JP2011005388A - Method of reducing catalyst containing copper oxide - Google Patents
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- JP2011005388A JP2011005388A JP2009149536A JP2009149536A JP2011005388A JP 2011005388 A JP2011005388 A JP 2011005388A JP 2009149536 A JP2009149536 A JP 2009149536A JP 2009149536 A JP2009149536 A JP 2009149536A JP 2011005388 A JP2011005388 A JP 2011005388A
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Abstract
Description
本発明は、酸化銅含有触媒の還元方法に関するものである。更に詳しくは、本発明は、酸化銅含有触媒が充填された触媒充填部と気液分離部を備える反応器を用いて、触媒充填部に水素を含む気体と液体を導入して酸化銅含有触媒を還元する方法であって、還元によって得られる触媒中の金属銅のシンタリングを防止することができ、かつ触媒の強度を高く保持することができる酸化銅含有触媒の還元方法に関するものである。 The present invention relates to a method for reducing a copper oxide-containing catalyst. More specifically, the present invention relates to a copper oxide-containing catalyst by introducing a gas and a liquid containing hydrogen into the catalyst filling portion using a reactor equipped with a catalyst filling portion filled with a copper oxide-containing catalyst and a gas-liquid separation portion. The present invention relates to a method for reducing a copper oxide-containing catalyst capable of preventing sintering of metallic copper in a catalyst obtained by reduction and maintaining high strength of the catalyst.
酸化銅含有触媒は、通常、反応に使用する前に触媒中の酸化銅を金属銅に予め還元して用いられる。例えば、特許文献１には、固定床断熱式反応器に充填された酸化銅含有触媒にエチルベンゼン、水素、メタンを通過させて還元した後、アセトフェノンを１−フェニルエチルアルコールへ水素化する方法が開示されている。 The copper oxide-containing catalyst is usually used by reducing the copper oxide in the catalyst into metallic copper in advance before use in the reaction. For example, Patent Document 1 discloses a method of hydrogenating acetophenone to 1-phenylethyl alcohol after reduction by passing ethylbenzene, hydrogen, and methane through a copper oxide-containing catalyst packed in a fixed bed adiabatic reactor. Has been.
かかる状況において、本発明が解決しようとする課題は、酸化銅含有触媒が充填された触媒充填部と気液分離部を備える反応器を用いて、触媒充填部に水素を含む気体と液体を導入して酸化銅含有触媒を還元する方法であって、還元によって得られる触媒中の金属銅のシンタリングを防止することができ、かつ触媒の強度を高く保持することができる酸化銅含有触媒の還元方法を提供する点にある。 In such a situation, the problem to be solved by the present invention is to introduce a gas and a liquid containing hydrogen into the catalyst filling part using a reactor equipped with a catalyst filling part filled with a copper oxide-containing catalyst and a gas-liquid separation part. Reduction of the copper oxide-containing catalyst, the sintering of the metal copper in the catalyst obtained by the reduction can be prevented and the strength of the catalyst can be kept high. The point is to provide a method.
すなわち、本発明は、酸化銅含有触媒が充填された触媒充填部と気液分離部を備える反応器を用いて、触媒充填部に水素を含む気体と液体を導入して酸化銅含有触媒を還元する方法であって、触媒充填部出口の液体に含まれる水分の濃度を１５００重量ｐｐｍ以下とする酸化銅含有触媒の還元方法に係るものである。 That is, the present invention reduces the copper oxide-containing catalyst by introducing a gas and a liquid containing hydrogen into the catalyst filling portion using a reactor equipped with a catalyst filling portion filled with a copper oxide-containing catalyst and a gas-liquid separation portion. The method relates to a method for reducing a copper oxide-containing catalyst in which the concentration of water contained in the liquid at the outlet of the catalyst filling unit is 1500 ppm by weight or less.
本発明の酸化銅含有触媒の還元方法によれば、還元によって得られる触媒中の金属銅のシンタリングを防止することができ、かつ触媒の強度を高く保持することができる。 According to the method for reducing a copper oxide-containing catalyst of the present invention, sintering of metallic copper in the catalyst obtained by reduction can be prevented, and the strength of the catalyst can be kept high.
本発明で用いられる酸化銅含有触媒とは、主成分として酸化銅（ＣｕＯ）を含んでいる触媒を意味する。触媒中のＣｕＯの含有量は、通常１０〜９０重量％、好ましくは２０〜８０重量％である。触媒中のＣｕＯ以外の成分としてはＣｒ2Ｏ3、ＺｎＯ、Ｆｅ2Ｏ3、Ａｌ2Ｏ3、ＺｒＯ2、ＴｉＯ2、ＳｉＯ2、ＭｎＯ2、Ｃｏ2Ｏ3、ＮｉＯ、ＢａＯ、ＣａＯ、ＭｇＯ、ＮａＯＨ、ＫＯＨ、Ｎａ2ＣＯ3、Ｋ2ＣＯ3などを含有してもよい。
触媒は共沈法、沈着法、混練法により製造することができる。共沈法によって触媒を製造する場合、硝酸銅の水溶液に水酸化ナトリウム、炭酸ソーダーまたは炭酸アンモニウムを加えて、水酸化物、塩基性炭酸塩として沈殿させ、水洗、乾燥後、過熱分解した後、触媒粉体を得る。固定床反応器に充填する場合には該粉体とグラファイト、シリカゾル、アルミナなどのバインダーを添加後、混練、打錠成型又は押し出し成型によって、ペレットに成型された触媒を用いる。
The copper oxide-containing catalyst used in the present invention means a catalyst containing copper oxide (CuO) as a main component. The content of CuO in the catalyst is usually 10 to 90% by weight, preferably 20 to 80% by weight. As a component other than CuO in the catalyst Cr 2 O 3, ZnO, Fe 2 O 3, Al 2 O 3, ZrO 2, TiO 2, SiO 2, MnO 2, Co 2 O 3, NiO, BaO, CaO, MgO , NaOH, KOH, Na 2 CO 3 , K 2 CO 3 and the like may be contained.
The catalyst can be produced by a coprecipitation method, a deposition method, or a kneading method. When producing a catalyst by the coprecipitation method, sodium hydroxide, sodium carbonate or ammonium carbonate is added to an aqueous solution of copper nitrate to precipitate it as a hydroxide or basic carbonate, washed with water, dried, and then thermally decomposed. A catalyst powder is obtained. When packed in a fixed bed reactor, the powder and a binder such as graphite, silica sol, and alumina are added, and then a catalyst formed into pellets by kneading, tableting or extrusion is used.
本発明で用いられる液体としては、還元条件下で液体であるものであり、例えば、ヘキサン、ヘプタン、ベンゼン、トルエン、キシレン、エチルベンゼン、クメンなどの炭化水素、及びこれらの混合溶媒をあげることができる。 The liquid used in the present invention is a liquid under reducing conditions, and examples thereof include hydrocarbons such as hexane, heptane, benzene, toluene, xylene, ethylbenzene, cumene, and mixed solvents thereof. .
還元温度は、還元速度を速めるという観点や金属銅のシンタリングを防ぐという観点から、通常４０〜２００℃であり、好ましくは１３０〜２００℃である。
還元圧力は、還元速度を速めるという観点や金属銅のシンタリングを防ぐという観点から、通常０．１〜２ＭＰａであり、好ましくは０．４〜１ＭＰａである。
The reduction temperature is usually 40 to 200 ° C., preferably 130 to 200 ° C. from the viewpoint of increasing the reduction rate and preventing sintering of metallic copper.
The reduction pressure is usually 0.1 to 2 MPa, preferably 0.4 to 1 MPa from the viewpoint of increasing the reduction rate and preventing sintering of metallic copper.
水分濃度が１５００重量ｐｐｍを超えないように酸化銅含有触媒を還元するために、反応温度または反応圧力などの反応条件を調整して、反応速度、すなわち、水の生成速度を制御することが好ましい。 In order to reduce the copper oxide-containing catalyst so that the water concentration does not exceed 1500 ppm by weight, it is preferable to adjust reaction conditions such as reaction temperature or reaction pressure to control the reaction rate, that is, the water generation rate. .
本発明で用いられる水素を含む気体としては、水素ガスのみで用いても良いし、窒素ガスのような不活性ガスで希釈しても良い。また、工業的用にはナフサを分解して得られるメタネーター水素を用いても良い。水素を含む気体中の水分は通常、室温で飽和蒸気圧以下に乾燥されたガスを用いることが好ましい。 The gas containing hydrogen used in the present invention may be used only with hydrogen gas, or may be diluted with an inert gas such as nitrogen gas. Further, for industrial use, methanator hydrogen obtained by decomposing naphtha may be used. As the moisture in the gas containing hydrogen, it is usually preferable to use a gas dried to a saturated vapor pressure or lower at room temperature.
本発明において、触媒充填部出口から抜き出された液体の水分濃度は、還元によって得られる触媒中の金属銅のシンタリングを防止し、触媒の強度を高く保持するという観点から、１５００重量ｐｐｍ以下である。 In the present invention, the water concentration of the liquid extracted from the catalyst filling portion outlet is 1500 ppm by weight or less from the viewpoint of preventing sintering of metallic copper in the catalyst obtained by reduction and maintaining high strength of the catalyst. It is.
触媒充填部出口から抜き出された液体の水分濃度は、触媒充填部出口から抜き出された液体をカールフィッシャー法やガスクロマトグラフ法によって測定することによって求められる。触媒充填部出口から抜き出された液体を冷却して水を分離させる場合には、冷却後の液体の水分濃度と分離された水分量から、触媒充填部出口から抜き出された液体の水分濃度を計算することができる。 The water concentration of the liquid extracted from the catalyst filling portion outlet is obtained by measuring the liquid extracted from the catalyst filling portion outlet by the Karl Fischer method or the gas chromatograph method. When the water extracted from the catalyst filling unit outlet is cooled to separate water, the water concentration of the liquid extracted from the catalyst filling unit outlet is determined based on the water concentration of the liquid after cooling and the separated water content. Can be calculated.
更に、本発明の還元方法としては、触媒充填部出口から抜き出された液体に含まれる水分を除去してから、水素を含む気体と液体を分離し、分離された液体を触媒充填部へリサイクル液体として導入する還元方法が、還元での液体の使用量を少なくでき、経済的であるために好ましい。 Furthermore, as a reduction method of the present invention, after removing moisture contained in the liquid extracted from the catalyst filling section outlet, the hydrogen-containing gas and liquid are separated, and the separated liquid is recycled to the catalyst filling section. The reduction method introduced as a liquid is preferable because the amount of liquid used in the reduction can be reduced and is economical.
触媒充填部出口から抜き出された液体に含まれる水分の除去方法としては、下記の方法が好ましい
一番目の方法としては、触媒充填部出口から抜き出された液体を冷却して水を除去してから、水素を含む気体と液体を分離し、分離された液体を触媒充填部に導入する還元方法が挙げられる。触媒充填部出口から抜き出された液体の冷却温度は、還元温度より低ければ良い。好ましくは、経済的であるという観点や、液体の水分濃度が高くなり金属銅のシンタリングが起きることを防止するという観点から、５〜３５℃である。
The following method is preferable as a method for removing water contained in the liquid drawn out from the catalyst filling unit outlet. As the first method, the liquid drawn out from the catalyst filling unit outlet is cooled to remove water. After that, there is a reduction method in which a gas containing hydrogen and a liquid are separated, and the separated liquid is introduced into the catalyst filling portion. The cooling temperature of the liquid withdrawn from the catalyst filling unit outlet may be lower than the reduction temperature. Preferably, the temperature is 5 to 35 ° C. from the viewpoint of economy and the prevention of sintering of metallic copper due to an increase in the water concentration of the liquid.
二番目の方法としては、触媒充填部出口から抜き出された液体に含まれる水分を、水素ガスを含む気体に水分を同伴し低減させてから、水素を含む気体と液体を分離し、分離された液体を触媒充填部に導入する還元方法が挙げられる。 The second method is to reduce the moisture contained in the liquid extracted from the outlet of the catalyst filling unit by entraining moisture in the gas containing hydrogen gas and then separating the gas and liquid containing hydrogen. And a reduction method in which the liquid is introduced into the catalyst filling portion.
三番目の方法としては、触媒充填部に、または触媒充填部出口から抜き出された液体に、乾燥した不活性ガスを導入し、触媒充填部出口から抜き出された液体に含まれる水分を、水素を含む気体および導入した不活性ガスに同伴させて低減し、水素を含む気体と液体を分離し、分離された液体を触媒充填部に導入する還元方法が挙げられる。不活性ガスとしては、安価で入手しやすいことから、窒素やメタンが好ましい。 As a third method, a dry inert gas is introduced into the catalyst filling part or the liquid withdrawn from the catalyst filling part outlet, and the moisture contained in the liquid withdrawn from the catalyst filling part outlet, There is a reduction method in which the gas containing hydrogen and the introduced inert gas are reduced, the gas containing hydrogen is separated from the liquid, and the separated liquid is introduced into the catalyst filling portion. As the inert gas, nitrogen and methane are preferable because they are inexpensive and easily available.
上記の二番目の還元方法において、水素ガスを含む気体に水分を同伴し低減させる方法としては、水素を含む気体で液体をバブリングする方法が挙げられる。上記の三番目の還元方法において、水素を含む気体および導入した不活性ガスに水分を同伴し低減させる方法としては、水素を含む気体で液体をバブリングする方法が挙げられる。バブリングする時の液体の温度は、水分を同伴し低減し易くするという観点や、液体が流出し、液体のロスが大きくなることを防ぐという観点から、５０〜２００℃が好ましい。 In the second reduction method described above, examples of a method for reducing moisture by entraining a gas containing hydrogen gas include a method of bubbling a liquid with a gas containing hydrogen. In the third reduction method described above, as a method for entraining and reducing moisture in the gas containing hydrogen and the introduced inert gas, a method of bubbling a liquid with a gas containing hydrogen can be given. The temperature of the liquid at the time of bubbling is preferably 50 to 200 ° C. from the viewpoint of facilitating reduction by entraining moisture, and from the viewpoint of preventing the liquid from flowing out and increasing the loss of the liquid.
本発明の方法によって還元された触媒の用途としては、ケトンの水素化に使用される。例えば、アセトフェノンを水素化する１−フェニルエチルアルコールの製造に使用できる。１−フェニルエチルアルコールは工業的にスチレンモノマーあるいは各種有機合成の中間体としての原料である。 The catalyst reduced by the method of the present invention is used for hydrogenation of ketones. For example, it can be used to produce 1-phenylethyl alcohol for hydrogenating acetophenone. 1-Phenylethyl alcohol is industrially a raw material as a styrene monomer or an intermediate for various organic synthesis.
次に本発明を実施例により説明する。
実施例１
ＳＵＳ−３１６Ｌ製の管（内径：１４ｍｍφ、長さ：１２００ｍｍＬ）に温度鞘管（外径：３ｍｍφ）をセットした中に、酸化銅を６３重量％含有した触媒（直径１．４ｍｍφ、長さ４〜８ｍｍの円柱状)を125ｇ(充填長：１０００ｍｍ)充填した（触媒充填部（５））。触媒充填部出口から抜き出された液体を冷却する冷却器（８）、圧力調整器（９）、冷却後の液体と水を分離する為のガラス製油水分離器（１０）を設置した（冷却器（８）と圧力調整器（９）と油水分離器（１０）が気液分離部である）。又、気液分離部で気体と分離された液体を、リサイクル液体（１１）として触媒充填部（５）へ導入して、還元反応を行った。
最初に窒素をマスフローコントローラーを通じて９０Ｎｍｌ／ｍｉｎ、リサイクル液体（水分濃度が３３０重量ｐｐｍのリサイクルエチルベンゼン）を７５０ｇ／ｈｒ供給し、反応器内の圧力を０．５ＭＰａになるように圧力調整器で調整した。液体の流出を確認後、触媒充填部（５）の入口部の予熱器の温度を上げ、触媒充填部（５）の入口温度が１５０℃を超えないように温度調整を行った。
温度を１５０℃に調整した後に、液体（水分濃度が３３０重量ｐｐｍのエチルベンゼン）を５０ｇ／ｈｒ、続いて、メタンの濃度が１６体積％であるメタンと水素の混合ガスを９０Ｎｍｌ／ｍｉｎで供給し、窒素ガスをストップした。この時点を還元反応の開始時刻（時刻０）として、触媒充填部（５）を加熱し、触媒充填部（５）の温度を１５０℃に維持して還元反応を開始した。開始後（時刻０から）２時間おきに油水分離器（１０）に回収された水の重量と、リサイクル液中の水分濃度を測定したところ、触媒充填部（５）から抜き出された液体の水分濃度は９８０重量ｐｐｍと計算された。最終的には１８時間の還元反応を行った。還元率は５８％と計算された。窒素雰囲気下で触媒を抜き出し、窒素で触媒を乾燥した後、触媒充填部（５）の中間部の触媒について乳鉢ですりつぶし、Ｒｉｇａｋｕ ｕｌｔｒａＸ−１８（電圧；５０ｋｖ、電源；１００ｍＡ、ＸＲａｙ Ｃｕ−Ｋα）でＸＲＤ分析を行った。Ｃｕ0の結晶子サイズについて測定した結果２θ＝４３．３度、１２３Åであった。また、触媒強度についても、ＸＲＤ同様に触媒充填部（５）の中間部の触媒を選択し、Ｆｕｊｉｗａｒａ Ｈａｒｄｎｅｓｓ Ｔｅｓｔｅｒで測定を行ったところ、１８（Ｎ）であった。結果については表１に示す。
Next, the present invention will be described with reference to examples.
Example 1
A catalyst (diameter 1.4 mmφ, length 4) containing 63% by weight of copper oxide in a temperature sheath tube (outer diameter: 3 mmφ) set in a tube made of SUS-316L (inner diameter: 14 mmφ, length: 1200 mmL). ˜8 mm cylindrical shape) was filled with 125 g (filling length: 1000 mm) (catalyst filling portion (5)). A cooler (8) for cooling the liquid extracted from the catalyst filling unit outlet, a pressure regulator (9), and a glass oil / water separator (10) for separating the cooled liquid and water were installed (cooling). (8), pressure regulator (9), and oil-water separator (10) are gas-liquid separators). Further, the liquid separated from the gas in the gas-liquid separation part was introduced into the catalyst filling part (5) as a recycle liquid (11) to carry out a reduction reaction.
First, nitrogen was supplied through a mass flow controller at 90 Nml / min and a recycle liquid (recycled ethylbenzene having a moisture concentration of 330 ppm by weight) was supplied at 750 g / hr, and the pressure inside the reactor was adjusted to 0.5 MPa with a pressure regulator. . After confirming the outflow of the liquid, the temperature of the inlet of the catalyst filling section (5) was raised and the temperature was adjusted so that the inlet temperature of the catalyst filling section (5) did not exceed 150 ° C.
After adjusting the temperature to 150 ° C., liquid (ethylbenzene having a water concentration of 330 ppm by weight) is supplied at 50 g / hr, and then a mixed gas of methane and hydrogen with a methane concentration of 16% by volume is supplied at 90 Nml / min. Nitrogen gas was stopped. With this time as the start time (time 0) of the reduction reaction, the catalyst filling portion (5) was heated, and the temperature of the catalyst filling portion (5) was maintained at 150 ° C. to start the reduction reaction. After the start (from time 0), the weight of water collected in the oil / water separator (10) every 2 hours and the water concentration in the recycle liquid were measured, and the liquid extracted from the catalyst filling section (5) was measured. The water concentration was calculated to be 980 ppm by weight. Finally, a reduction reaction was performed for 18 hours. The reduction rate was calculated as 58%. After extracting the catalyst under nitrogen atmosphere and drying the catalyst with nitrogen, the catalyst in the middle part of the catalyst filling part (5) is ground in a mortar, Rigaku ultraX-18 (voltage: 50 kv, power supply: 100 mA, XRay Cu-Kα) XRD analysis was performed. The measurement result of the crystallite size of Cu 0 was 2θ = 43.3 ° and 123 °. Further, the catalyst strength was 18 (N) when an intermediate catalyst in the catalyst packed portion (5) was selected as in XRD and measured with Fujiwara Hardness Tester. The results are shown in Table 1.
還元率の計算：生成水重量（ｇ）÷理論生成水重量（ｇ）
理論生成水重量（ｇ）：触媒重量×ＣｕＯ濃度÷１００÷ＣｕＯ分子量×水分子量
ＣｕＯ濃度：６３（重量％）
ＣｕＯ分子量：７９．５（ｇ／ｍｏｌ）
水分子量：１８．０（ｇ／ｍｏｌ）
Calculation of reduction rate: weight of generated water (g) ÷ theoretically generated water weight (g)
Theoretical water weight (g): catalyst weight × CuO concentration ÷ 100 ÷ CuO molecular weight × water molecular weight CuO concentration: 63 (% by weight)
CuO molecular weight: 79.5 (g / mol)
Water molecular weight: 18.0 (g / mol)
水分濃度（重量ｐｐｍ）
ｉｎ：平沼 ＡＱ−６カールフィッシャーにて測定
ｏｕｔ：（液体流量（ｇ／ｈ）×ｏｕｔ液体中の水分濃度（重量ｐｐｍ）÷１０６
＋水生成流量（ｇ／ｈ））÷液体流量（ｇ／ｈ）×１０６
Water concentration (ppm by weight)
in: measured by Hiranuma AQ-6 Karl Fischer out: (liquid flow rate (g / h) × out water concentration in liquid (weight ppm) ÷ 10 6
+ Water production flow rate (g / h)) ÷ liquid flow rate (g / h) × 10 6
結晶子サイズ（Å）：Ｒｉｇａｋｕ ｕｌｔｒａＸ−１８
（電圧；５０ｋｖ、電源；１００ｍＡ、ＸＲａｙ Ｃｕ−Ｋα）
Ｓｃｈｅｒｒｅｒの式による
Crystallite size (Å): Rigaku ultraX-18
(Voltage: 50 kv, power supply: 100 mA, XRay Cu-Kα)
According to Scherrer's formula
触媒強度（Ｎ）：Ｆｕｊｉｗａｒａ Ｈａｒｄｎｅｓｓ Ｔｅｓｔｅｒ
触媒２０個の横方向の平均強度（長さ４．５ｍｍ以上）
Catalyst strength (N): Fujiwara Hardness Tester
20 horizontal average strength of catalyst (length 4.5mm or more)
実施例２
還元時間を１００時間とした以外は実施例１と同様に還元反応を行った。約４６時間までにほぼ理論量の生成水が留出したが、その後、１００時間まで、同一条件で還元反応を行った。還元反応開始（時刻０）から４６時間で触媒充填部（５）出口の液体の水分濃度は９６０重量ｐｐｍ、還元率は１０１％と計算され、結晶子サイズ１０９Å、触媒強度は１７Ｎであった。
Example 2
The reduction reaction was performed in the same manner as in Example 1 except that the reduction time was 100 hours. Almost the theoretical amount of produced water was distilled off by about 46 hours, and then the reduction reaction was carried out under the same conditions until 100 hours. After 46 hours from the start of the reduction reaction (time 0), the water concentration of the liquid at the outlet of the catalyst filling section (5) was calculated to be 960 ppm by weight, the reduction rate was calculated to be 101%, the crystallite size was 109 kg, and the catalyst strength was 17N.
実施例３
還元温度を１２０℃、還元時間を４９時間とした以外は実施例１と同様に還元反応を行った。この時の触媒充填部（５）出口の液体の水分濃度は６２０重量ｐｐｍ、還元率は５６％と計算され、結晶子サイズ１１４Å、触媒強度は１８Ｎであった。
Example 3
The reduction reaction was performed in the same manner as in Example 1 except that the reduction temperature was 120 ° C. and the reduction time was 49 hours. At this time, the water concentration of the liquid at the outlet of the catalyst filling portion (5) was calculated to be 620 ppm by weight, the reduction rate was calculated to be 56%, the crystallite size was 114 kg, and the catalyst strength was 18N.
実施例４
還元圧力を０．９Ｍｐａ、還元時間を１６時間とした以外は実施例１と同様に還元反応を行った。この時の触媒充填部（５）出口の液体の水分濃度は１１００重量ｐｐｍ、還元率は５６％と計算され、結晶子サイズ１３１Å、触媒強度は２１Ｎであった。
Example 4
The reduction reaction was performed in the same manner as in Example 1 except that the reduction pressure was 0.9 Mpa and the reduction time was 16 hours. At this time, the liquid concentration at the outlet of the catalyst filling portion (5) was calculated to be 1100 ppm by weight, the reduction rate was calculated to be 56%, the crystallite size was 131 kg, and the catalyst strength was 21N.
比較例１
還元温度を２１０℃、還元時間を６時間とした以外は実施例１と同様に還元反応を行った。この時の触媒充填部（５）出口の液体の水分濃度は１８４０重量ｐｐｍ、還元率は５２％と計算され、結晶子サイズ１７７Å、触媒強度は２４Ｎであった。
Comparative Example 1
A reduction reaction was performed in the same manner as in Example 1 except that the reduction temperature was 210 ° C. and the reduction time was 6 hours. At this time, the water concentration of the liquid at the outlet of the catalyst filling portion (5) was calculated to be 1840 ppm by weight, the reduction rate was calculated to be 52%, the crystallite size was 177 mm, and the catalyst strength was 24N.
比較例２
水を１．２ｇ／ｈ供給し、入口の水分濃度を１８３０重量ｐｐｍとして、還元時間を３７時間とした以外は実施例１と同様に還元反応を行った。この時の触媒充填部（５）出口の液体の水分濃度は２３５０重量ｐｐｍ、還元率は７２％と計算され、結晶子サイズ１８８Å、触媒強度は１７Ｎであった。
Comparative Example 2
The reduction reaction was performed in the same manner as in Example 1 except that 1.2 g / h of water was supplied, the water concentration at the inlet was 1830 ppm by weight, and the reduction time was 37 hours. At this time, the water concentration of the liquid at the outlet of the catalyst filling portion (5) was calculated to be 2350 ppm by weight, the reduction rate was calculated to be 72%, the crystallite size was 188 kg, and the catalyst strength was 17N.
比較例３
水を２．４ｇ／ｈ供給し、入口の水分濃度を３３００重量ｐｐｍとして、還元圧力を０．９ＭＰａ、還元時間を３２時間とした以外は実施例１と同様に還元反応を行った。この時の触媒充填部（５）出口の液体の水分濃度は３９８０重量ｐｐｍ、還元率は８３％と計算され、結晶子サイズ２８９Å、触媒強度は２Ｎであった。
Comparative Example 3
A reduction reaction was performed in the same manner as in Example 1 except that water was supplied at 2.4 g / h, the water concentration at the inlet was 3300 ppm by weight, the reduction pressure was 0.9 MPa, and the reduction time was 32 hours. At this time, the moisture concentration of the liquid at the outlet of the catalyst filling portion (5) was calculated to be 3980 ppm by weight, the reduction rate was 83%, the crystallite size was 289 kg, and the catalyst strength was 2N.
（１）窒素
（２）水素
（３）液体
（４）水
（５）触媒充填部
（６）予熱器
（７）熱電対
（８）冷却器
（９）圧力調整器
（１０）油水分離器
（１１）リサイクル液体
（１２）リサイクルポンプ
（１３）ｖｅｎｔ ｇａｓ
（１４）パージ
(1) Nitrogen (2) Hydrogen (3) Liquid (4) Water (5) Catalyst filling section (6) Preheater (7) Thermocouple (8) Cooler (9) Pressure regulator (10) Oil-water separator ( 11) Recycled liquid (12) Recycle pump (13) Vent gas
(14) Purge
Claims (4)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2009149536A JP2011005388A (en) | 2009-06-24 | 2009-06-24 | Method of reducing catalyst containing copper oxide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2009149536A JP2011005388A (en) | 2009-06-24 | 2009-06-24 | Method of reducing catalyst containing copper oxide |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2011005388A true JP2011005388A (en) | 2011-01-13 |
Family
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105709858A (en) * | 2014-12-01 | 2016-06-29 | 神华集团有限责任公司 | Catalyst continuous reducing apparatus and method |
| CN108043414A (en) * | 2017-12-06 | 2018-05-18 | 万华化学集团股份有限公司 | Hydrogenation of acetophenone prepares the catalyst of alpha-phenyl ethyl alcohol, preparation method and application |
-
2009
- 2009-06-24 JP JP2009149536A patent/JP2011005388A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105709858A (en) * | 2014-12-01 | 2016-06-29 | 神华集团有限责任公司 | Catalyst continuous reducing apparatus and method |
| CN108043414A (en) * | 2017-12-06 | 2018-05-18 | 万华化学集团股份有限公司 | Hydrogenation of acetophenone prepares the catalyst of alpha-phenyl ethyl alcohol, preparation method and application |
| CN108043414B (en) * | 2017-12-06 | 2019-07-30 | 万华化学集团股份有限公司 | Hydrogenation of acetophenone prepares the catalyst of alpha-phenyl ethyl alcohol, preparation method and application |
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