JPH0629204B2 - Method for producing high-concentration formalin - Google Patents
Method for producing high-concentration formalinInfo
- Publication number
- JPH0629204B2 JPH0629204B2 JP59201833A JP20183384A JPH0629204B2 JP H0629204 B2 JPH0629204 B2 JP H0629204B2 JP 59201833 A JP59201833 A JP 59201833A JP 20183384 A JP20183384 A JP 20183384A JP H0629204 B2 JPH0629204 B2 JP H0629204B2
- Authority
- JP
- Japan
- Prior art keywords
- absorption tower
- concentration
- formalin
- temperature
- weight
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Description
【発明の詳細な説明】 （産業上の利用分野） 本発明はメタノール、空気、水、ホルムアルデヒドから
成るガスを銀触媒と接触させてホルマリン（ホルムアル
デヒド水溶液）を製造する方法の改良に係わるもので、
複数直列より成る吸収塔の第１吸収塔において、第１吸
収塔液と反応生成ガスを向流接触させて高濃度ホルマリ
ンを製造する方法に関するものである。TECHNICAL FIELD The present invention relates to an improvement in a method for producing formalin (formaldehyde aqueous solution) by bringing a gas consisting of methanol, air, water and formaldehyde into contact with a silver catalyst.
The present invention relates to a method for producing high-concentration formalin by countercurrently contacting a first absorption tower liquid and a reaction product gas in a first absorption tower of an absorption tower composed of a plurality of series.
（従来技術およびその問題点） 一般に工業用に使用されているホルムアルデヒド水溶液
は、メタノールと空気を主原料として、水蒸気、不活性
ガスまたはホルムアルデヒドを添加した原料ガスを、銀
触媒（メタノール過剰法）あるいは鉄・モリブデン触媒
（空気過剰法）と接触させた後、得られる反応生成ガス
を複数直列の吸収塔へ導き、吸収塔で水またはホルマリ
ンに吸収凝縮させてホルマリンを製造している。(Prior art and its problems) Generally, an aqueous formaldehyde solution which is used for industrial purposes uses a raw material gas obtained by adding water vapor, an inert gas or formaldehyde to methanol and air as main raw materials, and using a silver catalyst (methanol excess method) or After contacting with an iron / molybdenum catalyst (excess air method), the obtained reaction product gas is guided to a plurality of absorption towers in series, and absorbed or condensed into water or formalin in the absorption tower to produce formalin.
しかし、従来のホルマリンはその組成の半分以上が水で
あり、ホルマリンを輸送する上でかなり不経済である。
またホルマリンの用途の大半は合板用尿素樹脂接着剤、
フェノール樹脂等の原料であるが、近年これらの樹脂は
その製品濃度を高くする傾向にあり、従つて、原料であ
るホルマリン中のホルムアルデヒド濃度５０重量％以上
と云う、いわゆる高濃度ホルマリンの要求が強くなつて
きた。また上記樹脂用ホルマリン以外の分野でも用途の
よつてはホルマリンの高濃度化の要求は強くなつてきて
いる。However, more than half of the composition of conventional formalin is water, which is considerably uneconomical in transporting formalin.
Most of the uses of formalin are urea resin adhesives for plywood,
Although they are raw materials for phenolic resins and the like, these resins tend to increase the product concentration in recent years, and therefore, there is a strong demand for so-called high-concentration formalin, which means that the concentration of formaldehyde in the raw material formalin is 50% by weight or more. I came here. Further, in fields other than the above-mentioned formalin for resins, there is a strong demand for higher concentration of formalin depending on applications.
この様な高濃度ホルマリンを得る方法としては、従来は
ホルムアルデヒド濃度５０重量％以下のホルマリンを、
減圧濃縮することによつて得られていた。しかし、この
方法はホルマリン製造設備とは別に濃縮設備、吸収塔お
よび吸収塔付帯設備、真空ポンプ等の設備が必要であ
り、且つホルマリン濃縮用蒸気も使用するので製造コス
トが高いという問題点がある。近年は高濃度ホルマリン
を製造する方法として、上記の様に減圧濃縮法によらず
ホルマリン製造工程で直接製造する方法が開発されてお
り、例えばメタノールと空気の反応によつて得られる反
応生成ガスと吸収塔で得られる低濃度ホルマリンを反応
器と吸収塔の間で接触させ低濃度ホルマリンを高濃度ホ
ルマリンとする方法（特開昭４９−１０１３１２）、反
応生成ガスの１部を冷却して低濃度ホルマリンとして１
部を凝縮分離した後、残存反応生成ガスを吸収させて高
濃度ホルマリンとする方法（特開昭５８−１４４３３
９）などがある。特開昭４９−１０１３１２の方法は、
低濃度ホルマリンを１５０〜７００℃の雰囲気で反応生
成ガスと接触させるため、得られる高濃度ホルマリンの
温度が高くなり、１部は重合が進みパラホルムアルデヒ
ドが生成したり、またカニッツァロ反応により高濃度ホ
ルマリン中のギ酸濃度が上昇する等の問題点がある。特
開昭５８−１４４３３９の方法では、反応生成ガスの冷
却器に用いる冷却水の温度について規定していないが、
冷却水温度が低い場合、冷却器の伝熱面で反応生成ガス
が急冷されて伝熱面にパラホルムアルデヒドが生成し、
経日的に冷却器の伝熱面の汚れ係数が大きくなる等の問
題点が考えられる。As a method for obtaining such a high-concentration formalin, conventionally, formalin having a formaldehyde concentration of 50% by weight or less is used.
It was obtained by concentrating under reduced pressure. However, this method requires equipment such as a concentration equipment, an absorption tower and equipment attached to the absorption tower, a vacuum pump, etc. in addition to the formalin production equipment, and has a problem that the production cost is high because the vapor for formalin enrichment is also used. . In recent years, as a method for producing high-concentration formalin, a method of directly producing in the formalin production step without the vacuum concentration method as described above has been developed, and for example, a reaction product gas obtained by the reaction of methanol and air and A method in which the low-concentration formalin obtained in the absorption tower is brought into contact between the reactor and the absorption tower to convert the low-concentration formalin into high-concentration formalin (Japanese Patent Laid-Open No. 49-101312), and a part of the reaction product gas is cooled to reduce the concentration. 1 as formalin
After the parts are condensed and separated, the residual reaction product gas is absorbed to form high-concentration formalin (JP-A-58-14433).
9) etc. The method of JP-A-49-101312 is
Since low-concentration formalin is brought into contact with the reaction product gas in an atmosphere of 150 to 700 ° C., the temperature of the high-concentration formalin obtained becomes high, and part of the polymerization proceeds to form paraformaldehyde, and the high-concentration formalin is produced by the Cannizzaro reaction. There is a problem that the concentration of formic acid in the inside increases. In the method of JP-A-58-144339, the temperature of the cooling water used in the cooler for the reaction product gas is not specified, but
When the cooling water temperature is low, the reaction product gas is rapidly cooled on the heat transfer surface of the cooler, and paraformaldehyde is generated on the heat transfer surface.
It is conceivable that the fouling coefficient of the heat transfer surface of the cooler will increase with time.
（問題を解決するための手段） 本発明者らはこれら従来技術の問題点を解決するため、
さらには既存のホルマリン製造設備をできるだけ改良せ
ずに高濃度ホルマリンを製造する方法について種々研究
を重ねた結果、メタノール、空気、水、ホルムアルデヒ
ドから成る原料ガスを銀触媒と接触させて得られる反応
生成ガスを、複数直列からなる吸収塔の内第１吸収塔へ
導き、循環している第１吸収塔液と反応生成ガスを向流
で気液接触させ、反応生成ガスの１部を吸収凝縮させる
ことにより、ホルムアルデヒド濃度５５〜６５重量％、
メタノール濃度2.5〜4.0重量％の高濃度ホルマリンを製
造する方法を見出し、本発明を完成させた。(Means for Solving Problems) In order to solve these problems of the conventional techniques, the present inventors have
Furthermore, as a result of various studies on a method for producing high-concentration formalin without improving the existing formalin production equipment as much as possible, the reaction product obtained by contacting a raw material gas consisting of methanol, air, water, and formaldehyde with a silver catalyst The gas is introduced into the first absorption tower of the absorption tower composed of a plurality of series, the circulating first absorption tower liquid and the reaction product gas are brought into gas-liquid contact in a counterflow, and a part of the reaction product gas is absorbed and condensed. As a result, formaldehyde concentration of 55 to 65% by weight,
The present invention has been completed by finding out a method for producing high-concentration formalin having a methanol concentration of 2.5 to 4.0% by weight.
すなわち、本発明はメタノール１モルに対して空気0.5
〜2.0モル、ホルムアルデヒド0.01〜0.1モル、水蒸気0.
3〜0.6モルからなる混合ガスを銀触媒と接触させ、得ら
れる反応生成ガスを複数直列より成る吸収塔の第１吸収
塔に導き、第１吸収液を循環させて反応生成ガスと第１
吸収塔液を交流接触することにより吸収・凝縮を行い、
第１吸収塔々底温度が７５〜９０℃、第１吸収塔々頂温
度が６７〜８５℃、第１吸収塔々底温度と第１吸収塔々
頂温度との温度差が３〜８℃となるように、第１吸収塔
液の循環ラインに設置した付属冷却器で冷却水に５５℃
以上の温水を用いて、第１吸収塔の塔底・塔頂温度を調
節しながら第１吸収塔よりホルムアルデヒド濃度５５〜
６５重量％、メタノール濃度2.5〜4.0重量％の高濃度ホ
ルマリンを製造する方法である。That is, the present invention uses 0.5 mol of air for 1 mol of methanol.
~ 2.0 mol, formaldehyde 0.01-0.1 mol, steam 0.
A mixed gas consisting of 3 to 0.6 mol is brought into contact with a silver catalyst, and the resulting reaction product gas is introduced into a first absorption tower of an absorption tower composed of a plurality of series, and the first absorption liquid is circulated so that the reaction product gas and the first
By absorbing and condensing the absorption tower liquid by alternating current contact,
The first absorption tower bottom temperature is 75 to 90 ° C, the first absorption tower top temperature is 67 to 85 ° C, and the temperature difference between the first absorption tower bottom temperature and the first absorption tower top temperature is 3 to 8 ° C. The cooling water to 55 ° C with the attached cooler installed in the circulation line of the first absorption tower liquid.
Using the above hot water, while controlling the tower bottom / top temperature of the first absorption tower, the formaldehyde concentration of the first absorption tower is 55-55.
This is a method for producing high-concentration formalin having 65% by weight and a methanol concentration of 2.5 to 4.0% by weight.
本発明を詳細に説明する。The present invention will be described in detail.
本発明は、メタノール１モルに対しホルムアルデヒド0.
01〜0.1モル、空気0.5〜2.0モルの混合ガスを得た後、
１００〜２４０℃に加熱し、この混合ガスに水蒸気をメ
タノール１モルに対し0.3〜0.6モルに加えて、メタノー
ル、空気、水、ホルムアルデヒドの４成分混合ガス（以
下原料ガスと呼ぶ）とし、この原料ガスを１２０〜２４
０℃の温度に保ちながら反応器へ導く。上記水蒸気添加
後反応器迄の配管は、凝縮が起きないように保温材を取
付け、必要に応じて原料ガスを加熱できるようにしてお
く。これは凝縮が起きた場合、凝縮したものがホルムア
ルデヒド水溶液となり、それが加熱されてパラホルムア
ルデヒドとなり、さらにタール状物質へ変化し、配管及
びメタノール蒸発器と反応器の間に設置した原料の伝熱
面等を汚し、運転を困難な状態にするためである。反応
器へ導かれた原料ガスは、５５０℃〜７００℃の温度の
銀触媒と接触させ、メタノールの脱水素反応を行なわせ
た後の反応生成ガスを反応器と一体構造となつた廃熱ボ
イラーで１３０〜１６０℃迄温度を下げた後、複数直列
から成る吸収塔の内、第１吸収塔に導く、第１吸収塔に
おいて第１吸収塔液を循環し、反応生成ガスと第１吸収
塔液を向流で気液接触させ、反応生成ガスの１部を吸収
凝縮させ、この吸収凝縮に伴う吸収熱を第１吸収塔液の
循環ラインに設置した第１吸収塔冷却器で脱熱し、第１
吸収塔々頂温度を６７〜８５℃、第１吸収塔々底液相温
度を７５〜９０℃、更に第１吸収塔々頂温度と第１吸収
塔々底液相温度との温度差が３〜８℃とすることによっ
て、ホルムアルデヒド濃度５５〜６５重量％、メタノー
ル濃度2.5〜4.0重量％の高濃度ホルマリンを得ることが
できる。温度差が小さすぎると、得られる高濃度ホルマ
リンの量が非常に少なくなり、このためか重合物が生成
して連続運転ができないので工業的に好ましくなく、温
度差が大きすぎると高濃度でないホルマリンが得られる
ので好ましくない。但し、第１吸収塔冷却器の冷却水温
度は５５℃以上としなければならない。好ましくは５８
〜６０℃が最適である。これは第１吸収塔で製造される
高濃度ホルマリンは、それ自体を５５℃以下の温度にす
ると白濁を開始し、これがパラホルムアルデヒドの固形
物として高濃度ホルマリン中に存在する様になるので、
このパラホルムアルデヒドが第１吸収塔冷却器の伝熱面
に付着し、伝熱面の汚れ係数が大きくなつて連続運転が
できなくなる。しかし、冷却水温度をあまり高くすると
第１吸収塔冷却器の設計を行う場合、伝熱面積が大きく
なり不経済である。さらに第１吸収塔冷却器の冷却水温
度を５５℃以上とするために、蒸気等他の熱源を用いて
は不経済であるので、冷却水温度を５５℃にするために
は、例えば図１に示す様な設備が経済的である。In the present invention, formaldehyde is 0.
After obtaining a mixed gas of 01-0.1 mol and air 0.5-2.0 mol,
This material is heated to 100 to 240 ° C., and steam is added to this mixed gas in an amount of 0.3 to 0.6 mol per 1 mol of methanol to obtain a four component mixed gas of methanol, air, water and formaldehyde (hereinafter referred to as raw material gas). 120 to 24 gas
Lead to the reactor while maintaining a temperature of 0 ° C. A heat insulating material is attached to the pipe up to the reactor after the addition of water vapor so that condensation does not occur, and the raw material gas can be heated if necessary. When condensation occurs, the condensed matter becomes an aqueous formaldehyde solution, which is heated to paraformaldehyde, and further changes into tar-like substances, and heat transfer of the raw materials installed in the pipe and between the methanol evaporator and the reactor. This is to make the surface and the like dirty and make driving difficult. The raw material gas introduced into the reactor is brought into contact with a silver catalyst at a temperature of 550 ° C. to 700 ° C., and the reaction product gas after carrying out the dehydrogenation reaction of methanol is integrated with the reactor to form a waste heat boiler. After the temperature is lowered to 130 to 160 ° C. in the first absorption tower, the first absorption tower liquid is circulated in the first absorption tower among the absorption towers composed of a plurality of series, and the reaction product gas and the first absorption tower are circulated. The liquid is brought into gas-liquid contact in a countercurrent manner, a part of the reaction product gas is absorbed and condensed, and the heat of absorption accompanying this absorption and condensation is deheated by the first absorption tower cooler installed in the circulation line of the first absorption tower liquid, First
The absorption tower top temperature is 67 to 85 ° C., the first absorption tower bottom liquid phase temperature is 75 to 90 ° C., and the temperature difference between the first absorption tower top liquid temperature and the first absorption tower bottom liquid phase temperature is 3 By setting the temperature to 8 ° C, high-concentration formalin having a formaldehyde concentration of 55 to 65 wt% and a methanol concentration of 2.5 to 4.0 wt% can be obtained. If the temperature difference is too small, the amount of high-concentration formalin obtained will be very small, and for this reason it is not industrially preferable because a polymer is generated and continuous operation cannot be performed. Is obtained, which is not preferable. However, the cooling water temperature of the first absorption tower cooler must be 55 ° C or higher. Preferably 58
The optimum temperature is -60 ° C. This is because the high-concentration formalin produced in the first absorption tower starts to turn cloudy when it is heated to a temperature of 55 ° C. or lower, and it becomes present in the high-concentration formalin as solids of paraformaldehyde.
This paraformaldehyde adheres to the heat transfer surface of the first absorption tower cooler, and the fouling coefficient of the heat transfer surface increases, making continuous operation impossible. However, if the temperature of the cooling water is too high, the heat transfer area becomes large when designing the first absorption tower cooler, which is uneconomical. Further, since it is uneconomical to use other heat sources such as steam in order to make the cooling water temperature of the first absorption tower cooler 55 ° C. or higher, in order to make the cooling water temperature 55 ° C., for example, FIG. The equipment shown in is economical.
図１について具体的に説明すると、冷却水タンク４に冷
却水として工業用水またはボイラー用軟水等Ｅを入れ、
冷却水ポンプ５にて第１吸収塔冷却器３へ供給し、該冷
却器３で循環させている第１吸収塔液Ｄと熱交換させた
後の冷却廃水E´を冷却水タンク４へ戻す途中に、冷却
廃水E´を脱熱して冷却水タンク４の温度を５５℃以上
に温度調節するための熱交換器６を設置することによつ
て、第１吸収塔冷却器３の冷却水Ｅ温度を５５℃以上に
温度調節する事が可能である。1 will be described in detail. Industrial water or boiler soft water E as cooling water is put in the cooling water tank 4,
The cooling water pump 5 supplies the cooling water to the first absorption tower cooler 3 and returns the cooling wastewater E ′ after heat exchange with the first absorption tower liquid D circulated in the cooling equipment 3 to the cooling water tank 4. The cooling water E of the first absorption tower cooler 3 is provided by installing a heat exchanger 6 for removing heat from the cooling wastewater E ′ and adjusting the temperature of the cooling water tank 4 to 55 ° C. or more on the way. It is possible to adjust the temperature to 55 ° C or higher.
図２について具体的に説明すると、本図は図１の第１吸
収塔冷却水の温度調節機構を取り入れたホルマリン製造
設備を示すものであり、メタノール蒸発器１０でメタノ
ールａ、ホルムアルデヒドガスまたはホルマリンｂを空
気ｃを吹きこみながら蒸発させた後、１〜２kg／cm2ｇ
飽和蒸気ｄを添加しメタノール、ホルムアルデヒド、空
気と水からなる混合ガスＡを予熱器２０で１２０〜２４
０℃の温度として、反応器３０に供給する。そして銀触
媒４０に接触させて得られた反応生成ガスＢを第１吸収
塔１に導き第１吸収塔１においてホルムアルデヒド濃度
５５〜６５％のホルマリンを製造し、第１吸収塔１で吸
収されなかつた未吸収ガスＣは第２吸収塔７でほぼ完全
に吸収されホルムアルデヒド濃度５０％以下のホルマリ
ンＩが得られる。Referring to FIG. 2 in detail, this figure shows a formalin production facility incorporating the temperature control mechanism of the first absorption tower cooling water of FIG. 1, in which the methanol evaporator 10, the formaldehyde gas or the formalin b is used. After evaporating while blowing in air c, 1-2 kg / cm 2 g
A saturated gas d is added, and a mixed gas A composed of methanol, formaldehyde, air and water is fed to the preheater 20 for 120 to 24
The reactor 30 is fed at a temperature of 0 ° C. Then, the reaction product gas B obtained by contacting with the silver catalyst 40 is guided to the first absorption tower 1 to produce formalin having a formaldehyde concentration of 55 to 65% in the first absorption tower 1 and not absorbed in the first absorption tower 1. The unabsorbed gas C is almost completely absorbed in the second absorption tower 7, and formalin I having a formaldehyde concentration of 50% or less is obtained.
本発明はこの様な方法で第１吸収塔から高濃度ホルマリ
ンを得ることが出来る。The present invention can obtain high-concentration formalin from the first absorption tower by such a method.
尚、本発明はこの様に第１吸収塔の操作温度を高くして
いるので、第１吸収塔での未吸収有効成分（HCHO、CH3O
H等）は、やや多くなるが、これは後続する第２吸収塔
以下の吸収塔の吸収液温度を下げることによつて、最終
吸収塔からの有効成分の逸散を防止することが出来る。Since the present invention raises the operating temperature of the first absorption tower in this way, the unabsorbed effective components (HCHO, CH 3 O) in the first absorption tower are used.
H and the like) are slightly increased, but this can prevent the escape of the active ingredient from the final absorption tower by lowering the temperature of the absorption liquid in the absorption towers subsequent to the second absorption tower.
例えば後半の吸収塔の吸収液のホルムアルデヒド濃度が
２〜３０重量％、メタノール濃度が1.0重量％以上あれ
ば、後半の吸収塔冷却器の冷却水温度は０℃以下の冷媒
を用いても良い。For example, if the formaldehyde concentration of the absorbing liquid in the latter half of the absorption tower is 2 to 30% by weight and the methanol concentration is 1.0% by weight or more, the cooling water temperature of the latter half absorption tower cooler may be 0 ° C. or lower.
（発明の効果） 本発明は、この様に既存のホルマリン製造設備を殆んど
変更することなく、高濃度ホルマリンを製造することを
可能にしたものであつて、極めて経済的な方法である。
然も得られた反応生成ガスや吸収液も高温に曝されるこ
ともないので、高濃度ホルマリン中の蟻酸の含有量も低
く品質面でも優れている。(Effects of the Invention) The present invention makes it possible to produce high-concentration formalin without changing the existing formalin production equipment, and is a very economical method.
Since the reaction product gas and the absorption liquid obtained are not exposed to high temperature, the content of formic acid in the high concentration formalin is low and the quality is excellent.
実施例−１ メタノール２３５重量部、空気３０１重量部、水８５重
量部、ホルムアルデヒド１１部から成る原料ガスを、６
２０℃の温度で銀触媒と接触させ、得られた反応生成ガ
スを、反応器と一体となつた廃熱ボイラーを用いて１５
０℃迄冷却した後、第１吸収塔へ導き、６０℃の冷却水
を用いて第１吸収塔々頂温度７８℃、第１吸収塔々底液
相温度を８２℃とすることによつて、第１吸収塔よりホ
ルムアルデヒド濃度６２重量％、メタノール濃度3.5重
量％、水分濃度34.5重量％、ギ酸濃度0.005重量％の高
濃度ホルマリンを連続して１２０日間無色透明な状態で
１５０部製造することができた。Example-1 A raw material gas consisting of 235 parts by weight of methanol, 301 parts by weight of air, 85 parts by weight of water, and 11 parts of formaldehyde was mixed with 6 parts by weight.
The reaction product gas is brought into contact with a silver catalyst at a temperature of 20 ° C., and the reaction product gas is used for 15
After cooling to 0 ° C., it is introduced into the first absorption tower and the cooling water of 60 ° C. is used to adjust the first absorption tower top temperature to 78 ° C. and the first absorption tower bottom liquid phase temperature to 82 ° C. , 150 parts of high concentration formalin having a formaldehyde concentration of 62% by weight, a methanol concentration of 3.5% by weight, a water concentration of 34.5% by weight and a formic acid concentration of 0.005% by weight can be continuously produced in a colorless and transparent state for 150 days from the first absorption tower. did it.
実施例２ メタノール１００重量部、空気１１０重量部、水２０重
量部、ホルムアルデヒド１０重量部からなる原料ガス
を、６２０℃の温度で銀触媒と接触させ、得られた反応
生成ガスを反応器と一体となった廃熱ボイラーを用いて
１５０℃迄冷却した後、第１吸収塔へ導き、第１吸収塔
々頂温度７８℃、第１吸収塔々底液相温度８５℃とする
ことによって、第１吸収塔よりホルムアルデヒド濃度５
９重量％、メタノール濃度3.2重量％、水分濃度37.8
％、ギ酸濃度0.005重量％の高濃度ホルマリンを連続し
て１２０日間無色透明な状態で９０部製造することがで
きた。尚、冷却器に使用した冷却水の温度は６２℃とし
た。Example 2 A raw material gas consisting of 100 parts by weight of methanol, 110 parts by weight of air, 20 parts by weight of water and 10 parts by weight of formaldehyde was contacted with a silver catalyst at a temperature of 620 ° C., and the obtained reaction product gas was integrated with a reactor. After cooling to 150 ° C. using the waste heat boiler, the first absorption tower has a top temperature of 78 ° C. and the first absorption tower has a bottom liquid phase temperature of 85 ° C. Formaldehyde concentration 5 from 1 absorption tower
9 wt%, methanol concentration 3.2 wt%, water concentration 37.8
%, Formalin having a formic acid concentration of 0.005% by weight could be continuously produced for 90 days in an amount of 90 parts in a colorless and transparent state. The temperature of the cooling water used for the cooler was 62 ° C.
比較例１ 第１吸収塔々頂温度８５℃、第１吸収塔々底液相温度８
６℃とした以外は実施例１と全く同様にしてホルマリン
を製造した。得られたホルマリンはホルムアルデヒド濃
度72重量％、メタノール濃度２重量％、水分濃度２６
％、ギ酸濃度0.02重量％であったが、吸収塔内で重合物
が生成し、連続運転は不可能であった。尚、冷却器に使
用した冷却水の温度は６５℃とした。Comparative Example 1 First absorption tower top temperature 85 ° C., First absorption tower bottom liquid phase temperature 8
Formalin was produced in exactly the same manner as in Example 1 except that the temperature was set to 6 ° C. The obtained formalin has a formaldehyde concentration of 72% by weight, a methanol concentration of 2% by weight, and a water concentration of 26%.
%, The formic acid concentration was 0.02% by weight, but a polymer was generated in the absorption tower and continuous operation was impossible. The temperature of the cooling water used for the cooler was 65 ° C.
比較例２ 第１吸収塔々頂温度６５℃、第１吸収塔々底液相温度８
０℃とした以外は実施例１と全く同様にしてホルマリン
を製造した。得られたホルマリンはホルムアルデヒド濃
度48重量％、メタノール濃度４重量％、水分濃度４８
％、ギ酸濃度0.005重量％であった。尚、冷却器に使用
した冷却水の温度は５５℃とした。Comparative Example 2 First absorption tower top temperature 65 ° C., First absorption tower bottom liquid phase temperature 8
Formalin was produced in exactly the same manner as in Example 1 except that the temperature was 0 ° C. The obtained formalin has a formaldehyde concentration of 48% by weight, a methanol concentration of 4% by weight, and a water concentration of 48%.
%, The formic acid concentration was 0.005% by weight. The temperature of the cooling water used for the cooler was 55 ° C.
比較例３ 冷却器に使用した冷却水の温度を３０℃とした以外は実
施例１と全く同様にしてホルマリンを製造した。得られ
たホルマリンはホルムアルデヒド濃度62重量％、メタノ
ール濃度３．５重量％、水分濃度３４．５％、ギ酸濃度
0.005重量％であったが、わずか２週間で吸収塔内が白
濁を起こし、運転を停止した。Comparative Example 3 Formalin was produced in exactly the same manner as in Example 1 except that the temperature of the cooling water used in the cooler was 30 ° C. The obtained formalin has a formaldehyde concentration of 62% by weight, a methanol concentration of 3.5% by weight, a water concentration of 34.5%, a formic acid concentration.
The content was 0.005% by weight, but after only 2 weeks, the inside of the absorption tower became cloudy and the operation was stopped.
図１は本発明の方法を実施する循環ライン中の冷却ライ
ン部分を示す概略図であり、図２は図１の冷却ラインを
取り入れた本発明方法のホルマリン製造プロセス概略図
である。 ａ…メタノール、ｂ…ホルムアルデヒドガスまたはホル
マリン、ｃ…空気、ｄ…１〜２kg／cmｇ飽和蒸気、Ａ…
原料ガス、Ｂ…反応生成ガス、Ｃ…第１吸収塔出口ガ
ス、Ｄ…高濃度ホルマリン、Ｅ…第１吸収塔冷却器冷却
水、E´…第１吸収塔冷却器冷却廃水、Ｈ…工業用水、
Ｉ…低濃度ホルマリン、Ｊ…排ガス、１…第１吸収塔、
２…第１吸収塔循環ポンプ、３…第１吸収塔冷却器、４
…冷却水タンク、５…冷却水ポンプ、６…冷却廃水用熱
交換器、７…第２吸収塔、８…第２吸収塔冷却器、１０
…メタノール蒸発器、２０…原料ガス加熱器、３０…反
応器、４０…銀触媒。1 is a schematic view showing a cooling line portion in a circulation line for carrying out the method of the present invention, and FIG. 2 is a schematic view of a formalin production process of the method of the present invention incorporating the cooling line of FIG. a ... Methanol, b ... Formaldehyde gas or formalin, c ... Air, d ... 1-2 kg / cmg saturated vapor, A ...
Raw material gas, B ... Reaction produced gas, C ... First absorption tower outlet gas, D ... High-concentration formalin, E ... First absorption tower cooler cooling water, E '... First absorption tower cooler cooling waste water, H ... Industrial Water,
I ... low concentration formalin, J ... exhaust gas, 1 ... first absorption tower,
2 ... 1st absorption tower circulation pump, 3 ... 1st absorption tower cooler, 4
... Cooling water tank, 5 ... Cooling water pump, 6 ... Cooling waste water heat exchanger, 7 ... Second absorption tower, 8 ... Second absorption tower cooler, 10
... Methanol evaporator, 20 ... Raw material gas heater, 30 ... Reactor, 40 ... Silver catalyst.
Claims (1)
ル、ホルムアルデヒド0.01〜0.1モル、水蒸気0.3〜0.6
モルからなる混合ガスを銀触媒と接触させ、得られる反
応生成ガスを複数直列より成る吸収塔の第１吸収塔に導
き、第１吸収液を循環させて反応生成ガスと第１吸収塔
液を交流接触することにより吸収・凝縮を行い、第１吸
収塔々底温度が７５〜９０℃、第１吸収塔々頂温度が６
７〜８５℃、第１吸収塔々底温度と第１吸収塔々頂温度
との温度差が３〜８℃となるように、第１吸収塔液の循
環ラインに設置した付属冷却器で冷却水に５５℃以上の
温水を用いて、第１吸収塔の塔底・塔頂温度を調節しな
がら第１吸収塔よりホルムアルデヒド濃度５５〜６５重
量％、メタノール濃度2.5〜4.0重量％の高濃度ホルマリ
ンを製造する方法。1. 0.5 to 2.0 mol of air, 0.01 to 0.1 mol of formaldehyde, and 0.3 to 0.6 of steam per mol of methanol.
A mixed gas composed of moles is brought into contact with a silver catalyst, and the resulting reaction product gas is guided to a first absorption tower of an absorption tower composed of a plurality of series, and the first absorption liquid is circulated to generate the reaction product gas and the first absorption tower liquid. Absorption / condensation is performed by contacting with alternating current, the bottom temperature of the first absorption tower is 75 to 90 ° C, and the top temperature of the first absorption tower is 6
7-85 ℃, the temperature difference between the first absorption tower bottom temperature and the first absorption tower top temperature is 3-8 ℃, cooled by the attached cooler installed in the circulation line of the first absorption tower liquid High-concentration formalin with a formaldehyde concentration of 55 to 65% by weight and a methanol concentration of 2.5 to 4.0% by weight from the first absorption tower while adjusting the bottom and top temperatures of the first absorption tower by using warm water of 55 ° C or higher as water. A method of manufacturing.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59201833A JPH0629204B2 (en) | 1984-09-28 | 1984-09-28 | Method for producing high-concentration formalin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59201833A JPH0629204B2 (en) | 1984-09-28 | 1984-09-28 | Method for producing high-concentration formalin |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6183139A JPS6183139A (en) | 1986-04-26 |
| JPH0629204B2 true JPH0629204B2 (en) | 1994-04-20 |
Family
ID=16447650
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP59201833A Expired - Lifetime JPH0629204B2 (en) | 1984-09-28 | 1984-09-28 | Method for producing high-concentration formalin |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0629204B2 (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102008059701A1 (en) * | 2008-11-29 | 2010-06-02 | Bayer Materialscience Ag | Process for the preparation of aqueous formaldehyde solutions |
| US8710267B2 (en) * | 2009-04-20 | 2014-04-29 | Basf Se | Process for preparing MDA via the stage of the aminal |
| CN104248939B (en) * | 2014-09-16 | 2017-04-12 | 江苏凯茂石化科技有限公司 | Methanol oxidizer in silver catalyst process formaldehyde device |
| CN110563903A (en) * | 2019-09-06 | 2019-12-13 | 无锡市华立石化工程有限公司 | preparation system and preparation process of urea formaldehyde pre-condensed liquid |
-
1984
- 1984-09-28 JP JP59201833A patent/JPH0629204B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6183139A (en) | 1986-04-26 |
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