JP2003112001A - Gas condensation method - Google Patents
Gas condensation methodInfo
- Publication number
- JP2003112001A JP2003112001A JP2001308549A JP2001308549A JP2003112001A JP 2003112001 A JP2003112001 A JP 2003112001A JP 2001308549 A JP2001308549 A JP 2001308549A JP 2001308549 A JP2001308549 A JP 2001308549A JP 2003112001 A JP2003112001 A JP 2003112001A
- Authority
- JP
- Japan
- Prior art keywords
- gas
- cooling tower
- boiling point
- condensing
- impurities
- 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
- 238000000034 method Methods 0.000 title claims abstract description 38
- 238000009833 condensation Methods 0.000 title claims description 10
- 230000005494 condensation Effects 0.000 title claims description 10
- 238000001816 cooling Methods 0.000 claims abstract description 127
- 238000009835 boiling Methods 0.000 claims abstract description 96
- 239000012535 impurity Substances 0.000 claims abstract description 69
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 claims description 36
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 239000002826 coolant Substances 0.000 claims description 15
- 238000005507 spraying Methods 0.000 abstract description 10
- 238000011112 process operation Methods 0.000 abstract description 6
- 239000007789 gas Substances 0.000 description 203
- 239000012495 reaction gas Substances 0.000 description 47
- 238000007254 oxidation reaction Methods 0.000 description 22
- STNJBCKSHOAVAJ-UHFFFAOYSA-N Methacrolein Chemical compound CC(=C)C=O STNJBCKSHOAVAJ-UHFFFAOYSA-N 0.000 description 21
- 230000003197 catalytic effect Effects 0.000 description 20
- 230000003647 oxidation Effects 0.000 description 20
- 239000000126 substance Substances 0.000 description 17
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 15
- 239000000047 product Substances 0.000 description 13
- 238000001556 precipitation Methods 0.000 description 12
- 239000012071 phase Substances 0.000 description 11
- 239000007921 spray Substances 0.000 description 11
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 10
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 10
- 230000007423 decrease Effects 0.000 description 10
- 239000012808 vapor phase Substances 0.000 description 10
- 239000007788 liquid Substances 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 6
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 6
- 238000007664 blowing Methods 0.000 description 6
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 6
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 5
- 238000000605 extraction Methods 0.000 description 5
- 238000011084 recovery Methods 0.000 description 5
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 3
- 239000011261 inert gas Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000010791 quenching Methods 0.000 description 3
- 230000000171 quenching effect Effects 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 229920000297 Rayon Polymers 0.000 description 2
- -1 acetaldehyde, aromatic compounds Chemical class 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 230000002265 prevention Effects 0.000 description 2
- 239000013076 target substance Substances 0.000 description 2
- 101710192523 30S ribosomal protein S9 Proteins 0.000 description 1
- 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 1
- 102100032768 Complement receptor type 2 Human genes 0.000 description 1
- 101100321669 Fagopyrum esculentum FA02 gene Proteins 0.000 description 1
- 101000941929 Homo sapiens Complement receptor type 2 Proteins 0.000 description 1
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- ZWLPBLYKEWSWPD-UHFFFAOYSA-N o-toluic acid Chemical compound CC1=CC=CC=C1C(O)=O ZWLPBLYKEWSWPD-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
Landscapes
- Vaporization, Distillation, Condensation, Sublimation, And Cold Traps (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
(57)【要約】
【課題】 凝縮対象物よりも沸点が高い不純物を含む気
体を冷却塔で凝縮する際に冷却塔の気体の入口部に析出
した高沸点不純物をプロセス運転中に簡便に、また、後
の工程の負荷を増大することなく除去し、プロセスを長
期間安定に運転できる気体の凝縮方法を提供する。
【解決手段】 本発明は、凝縮対象物よりも沸点が高い
不純物を含む気体を冷却塔で凝縮する際に、冷却塔の気
体の入口部に連続的または断続的に高沸物除去用ガスを
吹き付けることを特徴とする。
(57) [Summary] [PROBLEMS] When condensing a gas containing impurities having a boiling point higher than that of an object to be condensed in a cooling tower, high boiling impurities precipitated at an inlet of the gas in the cooling tower can be easily obtained during a process operation. In addition, the present invention provides a method for condensing gas, which can remove a subsequent process without increasing the load and can operate the process stably for a long time. SOLUTION: The present invention, when condensing a gas containing impurities having a boiling point higher than that of an object to be condensed in a cooling tower, continuously or intermittently supplies a high-boiling matter removing gas to an inlet of the gas in the cooling tower. It is characterized by spraying.
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、気体の凝縮方法、
より詳しくは、凝縮対象物よりも沸点が高い不純物を含
む気体を冷却塔で凝縮する方法に関する。TECHNICAL FIELD The present invention relates to a method for condensing a gas,
More specifically, the present invention relates to a method of condensing a gas containing impurities having a boiling point higher than that of an object to be condensed in a cooling tower.
【０００２】[0002]
【従来の技術】イソブチレンおよび／またはtert-ブチ
ルアルコールの接触気相酸化によりメタクロレインおよ
び／またはメタクリル酸を製造する際に、また、メタク
ロレインの接触気相酸化によりメタクリル酸を製造する
際に、原料ガスを接触気相酸化させた反応ガスから目的
生成物であるメタクロレインおよび／またはメタクリル
酸を捕集するのには、通常、冷却塔が用いられる。一
方、この反応ガス中には、目的生成物以外に、酢酸、ア
クロレイン、アクリル酸、アセトアルデヒドの他、テレ
フタル酸やトルイル酸などの芳香族化合物、タール状物
質等の高沸点不純物が含まれている。テレフタル酸等の
高沸点不純物は、冷却塔で反応ガスを冷却して目的生成
物を含む反応ガスの凝縮液と非凝縮ガスとを得る際に、
かかる凝縮液への溶解度が低いため、配管や塔壁等に析
出し、閉塞を起こすことがある。In the production of methacrolein and / or methacrylic acid by catalytic vapor phase oxidation of isobutylene and / or tert-butyl alcohol, and in the production of methacrylic acid by catalytic vapor phase oxidation of methacrolein, A cooling tower is usually used to collect methacrolein and / or methacrylic acid, which are target products, from the reaction gas obtained by catalytically vapor-oxidizing the raw material gas. On the other hand, the reaction gas contains acetic acid, acrolein, acrylic acid, acetaldehyde, aromatic compounds such as terephthalic acid and toluic acid, and high-boiling impurities such as tar-like substances, in addition to the desired product. . High-boiling-point impurities such as terephthalic acid, when cooling the reaction gas in the cooling tower to obtain the condensed liquid and the non-condensed gas of the reaction gas containing the target product,
Since the solubility in the condensate is low, it may be deposited on the pipe, the wall of the tower, or the like to cause clogging.
【０００３】また、プロピレンの接触気相酸化によりア
クロレインおよび／またはアクリル酸を製造する際に、
原料ガスを接触気相酸化させた反応ガスから目的生成物
であるアクロレインおよび／またはアクリル酸を捕集す
るのにも、通常、冷却塔が用いられる。この反応ガス中
には、目的生成物以外に、酢酸、ギ酸、アセトアルデヒ
ド、ホルムアルデヒドの他、タール状物質等の高沸点不
純物が含まれており、冷却塔で反応ガスを冷却して目的
生成物を含む反応ガスの凝縮液を得る際に、メタクロレ
インおよび／またはメタクリル酸を凝縮する場合と同
様、高沸点不純物が配管や塔壁等に析出し、閉塞を起こ
すことがある。Further, in producing acrolein and / or acrylic acid by catalytic gas phase oxidation of propylene,
A cooling tower is also usually used to collect acrolein and / or acrylic acid, which are target products, from a reaction gas obtained by catalytically vapor-oxidizing a raw material gas. In addition to the target product, this reaction gas contains acetic acid, formic acid, acetaldehyde, formaldehyde, and high-boiling impurities such as tar-like substances, and the reaction gas is cooled in a cooling tower to obtain the target product. When obtaining the condensate of the containing reaction gas, high boiling point impurities may be deposited on the pipes, the tower wall, etc., as in the case of condensing methacrolein and / or methacrylic acid, and blockage may occur.
【０００４】その対策として、特開昭５０−１２６６０
５号公報には、反応器出口から次の装置までの配管の管
壁面温度および冷却器の冷却面の温度を無水マレイン酸
の沸点以上に保ち、かつ、ガスの平均線速度を５ｍ／秒
以上に保つことにより、高沸点不純物の付着、成長を防
止することが開示されている。しかしながら、配管を保
温したり、冷却器の冷却面の温度を無水マレイン酸の沸
点以上で操作したり、反応ガスの線速度を上げることに
よって配管壁面、冷却器の冷却面における高沸点不純物
の析出は防ぐことができるが、反応ガス線速度が低下す
る冷却塔入口部における高沸点不純物の析出を防ぐこと
は非常に難しい。As a countermeasure, Japanese Patent Laid-Open No. 12660/1975
No. 5 discloses that the temperature of the pipe wall surface of the pipe from the reactor outlet to the next device and the temperature of the cooling surface of the cooler are maintained at the boiling point of maleic anhydride or higher, and the average linear velocity of gas is 5 m / sec or higher. It is disclosed that the high boiling point impurities are prevented from adhering and growing by keeping the temperature at 0. However, by keeping the pipe warm, operating the temperature of the cooling surface of the cooler above the boiling point of maleic anhydride, and increasing the linear velocity of the reaction gas, the precipitation of high boiling impurities on the pipe wall surface and the cooling surface of the cooler However, it is very difficult to prevent the precipitation of high-boiling impurities at the cooling tower inlet where the linear velocity of the reaction gas decreases.
【０００５】また、特開昭５１−２６７５号公報には、
冷却塔壁にガス吹込ノズルを塔底液面の中央部に向けて
斜め下向きに塔内部に突出させずに取り付け、高沸点不
純物を含有する反応生成ガスを直接塔底液面の中央部に
衝突させることが開示されている。これにより、ノズル
直付け廻りの塔壁以外は温度勾配が小さくなり、高沸点
不純物の析出を防ぐことができ、ノズル直付け廻りの塔
壁は凝縮液によって連続的に冷却され、また、重合禁止
剤に連続的に触れるので重合は起こらないと記載されて
いる。しかしながら、冷却塔入口ノズル部を塔内部へ突
出させずに取り付けた場合、急冷塔循環液（凝縮液）が
直接反応ガスに接触し、冷却塔入口部分で高沸点不純物
の析出が発生すると考えられる。Further, Japanese Patent Laid-Open No. 51-2675 discloses that
A gas injection nozzle was attached to the wall of the cooling tower diagonally downward toward the center of the bottom liquid level without protruding into the inside of the tower, and the reaction product gas containing high-boiling point impurities collided directly with the center of the bottom liquid surface. It is disclosed to do. As a result, the temperature gradient is reduced except for the column wall directly around the nozzle, and the precipitation of high boiling impurities can be prevented.The column wall directly around the nozzle is continuously cooled by the condensate, and polymerization is prohibited. It is stated that polymerization does not occur because the agent is continuously touched. However, if the cooling tower inlet nozzle is installed without protruding into the tower, it is considered that the quenching tower circulating liquid (condensate) directly contacts the reaction gas and precipitation of high-boiling impurities occurs at the cooling tower inlet. .
【０００６】また、特開昭５７−９１９４４号公報に
は、反応ガスを急冷塔の塔頂部より反応ガス供給口での
流速を１０ｍ／秒以上にて供給し、反応ガス供給口周囲
は２００℃以上の加熱気体雰囲気とし、かつ、反応ガス
供給口周囲に円環状に加熱気体を吹き込む口を有した急
冷塔を用いて、反応ガスと凝縮液とを並流接触させるこ
とにより、高沸点副生物の付着、成長を防止し、配管等
での閉塞を防止することが開示されている。また、特公
平７−６４７７４号公報には、反応器出口直後の反応生
成ガスに不活性ガスおよび／または反応循環ガスを供給
混合することにより、メタクロレインの後酸化を防止
し、かつ、テレフタル酸等の高沸点不純物の管壁への析
出を抑制できることが開示されている。しかしながら、
反応ガス供給口周囲に加熱気体を吹き込んだり、反応器
出口直後のガスに不活性ガス等を混合して高沸点不純物
の析出を抑制するには、膨大な量のガスが必要である場
合があり、装置が大きくなる上に、その後のメタクロレ
インやメタクリル酸の吸収・回収工程の負荷が増大する
こともある。Further, in JP-A-57-91944, the reaction gas is supplied from the top of the quenching tower at a flow rate of 10 m / sec or more at the reaction gas supply port, and the temperature around the reaction gas supply port is 200 ° C. By using a quenching tower having the above heated gas atmosphere, and having a port for blowing the heated gas in an annular shape around the reaction gas supply port, the reaction gas and the condensate are brought into parallel flow contact to obtain a high boiling by-product. It is disclosed to prevent the adhesion and growth of the above, and to prevent the clogging of the piping and the like. In addition, in Japanese Patent Publication No. 7-64774, the reaction product gas immediately after the reactor outlet is mixed with an inert gas and / or a reaction circulation gas to prevent post-oxidation of methacrolein and to prevent terephthalic acid. It is disclosed that the high boiling point impurities such as the above can be prevented from depositing on the pipe wall. However,
A huge amount of gas may be required to blow heated gas around the reaction gas supply port or to mix inert gas with the gas immediately after the reactor outlet to suppress precipitation of high-boiling impurities. In addition to the increase in the size of the device, the load of the subsequent methacrolein and methacrylic acid absorption / recovery process may increase.
【０００７】このように、イソブチレン等の接触気相酸
化によりメタクロレインおよび／またはメタクリル酸を
製造する際に、また、プロピレンの接触気相酸化により
アクロレインおよび／またはアクリル酸を製造する際に
も、反応器出口ガス（反応ガス）を冷却塔で冷却して目
的生成物の凝縮液を得るときの高沸点不純物の析出、特
に、反応ガスの平均線速度が低下する冷却塔のガス入口
部における高沸点不純物の析出は、連続運転を妨げるも
のとして問題になる場合があり、ガス入口部に析出した
高沸点不純物を簡便に、また、後の工程の負荷を増大す
ることなく抑制する方法が求められている。Thus, when producing methacrolein and / or methacrylic acid by catalytic vapor phase oxidation of isobutylene and the like, and also when producing acrolein and / or acrylic acid by catalytic vapor phase oxidation of propylene, Precipitation of high-boiling-point impurities when the reactor outlet gas (reaction gas) is cooled in a cooling tower to obtain a condensate of the target product, especially the high temperature at the gas inlet of the cooling tower where the average linear velocity of the reaction gas decreases. Deposition of boiling point impurities may be a problem because it hinders continuous operation.Therefore, there is a demand for a method of simply suppressing high boiling point impurities deposited at the gas inlet portion and suppressing the load of subsequent steps without increasing. ing.
【０００８】[0008]
【発明が解決しようとする課題】本発明は、凝縮対象物
よりも沸点が高い不純物を含む気体を冷却塔で凝縮する
際に冷却塔の気体の入口部に析出した高沸点不純物をプ
ロセス運転中に簡便に、また、後の工程の負荷を増大す
ることなく除去し、プロセスを長期間安定に運転できる
気体の凝縮方法を提供することを目的とする。SUMMARY OF THE INVENTION According to the present invention, when a gas containing an impurity having a boiling point higher than that of an object to be condensed is condensed in the cooling tower, the high boiling point impurity deposited at the gas inlet of the cooling tower is in process operation. It is an object of the present invention to provide a gas condensing method that can be simply and easily removed without increasing the load of the subsequent steps and can stably operate the process for a long period of time.
【０００９】[0009]
【課題を解決するための手段】本発明者らは、数々の改
良を試みたが、最終的には高沸点不純物の析出を長期に
渡って防ぐことは困難であるという結論に達した。そこ
で、プロセス運転中に析出した高沸点不純物による汚れ
をプロセスの運転を継続しながら除去することを目的と
して鋭意検討を行った結果、本発明をなすに至った。Means for Solving the Problems The inventors of the present invention have made various attempts, but finally concluded that it is difficult to prevent precipitation of high-boiling-point impurities over a long period of time. Therefore, as a result of intensive studies aimed at removing stains due to high-boiling-point impurities deposited during the process operation while continuing the process operation, the present invention has been accomplished.
【００１０】すなわち、本発明の上記目的は以下の本発
明により達成できる。
（１）凝縮対象物よりも沸点が高い不純物を含む気体
（凝縮性蒸気）を冷却塔に導入し、冷却凝縮する方法で
あって、前記冷却塔の気体の入口部に連続的または断続
的に高沸物除去用ガスを吹き付けることを特徴とする気
体の凝縮方法。
（２）前記冷却塔の気体の入口部に、導入される気体と
冷却媒体とが直接接触するのを防ぐための冷却塔内部へ
の突起部が設けられていることを特徴とする前記（１）
の気体の凝縮方法。
（３）前記突起部内に、前記高沸物除去用ガスを噴出す
るノズルが設置されており、このノズルから高沸物除去
用ガスを前記突起部の内側に吹き付けることを特徴とす
る前記（２）の気体の凝縮方法。
（４）前記冷却塔の気体の入口部の圧力損失が運転開始
時の値から０．３〜４ｋＰａ上昇したときに、前記冷却
塔の気体の入口部に高沸物除去用ガスを３〜１８００秒
間吹き付けることを特徴とする前記（１）〜（３）のい
ずれかの気体の凝縮方法。
（５）前記高沸物除去用ガスが水蒸気であることを特徴
とする前記（１）〜（４）のいずれかの気体の凝縮方
法。
（６）前記凝縮対象物が（メタ）アクロレインおよび／
または（メタ）アクリル酸であることを特徴とする前記
（１）〜（５）のいずれかの気体の凝縮方法。That is, the above object of the present invention can be achieved by the following present invention. (1) A method of introducing a gas (condensable vapor) containing impurities having a boiling point higher than that of an object to be condensed into a cooling tower and cooling and condensing the same, continuously or intermittently at the gas inlet portion of the cooling tower. A method for condensing a gas, which comprises spraying a gas for removing a high-boiling substance. (2) The gas inlet of the cooling tower is provided with a protrusion to the inside of the cooling tower for preventing direct contact between the introduced gas and the cooling medium. )
Method of gas condensation. (3) A nozzle for ejecting the high boiling point removing gas is installed in the protrusion, and the high boiling point removing gas is blown from the nozzle to the inside of the protrusion. ) Gas condensation method. (4) When the pressure loss at the gas inlet of the cooling tower is increased by 0.3 to 4 kPa from the value at the start of the operation, the high boiling point removing gas is supplied at 3 to 1800 at the gas inlet of the cooling tower. The method for condensing a gas according to any one of the above (1) to (3), characterized by spraying for a second. (5) The method for condensing a gas according to any one of (1) to (4), wherein the high boiling point removing gas is water vapor. (6) The condensation object is (meth) acrolein and / or
Alternatively, the method for condensing a gas according to any one of (1) to (5) above, which is (meth) acrylic acid.
【００１１】[0011]
【発明の実施の形態】本発明では、凝縮対象物よりも沸
点が高い不純物（高沸点不純物）を含む気体を冷却塔で
凝縮する際に、冷却塔の気体の入口部に連続的または断
続的に高沸物除去用ガスを吹き付けて、析出した高沸点
不純物を除去する。高沸物除去用ガスは連続的に吹き付
けてもよいが、高沸物除去用ガスの使用量を抑制でき、
凝縮後の目的物の吸収・回収工程の負荷を減らせるの
で、断続的に吹き付けることが好ましい。BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, when a gas containing an impurity having a boiling point higher than that of a substance to be condensed (high boiling point impurity) is condensed in a cooling tower, the gas is continuously or intermittently introduced into the gas inlet portion of the cooling tower. A high-boiling-point removing gas is blown onto the surface to remove the precipitated high-boiling-point impurities. The high boiling point removal gas may be continuously sprayed, but the amount of high boiling point removal gas can be suppressed,
Intermittent spraying is preferable because it can reduce the load of the step of absorbing and recovering the target substance after condensation.
【００１２】図１に、従来の一般的な冷却塔の図を示
す。凝縮対象物よりも沸点が高い不純物を含む気体（例
えば、（メタ）アクロレインおよび／または（メタ）ア
クリル酸の合成反応を行ない、反応器から出てきた反応
ガス）は、ガス導入ライン５より冷却塔１に導入され
る。そして、冷却塔１で導入された気体は冷却媒体（こ
こでは、凝縮液）で冷却され、凝縮対象物が凝縮する。
この凝縮対象物の凝縮液は、凝縮液ライン６より抜き出
され、凝縮水循環ポンプ２によって凝縮液抜き出しライ
ン７より次の工程へ送られるが、凝縮液の一部は熱交換
器３に送られて所定の温度に冷却された後、凝縮液循環
ライン８を通って冷却塔１内へスプレーされ、冷却塔に
導入した高沸点不純物を含む気体と再び接触する。な
お、従来の冷却塔のガス入口ノズル部分１０には、導入
される気体と冷却媒体とが直接接触するのを防ぐような
冷却塔内部への突起は設けられていない。FIG. 1 shows a diagram of a conventional general cooling tower. A gas containing an impurity having a boiling point higher than that of the substance to be condensed (for example, a reaction gas that has been synthesized from (meth) acrolein and / or (meth) acrylic acid and has come out of the reactor) is cooled from the gas introduction line 5. It is introduced into tower 1. Then, the gas introduced in the cooling tower 1 is cooled by a cooling medium (condensate in this case), and the condensation object is condensed.
The condensate of the condensate is extracted from the condensate line 6 and sent to the next step from the condensate withdrawal line 7 by the condensed water circulation pump 2, but a part of the condensate is sent to the heat exchanger 3. After being cooled to a predetermined temperature, it is sprayed into the cooling tower 1 through the condensate circulation line 8 and comes into contact with the gas containing the high boiling point impurities introduced into the cooling tower again. It should be noted that the gas inlet nozzle portion 10 of the conventional cooling tower is not provided with a protrusion to the inside of the cooling tower that prevents direct contact between the introduced gas and the cooling medium.
【００１３】ここで、冷却塔のガス入口部では、通常、
導入される気体の線速度が低下する。冷却塔ガス入口部
でガス線速度が低下するのは、配管径と冷却塔径の差に
よるものである。配管ハンドブック＜第４版＞配管工学
研究会編によれば、一般的な化学プラントの配管内低圧
ガスの線速度は１０〜２０ｍ／秒となっており、この速
度を目安に配管径が決定される。また、冷却塔径は、取
り扱う条件、取り扱う物質の物性を元に、気液の接触効
率、フラッディング防止、飛沫同伴防止などの観点から
設計される。その結果、ガス線速度は５ｍ／秒以下の場
合がほとんどと考えられる。したがって、ほとんどの場
合、冷却塔のガス入口部分では導入される気体の線速度
が低下する。そのため、さらには、導入される気体の線
速度が低下するのと同時に気体が冷却媒体（凝縮液）と
直接接触するため、冷却塔の気体の入口部に高沸点不純
物が析出すると考えられる。冷却塔の気体の入口部と
は、気体の線速度低下のために高沸点不純物が析出する
ところ、具体的には、冷却塔の気体の入口周囲の冷却塔
壁、および、冷却塔近くの配管壁面のことをいう。At the gas inlet of the cooling tower,
The linear velocity of the introduced gas decreases. The linear velocity of the gas decreases at the cooling tower gas inlet due to the difference between the pipe diameter and the cooling tower diameter. According to the Piping Handbook <4th Edition> Piping Engineering Study Group, the linear velocity of low-pressure gas in the pipes of general chemical plants is 10 to 20 m / sec, and the pipe diameter is determined based on this velocity. It The cooling tower diameter is designed from the viewpoints of gas-liquid contact efficiency, flooding prevention, entrainment prevention, etc., based on the handling conditions and the physical properties of the substances to be handled. As a result, it is considered that the gas linear velocity is almost 5 m / sec or less. Therefore, in most cases, the linear velocity of the introduced gas decreases at the gas inlet portion of the cooling tower. Therefore, further, since the linear velocity of the introduced gas decreases and the gas comes into direct contact with the cooling medium (condensate), it is considered that high-boiling impurities are deposited at the gas inlet of the cooling tower. The gas inlet part of the cooling tower is a place where high-boiling-point impurities are deposited due to a decrease in the linear velocity of the gas, specifically, the cooling tower wall around the gas inlet of the cooling tower and the pipe near the cooling tower. It refers to the wall surface.
【００１４】従来の方法では、このように析出した高沸
点不純物のために冷却塔ガス入口部が閉塞を起こすこと
があるという問題があった。In the conventional method, there is a problem that the cooling tower gas inlet may be blocked due to the high boiling point impurities thus deposited.
【００１５】本発明では、冷却塔の気体の入口部に析出
した高沸点不純物を、高沸物除去用ガスを吹き付けるこ
とによって、物理的に掻き落として除去する。これによ
り、冷却塔の気体の入口部が閉塞することを簡便に防止
でき、プロセスを長期間安定に運転できる。また、本発
明は、従来のものと比べて、多量のガスを冷却塔に導入
せずに優れた効果が得られるので、後の工程、例えばメ
タクロレインやメタクリル酸の吸収・回収工程、アクロ
レインやアクリル酸の吸収・回収工程の負荷をあまり増
大させることがない。In the present invention, the high boiling point impurities deposited at the gas inlet of the cooling tower are physically scraped off by blowing a high boiling point removal gas. Accordingly, it is possible to easily prevent the gas inlet portion of the cooling tower from being blocked, and the process can be stably operated for a long period of time. Further, the present invention, as compared with the conventional one, can obtain an excellent effect without introducing a large amount of gas into the cooling tower, so that the subsequent steps, for example, the absorption / recovery step of methacrolein and methacrylic acid, acrolein and It does not significantly increase the load of the acrylic acid absorption / recovery process.
【００１６】高沸物除去用ガスとしては、凝縮対象物と
反応しないものであれば特に限定されないが、不活性の
もの、例えば、水蒸気、窒素、アルゴン、ヘリウム、二
酸化炭素等が好ましい。また、高沸点不純物を物理的に
掻き落とすので、高沸物除去用ガスは密度の大きな状態
で供給することが好ましい。中でも、高沸物除去用ガス
としては、経済性と効果の点等から、水蒸気が好まし
い。高沸物除去用ガスは、１種を用いても２種以上を併
用してもかまわない。The high-boiling substance removing gas is not particularly limited as long as it does not react with the substance to be condensed, but an inert gas such as steam, nitrogen, argon, helium, carbon dioxide or the like is preferable. Further, since the high-boiling-point impurities are physically scraped off, it is preferable to supply the high-boiling-point removing gas in a state of high density. Among them, steam is preferable as the high boiling point removal gas from the viewpoints of economy and effect. The high boiling point removing gas may be used alone or in combination of two or more kinds.
【００１７】本発明が適用される、凝縮対象物よりも沸
点が高い不純物を含む気体としては特に限定されない。
中でも、本発明は、イソブチレンおよび／またはtert-
ブチルアルコールの接触気相酸化等により得られるメタ
クロレインおよび／またはメタクリル酸を含む反応ガ
ス、メタクロレインの接触気相酸化等により得られるメ
タクリル酸を含む反応ガスから目的生成物であるメタク
ロレインおよび／またはメタクリル酸を凝縮させて捕集
するのに好適であり、また、プロピレンの接触気相酸化
等により得られるアクロレインおよび／またはアクリル
酸を含む反応ガスから目的生成物であるアクロレインお
よび／またはアクリル酸を凝縮させて捕集するのにも好
適である。The gas containing impurities having a boiling point higher than that of the object to be condensed, to which the present invention is applied, is not particularly limited.
Among them, the present invention relates to isobutylene and / or tert-
Reaction gas containing methacrolein and / or methacrylic acid obtained by catalytic vapor phase oxidation of butyl alcohol, and methacrolein and / or a target product from a reaction gas containing methacrylic acid obtained by catalytic vapor phase oxidation of methacrolein It is also suitable for condensing and collecting methacrylic acid, and the target product acrolein and / or acrylic acid from a reaction gas containing acrolein and / or acrylic acid obtained by catalytic gas phase oxidation of propylene or the like. It is also suitable for condensing and collecting.
【００１８】ここで、イソブチレンおよび／またはtert
-ブチルアルコールの接触気相酸化の反応条件、メタク
ロレインの接触気相酸化の反応条件、プロピレンの接触
気相酸化の反応条件は、特に限定されず、公知の方法に
従って行えばよい。また、冷却塔に導入する反応ガスの
組成、高沸点不純物の含有量は製造方法等により異な
り、特に限定されない。Here, isobutylene and / or tert
-The reaction conditions for the catalytic gas phase oxidation of butyl alcohol, the reaction conditions for the catalytic gas phase oxidation of methacrolein, and the reaction conditions for the catalytic gas phase oxidation of propylene are not particularly limited and may be carried out according to known methods. The composition of the reaction gas introduced into the cooling tower and the content of high-boiling-point impurities vary depending on the production method and the like, and are not particularly limited.
【００１９】以下、本発明を図２、３を用いて詳細に説
明する。なお、図２、３は本発明を実施するためのプロ
セスの一例であり、本発明は図２、３により何ら制限さ
れない。The present invention will be described in detail below with reference to FIGS. 2 and 3 are examples of processes for carrying out the present invention, and the present invention is not limited to FIGS.
【００２０】本発明で用いる冷却塔は特に限定されない
が、通常、スプレー塔が用いられる。気体（凝縮性蒸
気）と冷却媒体とが並流（流れが同方向）するものであ
っても向流（流れが逆方向）するものであってもよい。The cooling tower used in the present invention is not particularly limited, but a spray tower is usually used. The gas (condensable vapor) and the cooling medium may flow in parallel (the flows are in the same direction) or may be countercurrent (the flows are in the opposite direction).
【００２１】また、冷却塔の運転条件、冷却塔に導入す
る高沸点不純物を含む気体の流速、温度、圧力は、公知
の方法に従い、凝縮対象物等により適宜決めればよい。The operating conditions of the cooling tower and the flow rate, temperature, and pressure of the gas containing high-boiling-point impurities introduced into the cooling tower may be appropriately determined according to the object of condensation and the like according to known methods.
【００２２】冷却媒体としては、通常、冷却塔で凝縮し
た気体の凝縮液を用いるが、これに限定されるものでは
ない。As the cooling medium, a condensed liquid of a gas condensed in a cooling tower is usually used, but the cooling medium is not limited to this.
【００２３】本発明で用いる冷却塔の一例を図２に、図
２に示す冷却塔の気体の入口部の拡大図を図３に示す。An example of the cooling tower used in the present invention is shown in FIG. 2, and an enlarged view of the gas inlet portion of the cooling tower shown in FIG. 2 is shown in FIG.
【００２４】凝縮対象物よりも沸点が高い不純物を含む
気体（例えば、（メタ）アクロレインおよび／または
（メタ）アクリル酸の合成反応を行ない、反応器から出
てきた反応ガス）は、ガス導入ライン５より冷却塔１に
導入される。そして、冷却塔１で導入された気体は冷却
媒体（ここでは、凝縮液）で冷却され、凝縮対象物が凝
縮する。この凝縮対象物の凝縮液は、凝縮液ライン６よ
り抜き出され、凝縮水循環ポンプ２によって凝縮液抜き
出しライン７より次の工程へ送られる。また、凝縮液の
一部は、熱交換器３に送られて所定の温度に冷却された
後、凝縮液循環ライン８を通って冷却塔１内へスプレー
され、冷却塔に導入した高沸点不純物を含む気体と再び
接触する。A gas containing an impurity having a boiling point higher than that of the substance to be condensed (for example, a reaction gas that has gone out of the reactor after the synthesis reaction of (meth) acrolein and / or (meth) acrylic acid) is introduced into the gas introduction line. 5 is introduced into the cooling tower 1. Then, the gas introduced in the cooling tower 1 is cooled by a cooling medium (condensate in this case), and the condensation object is condensed. The condensate of the condensation object is extracted from the condensate line 6 and sent to the next step from the condensate extraction line 7 by the condensed water circulation pump 2. Further, a part of the condensate is sent to the heat exchanger 3 and cooled to a predetermined temperature, and then sprayed into the cooling tower 1 through the condensate circulation line 8 and introduced into the cooling tower. Contact again with gas containing.
【００２５】本発明で用いる冷却塔は、従来の冷却塔と
違い、気体の入口部に水蒸気等の高沸物除去用ガスを吹
き付ける構造をしている。高沸物除去用ガスは、気体の
入口部に設置された高沸物除去用ガススプレーノズルよ
り高沸点不純物が析出する気体の入口部に吹き付けられ
る。高沸物除去用ガスは、プロセスガス（凝縮対象物よ
りも沸点が高い不純物を含む気体）の流れに逆らわない
方向から吹き付けることが好ましい。高沸物除去用ガス
スプレーノズルの構造および個数については特に限定さ
れないが、析出する高沸点不純物全面に吹き付けられる
ような構造および個数が好ましい。また、高沸物除去用
ガスラインもノズルに合わせて設置すればよい。Unlike the conventional cooling tower, the cooling tower used in the present invention has a structure in which a high boiling point removing gas such as water vapor is blown to the gas inlet. The high-boiling-point removing gas is sprayed from the high-boiling-point removing gas spray nozzle installed at the gas inlet to the gas inlet where high-boiling impurities are deposited. It is preferable that the high-boiling substance removing gas is blown from a direction that does not oppose the flow of the process gas (gas containing impurities having a higher boiling point than the object to be condensed). The structure and number of the high-boiling substance removing gas spray nozzle are not particularly limited, but a structure and number capable of being sprayed on the entire surface of the high-boiling-point impurities to be precipitated are preferable. Further, the high boiling point removal gas line may be installed in accordance with the nozzle.
【００２６】図２に示す冷却塔１では、ガス入口ノズル
部分１１に、導入される気体と冷却媒体（凝縮液）とが
直接接触するのを防ぐような冷却塔内部への突起（ガス
ノズル突起部）を有している。この冷却塔の気体の入口
部の拡大図を図３に示す。In the cooling tower 1 shown in FIG. 2, projections (gas nozzle projections) to the inside of the cooling tower that prevent the introduced gas and the cooling medium (condensate) from directly contacting the gas inlet nozzle portion 11 )have. An enlarged view of the gas inlet of the cooling tower is shown in FIG.
【００２７】ガス入口ノズル部分に塔内部への突起がな
い従来の冷却塔では、冷却塔の気体の入口部で導入され
る気体の線速度が低下するのと同時に、気体が冷却媒体
と直接接触するため高沸点不純物が析出すると考えられ
る。一方、図２、３に示す冷却塔では、気体の線速度が
低下する気体の入口部に、図３のような冷却塔内部への
ガスノズル突起部１２を設けている。このガスノズル突
起部１２は、冷却塔に導入される気体と冷却媒体（凝縮
液）との直接接触を防ぐもので、冷却媒体が気体に降り
かからないようにする屋根（覆い）のような役割を果た
すものである。In the conventional cooling tower in which the gas inlet nozzle portion has no protrusion to the inside of the tower, the linear velocity of the gas introduced at the gas inlet portion of the cooling tower decreases, and at the same time, the gas directly contacts the cooling medium. Therefore, it is considered that high-boiling point impurities are deposited. On the other hand, in the cooling towers shown in FIGS. 2 and 3, the gas nozzle projection 12 to the inside of the cooling tower as shown in FIG. 3 is provided at the gas inlet where the linear velocity of the gas decreases. The gas nozzle projections 12 prevent direct contact between the gas introduced into the cooling tower and the cooling medium (condensate), and serve as a roof (cover) for preventing the cooling medium from falling onto the gas. It is a thing.
【００２８】本発明では、冷却塔の気体の入口部に高沸
物除去用ガスを吹き付ける構造を有していれば突起部を
設けなくてもかまわないが、このような冷却塔内部への
ガスノズル突起部１２を設けることが好ましい。気体の
線速度が低下する冷却塔の気体の入口部において導入さ
れる気体と冷却媒体とが直接接触するのを防止すること
で高沸点不純物の析出を抑制でき、しかも、高沸点不純
物が主にガスノズル突起部の内側（覆いの下側）に析出
するので、そこに高沸物除去用ガスを吹き付けることで
析出する高沸点不純物を十分に除去できてプロセスを長
期間安定に運転できる。In the present invention, the protrusion may not be provided as long as it has a structure for blowing the high boiling point removing gas to the gas inlet portion of the cooling tower, but such a gas nozzle into the cooling tower is provided. It is preferable to provide the protrusion 12. The precipitation of high-boiling impurities can be suppressed by preventing direct contact between the gas introduced at the gas inlet of the cooling tower where the linear velocity of the gas decreases and the cooling medium, and high-boiling impurities are mainly Since the gas is deposited on the inner side of the gas nozzle protrusion (the lower side of the cover), the high boiling point impurities that are deposited can be sufficiently removed by spraying the high boiling point removal gas, and the process can be stably operated for a long period of time.
【００２９】ガスノズル突起部１２の構造としては、気
体の入口部で冷却塔に導入される気体と冷却媒体とが直
接接触しなければ特に限定されない。具体的には、例え
ば、図３に示すような冷却塔と配管との接続部分の上か
ら下まで覆うような半円状の覆いを設ける他、配管の大
きさに合わせて管状の突起部を設けてもよく、その他の
形状にしてもよい。また、その大きさも、気体の入口部
の冷却塔壁、配管壁面への高沸点不純物の析出が抑制で
きれば特に限定されないが、冷却塔と配管との接続部分
の一部を覆うような突起部を設けるよりも全体を覆うよ
うな突起部を設けることが好ましい。The structure of the gas nozzle projection 12 is not particularly limited as long as the gas introduced into the cooling tower at the gas inlet does not come into direct contact with the cooling medium. Specifically, for example, in addition to providing a semi-circular cover that covers the connecting portion between the cooling tower and the pipe as shown in FIG. 3 from the top to the bottom, a tubular protrusion is provided according to the size of the pipe. It may be provided or may have another shape. Further, the size thereof is not particularly limited as long as it can suppress precipitation of high-boiling-point impurities on the wall of the cooling tower at the inlet of the gas and the wall surface of the pipe, but a protrusion that covers a part of the connecting portion between the cooling tower and the pipe is provided. It is preferable to provide a protrusion that covers the whole rather than providing it.
【００３０】そして、ガスノズル突起部１２の内側（覆
いの下側）に析出する高沸点不純物については、ガスノ
ズル突起部１２内に設置されている高沸物除去用ガスラ
イン１３の高沸物除去用ガススプレーノズル１４より高
沸物除去用ガスを吹き付け、析出した高沸点不純物を除
去する。高沸物除去用ガスは、図３に示すように、ガス
ノズル突起部１２の内側の面（覆いの下側の面）にプロ
セスガス流の上流側から吹き付けることが好ましい。The high-boiling-point impurities deposited inside the gas nozzle projection 12 (under the cover) are for removing high-boiling substances in the high-boiling-point removing gas line 13 installed in the gas nozzle projection 12. A gas for removing high boiling substances is sprayed from the gas spray nozzle 14 to remove the precipitated high boiling impurities. As shown in FIG. 3, it is preferable that the high-boiling-point removing gas is blown from the upstream side of the process gas flow onto the inner surface (the lower surface of the cover) of the gas nozzle protrusion 12.
【００３１】ガスノズル突起部１２内に設置されている
高沸物除去用ガスラインおよび高沸物除去用ガススプレ
ーノズルの構造および個数については特に限定されない
が、析出する高沸点不純物全面に吹き付けられるような
構造および個数が好ましい。The structure and number of the high boiling point removing gas line and the high boiling point removing gas spray nozzle installed in the gas nozzle projection 12 are not particularly limited, but the high boiling point impurities are sprayed over the entire surface. Different structures and numbers are preferred.
【００３２】吹き付ける高沸物除去用ガス、好ましくは
水蒸気については、析出する高沸点不純物を除去できる
エネルギーをもっていることが好ましく、具体的には、
高沸物除去用ガスのもつエネルギーが大きくて高沸点不
純物を十分除去できるので０．３ＭＰａ以上、特に２Ｍ
Ｐａ以上が好ましい。また、経済的という点から２０Ｍ
Ｐａ以下、特に８ＭＰａ以下が好ましい。It is preferable that the high-boiling-point removing gas, preferably steam, to be sprayed has energy capable of removing the high-boiling-point impurities that precipitate.
Since the high boiling point gas has a large energy and can sufficiently remove high boiling impurities, it is 0.3 MPa or more, especially 2 M
Pa or more is preferable. Also, 20M from the economical point of view
Pa or less, especially 8 MPa or less is preferable.
【００３３】吹き付ける高沸物除去用ガスの温度は特に
限定されないが、通常、加熱する必要はない。The temperature of the high boiling point removing gas to be sprayed is not particularly limited, but it is usually not necessary to heat it.
【００３４】イソブチレンおよび／またはtert-ブチル
アルコールの接触気相酸化等により得られるメタクロレ
インおよび／またはメタクリル酸を含む反応ガス、メタ
クロレインの接触気相酸化等により得られるメタクリル
酸を含む反応ガスから目的生成物であるメタクロレイン
および／またはメタクリル酸を凝縮させて捕集する場
合、また、プロピレンの接触気相酸化等により得られる
アクロレインおよび／またはアクリル酸を含む反応ガス
から目的生成物であるアクロレインおよび／またはアク
リル酸を凝縮させて捕集する場合、高沸物除去用ガスと
して、原料ガスの接触気相酸化により目的生成物を製造
する際の酸化反応熱を回収して得られる水蒸気を用いる
ことも可能である。From a reaction gas containing methacrolein and / or methacrylic acid obtained by catalytic vapor phase oxidation of isobutylene and / or tert-butyl alcohol, a reaction gas containing methacrylic acid obtained by catalytic vapor phase oxidation of methacrolein, etc. When the target product methacrolein and / or methacrylic acid is condensed and collected, the target product acrolein is obtained from the reaction gas containing acrolein and / or acrylic acid obtained by catalytic gas phase oxidation of propylene. In the case of condensing and / or collecting acrylic acid, water vapor obtained by recovering the heat of oxidation reaction when a target product is produced by catalytic vapor phase oxidation of a raw material gas is used as a high boiling point removal gas. It is also possible.
【００３５】高沸物除去用ガスは連続的に吹き付けても
かまわないが、断続的に吹き付けることが好ましく、冷
却塔の気体の入口部における圧力損失を測定し、所定の
圧力損失に達したときに高沸物除去用ガスを吹き付ける
ことが特に好ましい。不必要に水等の高沸物除去用ガス
を系内に入れると、凝縮させた目的物の回収工程などの
後の工程、例えば、（メタ）アクロレインおよび／また
は（メタ）アクリル酸の吸収・回収工程の負荷が増大し
てくる場合もあるからである。The high boiling point removing gas may be continuously blown, but it is preferable to intermittently blow it. When the pressure loss at the gas inlet of the cooling tower is measured and a predetermined pressure loss is reached, It is particularly preferable to blow a high boiling point removing gas onto the. When a high boiling point removal gas such as water is unnecessarily introduced into the system, a step after the step of collecting the condensed target substance, for example, absorption of (meth) acrolein and / or (meth) acrylic acid This is because the load of the recovery process may increase.
【００３６】ここで、圧力損失とは、ガス導入ライン
（凝縮対象物を含む気体が導入される配管）内の圧力と
冷却塔の気相部の圧力との差をいう。Here, the pressure loss means the difference between the pressure in the gas introduction line (pipe for introducing the gas containing the object to be condensed) and the pressure in the vapor phase portion of the cooling tower.
【００３７】高沸物除去用ガスを吹き付けるときの冷却
塔の気体の入口部における圧力損失としては、運転開始
時の圧力損失の値からの上昇値が０．３ｋＰａ以上であ
ることが好ましく、運転開始時の圧力損失の値からの上
昇値が４ｋＰａ以下、特に２ｋＰａ以下であることが好
ましい。気体の入口部における圧力損失の運転開始時か
らの上昇値がこの範囲より小さければ、ほとんど高沸点
不純物は析出しておらず、プロセス運転上特に問題にな
ることはあまりない。また、気体の入口部における圧力
損失の運転開始時からの上昇値があまりに大きくなり過
ぎると、高沸物除去用ガスを吹き付ける効果が得られに
くくなることがあり、析出した高沸点不純物を十分に除
去できない場合がある。The pressure loss at the gas inlet of the cooling tower when the high boiling point gas is blown is preferably 0.3 kPa or more from the pressure loss value at the start of operation. It is preferable that the increase value from the pressure loss value at the start is 4 kPa or less, and particularly 2 kPa or less. If the value of increase in pressure loss at the gas inlet from the start of operation is smaller than this range, almost no high-boiling point impurities are deposited, and there is not much problem in process operation. Further, if the increase value of the pressure loss at the gas inlet from the start of operation becomes too large, it may be difficult to obtain the effect of spraying the high-boiling-point removing gas, and the precipitated high-boiling-point impurities may be insufficient. Sometimes it cannot be removed.
【００３８】高沸物除去用ガスを吹き付ける時間は、十
分な高沸物除去用ガス吹き付けの効果が得られ、析出し
た高沸点不純物を十分に除去できるので３秒以上、特に
１０秒以上が好ましい。また、高沸物除去用ガスを吹き
付ける時間は、１８００秒以下、特に３００秒以下が好
ましい。高沸物除去用ガスを吹き付ける時間があまりに
長くなると、不必要に水蒸気等の高沸物除去用ガスを系
内に入れることになり、凝縮させた目的物の回収工程な
どの後の工程、例えば、（メタ）アクロレインおよび／
または（メタ）アクリル酸の吸収・回収工程の負荷が増
大してくることがある。The time for blowing the high boiling point removing gas is preferably 3 seconds or more, particularly 10 seconds or more, because the effect of blowing the high boiling point removing gas is sufficiently obtained and the precipitated high boiling point impurities can be sufficiently removed. . Further, the time for blowing the high boiling point removing gas is preferably 1800 seconds or less, and particularly preferably 300 seconds or less. If the time for spraying the high boiling point removing gas becomes too long, the high boiling point removing gas such as water vapor is unnecessarily put into the system, and the subsequent step such as the step of collecting the condensed target object, for example, , (Meth) acrolein and /
Alternatively, the load of the (meth) acrylic acid absorption / recovery process may increase.
【００３９】ガス導入ライン５は、冷却塔に導入される
気体中の高沸点不純物の析出を防ぐためにその気体の露
点以上に保温することが好ましい。特に、イソブチレン
および／またはtert-ブチルアルコールの接触気相酸化
等により得られるメタクロレインおよび／またはメタク
リル酸を含む反応ガス、メタクロレインの接触気相酸化
等により得られるメタクリル酸を含む反応ガス、また、
プロピレンの接触気相酸化等により得られるアクロレイ
ンおよび／またはアクリル酸を含む反応ガスを凝縮する
場合、反応器から冷却塔までの反応ガスの通るライン
（ガス導入ライン５）は、反応ガス中の高沸点不純物の
析出を防ぐために反応ガスの露点以上、具体的には、２
００〜２５０℃以上に保温することが好ましい。The gas introduction line 5 is preferably kept at a temperature above the dew point of the gas in order to prevent the precipitation of high boiling impurities in the gas introduced into the cooling tower. In particular, a reaction gas containing methacrolein and / or methacrylic acid obtained by catalytic gas phase oxidation of isobutylene and / or tert-butyl alcohol, a reaction gas containing methacrylic acid obtained by catalytic gas phase oxidation of methacrolein, and the like, ,
When condensing the reaction gas containing acrolein and / or acrylic acid obtained by catalytic gas phase oxidation of propylene, etc., the line (gas introduction line 5) through which the reaction gas passes from the reactor to the cooling tower is high in the reaction gas. In order to prevent precipitation of boiling point impurities, the dew point of the reaction gas should be higher than the dew point, specifically, 2
It is preferable to keep the temperature at 00 to 250 ° C or higher.
【００４０】また、配管表面あるいは冷却塔内部への突
起表面は、バス研磨仕上げ等を行ってもかまわない。Further, the surface of the pipe or the surface of the protrusion to the inside of the cooling tower may be subjected to a bath polishing finish or the like.
【００４１】高沸物除去用ガスの吹き付けにより除去し
た高沸点不純物は、通常、気体を凝縮した液（凝縮対象
物を主成分とする溶液）にはほとんど溶解しない。その
ため、図２に示すように、通常、凝縮液循環ポンプのサ
クションに設置したストレーナー４等により高沸点不純
物は系外に除去する。The high-boiling-point impurities removed by spraying the high-boiling-point-removing gas are usually hardly dissolved in the liquid in which the gas is condensed (the solution containing the substance to be condensed as the main component). Therefore, as shown in FIG. 2, high-boiling impurities are usually removed out of the system by a strainer 4 or the like installed in the suction of the condensate circulation pump.
【００４２】ストレーナーについては特に限定はなく、
内部に凝縮液から高沸点不純物を捕集できる目開きのス
クリーンを設置してあればよい。また、ストレーナーの
洗浄作業を行うため、２系列設けることが好ましく、容
易に洗浄できる構造、例えば逆洗式のストレーナーが好
ましい。The strainer is not particularly limited,
A screen with an opening that can collect high-boiling-point impurities from the condensate may be installed inside. Further, in order to perform the cleaning work of the strainer, it is preferable to provide two series, and a structure that can be easily cleaned, for example, a backwash strainer is preferable.
【００４３】高沸点不純物を除去した凝縮対象物を含む
凝縮液は、凝縮水循環ポンプによって凝縮液抜き出しラ
インより次の工程へ送られる。凝縮対象物が（メタ）ア
クロレインおよび／または（メタ）アクリル酸である場
合、通常、この凝縮液は蒸留や抽出操作等の手段で精製
されて目的生成物である（メタ）アクロレインおよび／
または（メタ）アクリル酸が得られる。The condensate containing the substance to be condensed from which high-boiling point impurities have been removed is sent to the next step from the condensate extraction line by the condensed water circulation pump. When the substance to be condensed is (meth) acrolein and / or (meth) acrylic acid, this condensate is usually purified by a means such as distillation or extraction operation to obtain the target product (meth) acrolein and / or
Alternatively, (meth) acrylic acid is obtained.
【００４４】[0044]
【実施例】［実施例１］反応器においてtert-ブチルア
ルコールの接触気相酸化を行ない、メタクロレインを含
む反応器出口ガス（反応ガス）を図２に示すような冷却
塔１へガス導入ライン５より導入した。この反応ガスの
組成は、メタクロレイン４．７モル％、水１６．９モル
％、非凝縮性ガス７７．７モル％、その他(高沸点不純
物を含む)０．７モル％であった。また、この反応ガス
を冷却塔に導く前に熱交換器により２００℃に冷却し
た。そのときの反応ガスの圧力はゲージ圧で４０ｋＰａ
であった。[Example] [Example 1] A catalytic gas phase oxidation of tert-butyl alcohol was carried out in a reactor, and a reactor outlet gas (reaction gas) containing methacrolein was introduced into a cooling tower 1 as shown in FIG. It was introduced from 5. The composition of this reaction gas was 4.7 mol% of methacrolein, 16.9 mol% of water, 77.7 mol% of non-condensable gas, and 0.7 mol% of other (including high boiling point impurities). The reaction gas was cooled to 200 ° C. by a heat exchanger before being introduced into the cooling tower. The pressure of the reaction gas at that time is 40 kPa in gauge pressure.
Met.
【００４５】運転を開始した当初の冷却塔の気体の入口
部における圧力損失は０．４ｋＰａであった。運転中
は、凝縮液の循環量を１０００〜１４００Ｌ／Ｈ、凝縮
液の温度を５０〜５５℃、冷却塔から抜き出される反応
ガスの温度を６０〜６５℃となるようにし、熱交換器３
で冷却した凝縮液を冷却塔内にスプレーした。At the beginning of the operation, the pressure loss at the gas inlet of the cooling tower was 0.4 kPa. During the operation, the circulation amount of the condensate is set to 1000 to 1400 L / H, the temperature of the condensate is set to 50 to 55 ° C., the temperature of the reaction gas extracted from the cooling tower is set to 60 to 65 ° C., and the heat exchanger 3
The condensate cooled in 1. was sprayed into the cooling tower.
【００４６】２０日間運転したところで冷却塔の気体の
入口部における圧力損失が１．６ｋＰａ（運転開始時か
らの上昇値１．２ｋＰａ）となったので、水蒸気スプレ
ーノズル１４より４ＭＰａの水蒸気を１２０秒間吹き付
けた。その結果、冷却塔の気体の入口部における圧力損
失は０．４ｋＰａとなった。After operating for 20 days, the pressure loss at the gas inlet of the cooling tower was 1.6 kPa (the increased value of 1.2 kPa from the start of the operation), so 4 MPa of steam was sprayed from the steam spray nozzle 14 for 120 seconds. Sprayed. As a result, the pressure loss at the gas inlet of the cooling tower was 0.4 kPa.
【００４７】さらに１８日間運転したところで冷却塔の
気体の入口部における圧力損失が１．６ｋＰａ（運転開
始時からの上昇値１．２ｋＰａ）となったので、水蒸気
スプレーノズル１４より４ＭＰａの水蒸気を１２０秒間
吹き付けた。その結果、冷却塔の気体の入口部における
圧力損失は０．５ｋＰａとなった。After a further 18 days of operation, the pressure loss at the gas inlet of the cooling tower was 1.6 kPa (an increase of 1.2 kPa from the start of the operation). Sprayed for seconds. As a result, the pressure loss at the gas inlet of the cooling tower was 0.5 kPa.
【００４８】このように冷却塔の気体の入口部における
圧力損失が所定の圧力に達したところで水蒸気スプレー
ノズルより間欠的に水蒸気を吹き付け、反応ガス入口部
に付着した高沸点不純物を除去しながら７００日以上連
続的にこのプロセスを運転することができた。なお、運
転中、２０日に１回程度、ストレーナー４の切り替えと
洗浄作業とを行った。As described above, when the pressure loss at the gas inlet of the cooling tower reaches a predetermined pressure, water vapor is sprayed intermittently from the water vapor spray nozzle to remove the high boiling impurities adhering to the reaction gas inlet 700 It was possible to operate this process continuously for more than a day. During the operation, the strainer 4 was switched and the cleaning work was performed about once every 20 days.
【００４９】［比較例１］冷却塔の気体の入口部におけ
る間欠的な水蒸気の吹き付けを行わない以外は実施例１
と同じ条件でプロセスを運転したところ、運転開始４３
日目で冷却塔の気体の入口部における圧力損失は３ｋＰ
ａとなり、さらに運転を続行した結果、８２日目に冷却
塔の気体の入口部における圧力損失が１０ｋＰａを越
え、連続運転が困難になったので運転を停止した。運転
停止後に冷却塔内部を確認したところ、冷却塔の気体の
入口部のほとんどが析出した高沸点不純物により閉塞し
ていた。[Comparative Example 1] Example 1 except that intermittent spraying of water vapor was not performed at the gas inlet of the cooling tower.
When the process was operated under the same conditions as above, operation started 43
On the first day, the pressure loss at the gas inlet of the cooling tower is 3 kP
As a result, the operation was continued, and as a result, the pressure loss at the gas inlet of the cooling tower exceeded 10 kPa on the 82nd day, and continuous operation became difficult, so the operation was stopped. When the inside of the cooling tower was checked after the operation was stopped, most of the gas inlet portion of the cooling tower was blocked by the precipitated high boiling impurities.
【００５０】［実施例２］反応器においてtert-ブチル
アルコールの接触気相酸化を行ない、メタクロレインお
よび／またはメタクリル酸を含む反応器出口ガス（反応
ガス）を図２に示すような冷却塔１へガス導入ライン５
より導入した。この反応ガスの組成は、メタクロレイン
０．６モル％、メタクリル酸３．０モル％、水１３．７
モル％、非凝縮性ガス８２．７モル％、その他(高沸点
不純物を含む)０．１モル％であった。また、この反応
ガスを冷却塔に導く前に熱交換器により２５０℃に冷却
した。そのときの反応ガスの圧力はゲージ圧で３８ｋＰ
ａであった。[Example 2] A catalytic gas phase oxidation of tert-butyl alcohol was carried out in the reactor, and the reactor outlet gas (reaction gas) containing methacrolein and / or methacrylic acid was cooled by a cooling tower 1 as shown in FIG. Gas introduction line 5
Introduced more. The composition of this reaction gas was as follows: methacrolein 0.6 mol%, methacrylic acid 3.0 mol%, water 13.7
It was 8 mol% of non-condensable gas and 0.1 mol% of others (including high boiling point impurities). The reaction gas was cooled to 250 ° C. by a heat exchanger before being introduced into the cooling tower. The pressure of the reaction gas at that time is 38 kP in gauge pressure.
It was a.
【００５１】運転を開始した当初の冷却塔の気体の入口
部における圧力損失は０．４ｋＰａであった。運転中
は、凝縮液の循環量を１０００〜１４００Ｌ／Ｈ、凝縮
液の温度を４０〜４５℃、冷却塔から抜き出される反応
ガスの温度を５０〜５５℃となるようにし、熱交換器３
で冷却した凝縮液を冷却塔内にスプレーした。At the beginning of the operation, the pressure loss at the gas inlet of the cooling tower was 0.4 kPa. During the operation, the circulation amount of the condensate is set to 1000 to 1400 L / H, the temperature of the condensate is set to 40 to 45 ° C., the temperature of the reaction gas extracted from the cooling tower is set to 50 to 55 ° C., and the heat exchanger 3
The condensate cooled in 1. was sprayed into the cooling tower.
【００５２】４０日間運転したところで冷却塔の気体の
入口部における圧力損失が２ｋＰａ（運転開始時からの
上昇値１．６ｋＰａ）となったので、水蒸気スプレーノ
ズル１４より４ＭＰａの水蒸気を１２０秒間吹き付け
た。その結果、冷却塔の気体の入口部における圧力損失
は０．４ｋＰａとなった。After operating for 40 days, the pressure loss at the gas inlet of the cooling tower was 2 kPa (increase value of 1.6 kPa from the start of operation), so 4 MPa of steam was sprayed from the steam spray nozzle 14 for 120 seconds. . As a result, the pressure loss at the gas inlet of the cooling tower was 0.4 kPa.
【００５３】さらに３６日間運転したところで冷却塔の
気体の入口部における圧力損失が２ｋＰａ（運転開始時
からの上昇値１．６ｋＰａ）となったので、水蒸気スプ
レーノズル１４より４ＭＰａの水蒸気を１２０秒間吹き
付けた。その結果、冷却塔の気体の入口部における圧力
損失は０．４ｋＰａとなった。After operating for another 36 days, the pressure loss at the gas inlet of the cooling tower was 2 kPa (increase value of 1.6 kPa from the start of operation), so 4 MPa of steam was sprayed from the steam spray nozzle 14 for 120 seconds. It was As a result, the pressure loss at the gas inlet of the cooling tower was 0.4 kPa.
【００５４】このように冷却塔の気体の入口部における
圧力損失が所定の圧力に達したところで水蒸気スプレー
ノズルより間欠的に水蒸気を吹き付け、反応ガス入口部
に付着した高沸点不純物を除去しながら７００日以上連
続的にこのプロセスを運転することができた。なお、運
転中、４０日に１回程度、ストレーナー４の切り替えと
洗浄作業とを行った。Thus, when the pressure loss at the gas inlet of the cooling tower reaches a predetermined pressure, steam is intermittently sprayed from the steam spray nozzle to remove the high boiling point impurities adhering to the reaction gas inlet 700 It was possible to operate this process continuously for more than a day. During the operation, the strainer 4 was switched and the cleaning work was performed about once every 40 days.
【００５５】［比較例２］冷却塔の気体の入口部におけ
る間欠的な水蒸気の吹き付けを行わない以外は実施例２
と同じ条件でプロセスを運転したところ、運転開始６５
日目で冷却塔の気体の入口部における圧力損失は３ｋＰ
ａとなり、さらに運転を続行した結果、１２０日目に冷
却塔の気体の入口部における圧力損失が１０ｋＰａを越
え、連続運転が困難になったので運転を停止した。運転
停止後に冷却塔内部を確認したところ、冷却塔の気体の
入口部のほとんどが析出した高沸点不純物により閉塞し
ていた。[Comparative Example 2] Example 2 was repeated except that intermittent spraying of water vapor was not performed at the gas inlet of the cooling tower.
When the process was operated under the same conditions as
On the first day, the pressure loss at the gas inlet of the cooling tower is 3 kP
As a result, the operation was continued, and as a result, the pressure loss at the gas inlet of the cooling tower exceeded 10 kPa on the 120th day, and continuous operation became difficult, so the operation was stopped. When the inside of the cooling tower was checked after the operation was stopped, most of the gas inlet portion of the cooling tower was blocked by the precipitated high boiling impurities.
【００５６】[0056]
【発明の効果】本発明によれば、凝縮対象物よりも沸点
が高い不純物を含む気体を冷却塔で凝縮する際に冷却塔
入口部に生じる高沸点不純物の析出をプロセス運転中に
簡便に、また、後の工程の負荷を増大することなく除去
し、プロセスを長期間安定に運転できる。According to the present invention, when a gas containing impurities having a boiling point higher than that of an object to be condensed is condensed in the cooling tower, precipitation of high-boiling impurities generated at the inlet of the cooling tower can be easily carried out during the process operation. Further, the process can be removed without increasing the load of the subsequent steps, and the process can be stably operated for a long time.
【図面の簡単な説明】[Brief description of drawings]
【図１】一般的な冷却塔の概略図である。FIG. 1 is a schematic view of a general cooling tower.
【図２】本発明を実施するためのプロセスの一例であ
り、本発明で用いる冷却塔の概略図である。FIG. 2 is an example of a process for carrying out the present invention and is a schematic view of a cooling tower used in the present invention.
【図３】図２に示す冷却塔の気体の入口部の拡大図であ
る。3 is an enlarged view of a gas inlet of the cooling tower shown in FIG.
１ 冷却塔 ２ 凝縮水循環ポンプ ３ 熱交換器 ４ ストレーナー ５ ガス導入ライン ６ 凝縮液ライン ７ 凝縮液抜き出しライン ８ 凝縮液循環ライン ９ 反応ガス抜き出しライン １０ ガス入口ノズル部分(突起なし) １１ ガス入口ノズル部分(突起あり) １２ ガスノズル突起部 １３ 高沸物除去用ガスライン １４ 高沸物除去用ガススプレーノズル １５ 高沸物除去用ガス導入部 1 cooling tower 2 Condensed water circulation pump 3 heat exchanger 4 strainers 5 gas introduction line 6 Condensate line 7 Condensate extraction line 8 Condensate circulation line 9 Reaction gas extraction line 10 Gas inlet nozzle part (no protrusion) 11 Gas inlet nozzle (with protrusion) 12 Gas nozzle protrusion 13 High boiling point removal gas line 14 Gas spray nozzle for high boiling point removal 15 Gas introduction part for high boiling point removal
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ テーマコート゛(参考） Ｃ０７Ｃ 51/235 Ｃ０７Ｃ 51/235 51/25 51/25 51/43 51/43 57/055 57/055 Ｂ Ｆ２８Ｂ 9/08 Ｆ２８Ｂ 9/08 (72)発明者 安藤 佳正 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 山近 肇 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 Ｆターム(参考） 4D076 AA01 AA16 AA24 BC12 BC25 CB02 CD21 CD42 EA02Z EA14Z EA23Z FA02 FA12 JA02 4H006 AA02 AC45 AC46 AD18 BS10─────────────────────────────────────────────────── ─── Continued Front Page (51) Int.Cl. 7 Identification Code FI Theme Coat (Reference) C07C 51/235 C07C 51/235 51/25 51/25 51/43 51/43 57/055 57/055 B F28B 9/08 F28B 9/08 (72) Inventor Yoshimasa Ando 20-1 Miyuki-cho, Otake-shi, Hiroshima Mitsubishi Rayon Co., Ltd. Otake Works (72) Inventor Hajime Yamanaka 20-1 Miyuki-cho, Otake-shi, Hiroshima No. Mitsubishi Rayon Co., Ltd. O-Take F-term (reference) 4D076 AA01 AA16 AA24 BC12 BC25 CB02 CD21 CD42 EA02Z EA14Z EA23Z FA02 FA12 JA02 4H006 AA02 AC45 AC46 AD18 BS10
Claims (6)
む気体を冷却塔に導入し、冷却凝縮する方法であって、
前記冷却塔の気体の入口部に連続的または断続的に高沸
物除去用ガスを吹き付けることを特徴とする気体の凝縮
方法。1. A method of introducing a gas containing an impurity having a boiling point higher than that of an object to be condensed into a cooling tower and cooling and condensing the method.
A method for condensing a gas, characterized in that a gas for removing a high boiling point is continuously or intermittently blown to the gas inlet of the cooling tower.
る気体と冷却媒体とが直接接触するのを防ぐための冷却
塔内部への突起部が設けられていることを特徴とする請
求項１に記載の気体の凝縮方法。2. The gas inlet portion of the cooling tower is provided with a protrusion to the inside of the cooling tower for preventing direct contact between the introduced gas and the cooling medium. Item 2. A method for condensing a gas according to Item 1.
を噴出するノズルが設置されており、このノズルから高
沸物除去用ガスを前記突起部の内側に吹き付けることを
特徴とする請求項２に記載の気体の凝縮方法。3. A nozzle for ejecting the high-boiling-point removing gas is installed in the protrusion, and the high-boiling-point removing gas is blown to the inside of the protrusion from the nozzle. Item 3. A method for condensing a gas according to Item 2.
運転開始時の値から０．３〜４ｋＰａ上昇したときに、
前記冷却塔の気体の入口部に高沸物除去用ガスを３〜１
８００秒間吹き付けることを特徴とする請求項１〜３の
いずれかに記載の気体の凝縮方法。4. When the pressure loss at the gas inlet of the cooling tower rises by 0.3 to 4 kPa from the value at the start of operation,
A high boiling point removing gas is added to the gas inlet of the cooling tower in an amount of 3 to 1
The method for condensing gas according to claim 1, wherein the gas is sprayed for 800 seconds.
とを特徴とする請求項１〜４のいずれかに記載の気体の
凝縮方法。5. The method for condensing gas according to claim 1, wherein the high boiling point removing gas is water vapor.
および／または（メタ）アクリル酸であることを特徴と
する請求項１〜５のいずれかに記載の気体の凝縮方法。6. The method for condensing a gas according to claim 1, wherein the condensation object is (meth) acrolein and / or (meth) acrylic acid.
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|---|---|---|---|
| JP2001308549A JP4147015B2 (en) | 2001-10-04 | 2001-10-04 | Gas condensation method |
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|---|---|---|---|
| JP2001308549A JP4147015B2 (en) | 2001-10-04 | 2001-10-04 | Gas condensation method |
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| Publication Number | Publication Date |
|---|---|
| JP2003112001A true JP2003112001A (en) | 2003-04-15 |
| JP4147015B2 JP4147015B2 (en) | 2008-09-10 |
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|---|---|---|---|
| JP2001308549A Expired - Fee Related JP4147015B2 (en) | 2001-10-04 | 2001-10-04 | Gas condensation method |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005298384A (en) * | 2004-04-09 | 2005-10-27 | Asahi Kasei Chemicals Corp | Method for cooling reaction gas containing (meth) acrylic acid and / or (meth) acrolein |
| JP2007217403A (en) * | 2006-01-20 | 2007-08-30 | Nippon Shokubai Co Ltd | Purification method and production method of acrylic acid |
| JP2009537790A (en) * | 2006-05-23 | 2009-10-29 | バイエル・マテリアルサイエンス・アクチェンゲゼルシャフト | Device for gas cooling with formation of corrosive condensation products |
| JP2010503692A (en) * | 2006-09-15 | 2010-02-04 | ダウ グローバル テクノロジーズ インコーポレイティド | Acrylic acid production method |
| JP2014177417A (en) * | 2013-03-14 | 2014-09-25 | Mitsubishi Chemicals Corp | Method for manufacturing conjugated diene |
| JP2014189543A (en) * | 2013-03-28 | 2014-10-06 | Mitsubishi Chemicals Corp | Method for manufacturing conjugated diene |
| EP2930426A1 (en) * | 2014-04-11 | 2015-10-14 | Hans Full | Waste heat exchanger and method for recovery of heat from waste gases |
| JP2016112516A (en) * | 2014-12-16 | 2016-06-23 | Ｊｆｅケミカル株式会社 | Method for treating excess ammoniacal liquor |
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2001
- 2001-10-04 JP JP2001308549A patent/JP4147015B2/en not_active Expired - Fee Related
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005298384A (en) * | 2004-04-09 | 2005-10-27 | Asahi Kasei Chemicals Corp | Method for cooling reaction gas containing (meth) acrylic acid and / or (meth) acrolein |
| JP2007217403A (en) * | 2006-01-20 | 2007-08-30 | Nippon Shokubai Co Ltd | Purification method and production method of acrylic acid |
| JP2009537790A (en) * | 2006-05-23 | 2009-10-29 | バイエル・マテリアルサイエンス・アクチェンゲゼルシャフト | Device for gas cooling with formation of corrosive condensation products |
| JP2010503692A (en) * | 2006-09-15 | 2010-02-04 | ダウ グローバル テクノロジーズ インコーポレイティド | Acrylic acid production method |
| JP2014177417A (en) * | 2013-03-14 | 2014-09-25 | Mitsubishi Chemicals Corp | Method for manufacturing conjugated diene |
| JP2014189543A (en) * | 2013-03-28 | 2014-10-06 | Mitsubishi Chemicals Corp | Method for manufacturing conjugated diene |
| EP2930426A1 (en) * | 2014-04-11 | 2015-10-14 | Hans Full | Waste heat exchanger and method for recovery of heat from waste gases |
| JP2016112516A (en) * | 2014-12-16 | 2016-06-23 | Ｊｆｅケミカル株式会社 | Method for treating excess ammoniacal liquor |
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