・アクリル酸分離塔
１０３・・・薄層蒸発法 １０４・・・受器１・・
・アクリル酸供給ライン
２・・・アルコール供給ライン
３・・・エステル化反応器入口
４・・・エステル化反応器出口
５・・・アクリル酸分離塔塔底液抜き出しライン６・・
・高沸点物抜艶出しライン
７・・・循環液供給ライン
８・・・エステル相抜き出しライン
９・・・°水相抜き出しライン
第１図FIG. 1 depicts a flow sheet diagram illustrating a preferred embodiment of the invention. 101...Esterification reactor 102...Acrylic acid separation column 103...Thin layer evaporation method 104...Receiver 1...
- Acrylic acid supply line 2...Alcohol supply line 3...Esterification reactor inlet 4...Esterification reactor outlet 5...Acrylic acid separation column bottom liquid extraction line 6...
・High-boiling point removal polishing line 7...Circulating fluid supply line 8...Ester phase extraction line 9...°Aqueous phase extraction line Figure 1
Claims (2)
ールまたは脂環式アルコールとをエステル化反応器に供
給し、該反応器にて強酸性陽イオン交換樹脂を触媒とし
てアクリル酸の転化率が常に一定になる様に反応温度を
調節しながらエステル化反応させ、得られた反応生成物
をアクリル酸分離塔に導いて、アクリル酸分離塔の塔頂
からアクリル酸エステル、水および未反応アルコールを
留去させる一方、アクリル酸分離塔の塔底から実質的に
全量のアクリル酸を含む液を抜きだして循環液としてエ
ステル化反応器に循環させることを特徴とするアクリル
酸エステルの製造方法。(1) Acrylic acid and a lower aliphatic alcohol or alicyclic alcohol having 1 to 4 carbon atoms are supplied to an esterification reactor, and the acrylic acid is converted in the reactor using a strongly acidic cation exchange resin as a catalyst. The esterification reaction is carried out while adjusting the reaction temperature so that the reaction rate is always constant, and the resulting reaction product is led to an acrylic acid separation column, where acrylic ester, water, and unreacted ester are separated from the top of the acrylic acid separation column. A method for producing an acrylic acid ester, which comprises distilling off alcohol while extracting a liquid containing substantially the entire amount of acrylic acid from the bottom of an acrylic acid separation column and circulating it as a circulating liquid to an esterification reactor. .
水の濃度が５重量％以下であり、かつエステル化反応器
に新規に供給される原料液の量に対する循環液の量が１
〜５倍量である請求項（１）に記載の方法。(2) The concentration of acrylic acid in the circulating fluid is 50% by weight or more,
The concentration of water is 5% by weight or less, and the amount of circulating liquid is 1% relative to the amount of raw material liquid newly supplied to the esterification reactor.
The method according to claim 1, wherein the amount is ~5 times.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1100168A JPH0686406B2 (en) | 1989-04-21 | 1989-04-21 | Method for producing acrylic ester |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1100168A JPH0686406B2 (en) | 1989-04-21 | 1989-04-21 | Method for producing acrylic ester |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02279655A true JPH02279655A (en) | 1990-11-15 |
| JPH0686406B2 JPH0686406B2 (en) | 1994-11-02 |
Family
ID=14266789
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1100168A Expired - Lifetime JPH0686406B2 (en) | 1989-04-21 | 1989-04-21 | Method for producing acrylic ester |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0686406B2 (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1069893C (en) * | 1996-08-03 | 2001-08-22 | 中国石化齐鲁石油化工公司 | Process for producing methyl methacrylate and ethyl methacrylate |
| US6605738B1 (en) | 1996-05-29 | 2003-08-12 | Union Carbide Chemicals & Plastics Technology Corporation | Processes for refining butyl acrylate |
| KR100380017B1 (en) * | 1998-12-30 | 2003-09-26 | 주식회사 엘지화학 | Manufacturing method of unsaturated carboxylic ester by continuous process |
| JP2007284406A (en) * | 2006-04-20 | 2007-11-01 | Mitsui Chemicals Inc | Production method for thiol compound |
| US7491841B2 (en) | 2006-07-11 | 2009-02-17 | Nippon Shokubai Co., Ltd. | Process for producing acrylic ester |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS54106412A (en) * | 1978-02-08 | 1979-08-21 | Kyowa Yuka Kk | Method of purifying ester |
| JPS58159442A (en) * | 1982-03-17 | 1983-09-21 | Nippon Kayaku Co Ltd | Preparation of acrylic or methacrylic ester |
| JPS5912102A (en) * | 1982-07-12 | 1984-01-21 | Toshiba Corp | Labyrinth packing |
| JPS6320415A (en) * | 1986-07-12 | 1988-01-28 | Nippon Steel Corp | Method for controlling combustion of side burner of continuous heating furnace |
-
1989
- 1989-04-21 JP JP1100168A patent/JPH0686406B2/en not_active Expired - Lifetime
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS54106412A (en) * | 1978-02-08 | 1979-08-21 | Kyowa Yuka Kk | Method of purifying ester |
| JPS58159442A (en) * | 1982-03-17 | 1983-09-21 | Nippon Kayaku Co Ltd | Preparation of acrylic or methacrylic ester |
| JPS5912102A (en) * | 1982-07-12 | 1984-01-21 | Toshiba Corp | Labyrinth packing |
| JPS6320415A (en) * | 1986-07-12 | 1988-01-28 | Nippon Steel Corp | Method for controlling combustion of side burner of continuous heating furnace |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6605738B1 (en) | 1996-05-29 | 2003-08-12 | Union Carbide Chemicals & Plastics Technology Corporation | Processes for refining butyl acrylate |
| CN1069893C (en) * | 1996-08-03 | 2001-08-22 | 中国石化齐鲁石油化工公司 | Process for producing methyl methacrylate and ethyl methacrylate |
| KR100380017B1 (en) * | 1998-12-30 | 2003-09-26 | 주식회사 엘지화학 | Manufacturing method of unsaturated carboxylic ester by continuous process |
| JP2007284406A (en) * | 2006-04-20 | 2007-11-01 | Mitsui Chemicals Inc | Production method for thiol compound |
| US7491841B2 (en) | 2006-07-11 | 2009-02-17 | Nippon Shokubai Co., Ltd. | Process for producing acrylic ester |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0686406B2 (en) | 1994-11-02 |
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