WO2005072859A1

WO2005072859A1 - Filler for vapor-phase reaction

Info

Publication number: WO2005072859A1
Application number: PCT/JP2005/000938
Authority: WO
Inventors: Yasuhiko Mori
Original assignee: Sumitomo Chemical Company, Limited
Priority date: 2004-01-29
Filing date: 2005-01-19
Publication date: 2005-08-11

Abstract

Disclosed is a filler for vapor-phase reactions which is composed of an alumina having an aluminum content of about 90 weight% or more in terms of aluminum oxide. This filler can be continuously used for a long time since it hardly suffers from changes in properties or mass even after long use.

Description

Description Filler for gas phase reaction Technical field

The present invention relates to a filler for a gas phase reaction. Background art

A gas phase reactor in which a gaseous raw material compound is reacted is usually filled with a filler in order to improve the heat conductivity of the raw material compound and to support and dilute the solid catalyst.

For example, Japanese Patent Publication 4 7 4 0 7 9 2 JP page 2, ceramic Raschig rings (Rasching Ring) as a filler, i.e. silica filler (S i 0 ₂₎ composite oxide composed mainly of This filler is filled in the upper part of the gas phase reactor, and gaseous N— (β-hydroxyethyl) -12-pyrrolidone is supplied from the upper end of the gas phase reactor. A method of heating to 50 ° C. or higher is described. On page 2 of Japanese Patent Application Laid-Open No. 3-181451, a Raschig ring made of inorganic glass or stainless steel is disclosed as a filler, and this filler is filled in a gas phase reactor, A method is described in which gaseous N- (α-methoxyethyl) formamide is introduced and heated to 300 ° C or more to cause a thermal decomposition reaction.

Japanese Patent Application Laid-Open No. 2001-276660 discloses that a silica-alumina firing material containing at least 0.5% by weight of an alkali metal element and at least 10% by weight of silicon as an oxide is used as a filler. There is disclosed a filler obtained by carrying an alcohol compound on the resultant and then calcining the filler. The filler is charged into a gas phase reactor, and gaseous 2-ethoxyethanol is introduced into the reactor. A method is described in which a decomposition reaction is carried out by heating at a temperature of 100 ° C. or higher.

However, these conventional fillers are not always durable. For example, if they are used for a long period of time, the fillers are likely to deteriorate or lose their mass due to volatilization of components, and hydrogen chloride (HC) 1) This was particularly noticeable when acidic gas such as gas was used. Disclosure of the invention The present inventors have conducted intensive studies to develop a filler for a gas phase reactor having excellent durability. As a result, the aluminum content is about 90% by weight or more in terms of oxide, that is, in terms of aluminum oxide. The present inventors have found that a filler consisting of has little deterioration and mass change even when used for a long period of time, and can be used for a long period of time.

That is, the present invention provides a filler for a gas phase reaction comprising alumina having an aluminum content of about 90% by weight or more in terms of aluminum oxide.

As described above, the filler of the present invention has excellent durability and can be used for a long time. Brief Description of Drawings

1 to 3 are cross-sectional views of a gas-phase reaction reactor filled with a filler according to the present invention. BEST MODE FOR CARRYING OUT THE INVENTION

The filler in the present invention is made of alumina, and includes, for example, a crystalline material such as alumina and r-alumina, preferably an alumina. Also, powdered alumina (A 1 ₂ 0 ₃₎ may be a sintered body obtained by sintering a. In particular, a sintered body made of alumina is preferable because it has a small specific surface area and good thermal conductivity.

The alumina in the present invention contains aluminum (A 1) in an amount of about 90% by weight or more, preferably about 92% by weight or more in terms of aluminum oxide. It may contain substantially 100% by weight of aluminum oxide in terms of aluminum oxide without substantially containing metal components other than aluminum. The content of metal components other than aluminum may be 0% or less as long as they are about 10% by weight or less in terms of oxides. Examples of the metal component other than aluminum include silicon (SΠ, alkali metals such as sodium (Na) and potassium (K), and transition metals such as iron (F e) and titanium (T i). .

The specific surface area of the filler in the present invention are preferably lm ² Z g or less, more preferably 0. 5 m ² g or less, more preferably not more than 0. ² m 2 Z g, this case, the filling of the present invention The material is sufficiently durable even when a strongly acidic starting compound such as hydrogen chloride is reacted at a high temperature. The filler exhibits sufficient durability especially in a strong chlorinated atmosphere such as in the presence of hydrogen chloride containing no water. The specific surface area can be measured as a BET specific surface area by a nitrogen adsorption method. A sintered body made of alumina is preferred because it has a small specific surface area.

The size of the filler in the present invention can be 0.1 mm or more and 2 cm or less, and is preferably 1 mm or more and 1 cm or less.

The shape of the filler varies depending on the shape of the gas phase reactor in which it is used, the reaction conditions, and the like, and is appropriately selected. For example, it may be in the form of an amorphous powder, a sphere, or a column. The spherical shape is preferred because the filling into the reactor is easy, and the bulk density of the filling does not easily change depending on the filling rate. Various types of spherical alumina are commercially available, for example, as a powder frame medium, a catalyst carrier, and the like, and these commercially available aluminas can be used as the filler in the present invention.

Examples of commercially available alumina include “HD” (trade name) and rsSA-995j (both manufactured by Nitsukato Corporation).

The filler in the present invention can be used by filling a reactor for introducing and reacting a gaseous raw material compound.

Examples of such a raw material compound include strongly acidic compounds such as hydrogen chloride (H C 1), and olefins. Since the filler in the present invention has sufficient durability against strongly acidic compounds such as hydrogen chloride, it can be suitably used for the reaction.

The gas phase reaction is performed in the reactor filled with the filler according to the present invention. Examples of such a reaction include an oxidation reaction in which hydrogen chloride is used as a raw material compound (A) and oxygen (〇 ₂ ) is reacted therewith to produce chlorine (Cl ₂ ) as a reactant; Isomerization reaction to obtain an isomer of olefins as a reactant by using the olefins as a reactant; using olefins as a raw material compound, adding water and alcohols thereto, and forming a derivative of the olefins as a reactant An addition reaction to be obtained; and an oxidation reaction in which an olefin is used as a raw material compound and oxygen is reacted therewith to produce an olefin oxide as a reactant.

The gas-phase reaction reactor used in the present invention may be a fixed-bed reactor in which the packing material filled therein is fixed and used, or a moving-bed reactor in which the packing material is used while being moved. It may be a fluidized bed reactor which is used while being fluidized together with the raw material compound.

Hereinafter, embodiments of the present invention will be described with reference to FIGS. 1 to 3, but the present invention is not limited to such embodiments.

1 to 3 are cross-sectional views of a gas-phase reactor filled with a gas-phase reaction filler (1) used in the present invention as a filler. The gas phase reactor (2) fixes the filling material The fixed bed reactor used. The gas-phase reactor (2) includes a reaction tube as a reactor body (20), and further includes a jacket (21) that covers the reaction tube (20). A heating medium (3) flows through the jacket (21), and the reaction tube (20) is cooled or heated by the heating medium (3). The heat medium (3) is taken out of the jacket (21), for example, and then temperature-controlled by a heat exchanger (not shown) or the like, and is again introduced into the jacket (21). May be circulated. The type of the heat medium (3) is appropriately selected and used depending on the reaction temperature, and examples thereof include water, oil, molten salt, and ionic liquid. The number of reaction tubes (20) in the gas-phase reactor (2) is not particularly limited. For example, a single-tube gas-phase reactor having only one reaction tube (20), such as a gas-phase reactor (2) shown in FIGS. 1 and 2, or FIG. As shown in the gas-phase reactor (2), a multi-tube gas-phase reactor provided with two or more reaction tubes (20), and the plurality of reaction tubes (20) covered with a jacket (21). It may be.

By introducing the gaseous starting compound (A) into such a gas phase reactor (2), the starting compound (A) can be reacted. The raw material compound (A) is introduced into the reaction tube (20), while the reaction tube (20) is cooled or heated by the heating medium (3). The raw material mixture (A) introduced from the inlet (2a) reacts in the reaction tube, and the reactant (B) generated by the reaction is taken out from the outlet (2c).

In the present invention, the position of the filled filler (1) in the reaction tube (20) is not particularly limited. For example, as shown in FIG. 1, the filler (1) is used by being filled near the inlet (2a) on the upstream side of the reaction region (2b) in the reaction tube (20). Here, the reaction region (2b) is a region where most of the raw material compound (A) reacts, for example, a catalyst layer filled with a solid catalyst for the reaction. By filling the filler (1) in the vicinity of the inlet (2a), the raw material compound (A) introduced from the inlet is quickly heated to be led to the catalyst layer (2b). It is expected to support the solid catalyst and prevent the movement of the solid catalyst due to the wind pressure of the raw material compound (A).

Further, the filler (1) in the present invention may be used by filling it near the outlet (2c) downstream of the catalyst layer (2b). By filling the filler (1) in the vicinity of the outlet (2c), the catalyst layer (2b) is supported to prevent the movement of the catalyst due to the wind pressure of the raw material mixture (A), especially the scattering from the outlet. It can be expected that the reaction product (B) after the reaction is rapidly cooled.

Furthermore, the filler (1) according to the present invention may be used by filling the catalyst layer (2b) filled with the catalyst together with the catalyst. By filling the catalyst layer (2b) with the filler (1) together with the catalyst, the amount of catalyst per unit volume in the catalyst layer (2b) can be reduced and adjusted, and the heat transfer from the catalyst can be adjusted. Things can be expected. As shown in FIG. 2, when a single reaction tube (20) is filled with a plurality of catalyst layers (2b, 2), a layer (2d) partitioning between the catalyst layers (2b, 2b ') is formed. The filler (1) in the present invention may be filled. By using such a partition layer (2d), the catalyst in the catalyst layers (2b, 2b ') is prevented from moving and being mixed with the flow of the raw material compound (A) and the reactant (B). When the raw material compound (A) is heated in the upstream catalyst layer (2b), it can be expected that the heated raw material compound is cooled and led to the downstream catalyst layer (2b ′). Here, the divided catalyst layers (2b, 2b ') may be filled with the same composition of catalytic power or may be filled with different compositions of catalytic power.

In the reactor according to the present invention, as shown in the multitubular gas phase reactor in FIG. 3, a jacket (2) may be provided with a partition plate (4). The partition plate (4) supports the plurality of reaction tubes (20), fixes it to the jacket (21), and regulates or blocks the flow of the heat carrier (3) flowing through the jacket (21). Has a role. Examples of the partition plate (4) include a tube plate (41) for fixing the reaction tube (20) to the jacket (21) at the inlet (2a) of the reaction tube (20); and an outlet (2c) for the reaction tube (20). A tube plate (42) for fixing the reaction tube (20) to the jacket (21) by using an intermediate tube plate (43) for dividing the inside of the jacket (21) into a plurality of sections (21, 21 ') in the middle of the reaction tube (20). Baffle plate (44) for changing the direction of flow of heat carrier (3).

In addition, the intermediate tube plate (43) and the baffle plate (44) may be tightly fixed to the reaction tube (20), or may have a slight gap between the reaction tube (20) and The heat medium (3) flowing in the jacket (21) may move between the sections (21, 2Γ) through the gap. The baffle plate (44) changes the direction of flow of the heat medium (3) in the jacket (21) so that the heat medium (3) flows evenly in the entire jacket (21). The flow of the heat medium (3) in the jacket (21) is adjusted by the partition plates (4) such as the tube sheets (41, 42), the intermediate tube sheet (43), and the baffle plate (44).

Generally, in a multitubular gas-phase reactor provided with a partition plate (4) in a jacket (21), the inside of the jacket (21) is located near a portion where the reaction tube (20) is in contact with the partition plate (4). As a result, the heat medium (3) may stay, and the cooling and heating of the reaction tube (20) may become insufficient near that portion. However, in the present invention, by filling the filler (1) in a portion of the reaction tube (20) where the heat exchange tends to be insufficient, even if the flow of the heat medium (3) is sufficient. However, it is preferable that the entire reaction tube (20) can be sufficiently cooled or heated even if it is not. This is because the filler (1) used in the present invention is made of alumina having an aluminum content of 90% by weight or more, and exhibits good thermal conductivity. From the viewpoint of such good thermal conductivity, the filler (1) in the present invention preferably has a specific surface area of 1 m ² Zg or less. Good. A sintered body made of alumina is preferred because of its small specific surface area and particularly good thermal conductivity.

If the filler (1) in the present invention is filled near the portion where the reaction tube (20) and the partition plate (4) are in contact inside the reaction tube (20), heating is insufficient. This is preferable because it is possible to prevent a reduction in the reaction yield of the catalyst and a deterioration of the catalyst and a reaction tube due to insufficient cooling.

In the reaction tube (20), the starting compound (A) can be reacted at 600 ° C or lower, preferably 500 ° C or lower, more preferably 400 ° C or lower. The filler (1) in the present invention exhibits a remarkable durability effect at 200 ° C. or higher. It is preferably used in a reaction for reacting the starting compound (A) at a temperature of at least C, more preferably at least 300 ° C. Example

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.

Example 1

A spherical ceramic ball with a particle diameter of about 3 mm and a specific surface area of less than 0.1 m ² / g (measurement lower limit) measured by the BET method (Nitsukato Co., Ltd., “HD”, aluminum content in terms of oxides) _{_{(A 1 2 0 3) 9}} 3 wt%, silicon content (S I_〇 ₂₎ 5.4 wt%, potassium content (K ₂ 〇) 0.05 wt%, sodium content (Na ₂ 0) 0 . 3% by weight, the titanium content (Ti_〇 ₂₎ 0.1 wt%, iron content (Fe ₂ 〇 ₃₎ 0.15 wt%] using a 500 g as filler, the length of this inner diameter 25 mm of A 200 Omm nickel reaction tube was filled. Outside the reaction tube is covered with a jacket, the jacket [molten salt with NaN0 ₂ 50 wt% and KN0 ₃ 50 wt%; 350 "C] the heat medium. 0.C from one end of the introduction of the reaction tube, the large The gas was extracted from the other end while mixing and introducing hydrogen chloride gas and oxygen gas at a flow rate of 0.014 Nm ³ Z at a flow rate of 0.0305 Nm ³ / min in terms of atmospheric pressure. The ί¾¾ of the part was 350 ° C. After 100 hours, the internal filler was taken out and the mass was measured, and there was no change in the mass of the filler.

Example 2

In place of the alumina pole used in Example 1 as a filler, spherical alumina having a particle diameter of about 3 mm and a specific surface area of 140 m ² Zg (“NKHD-24”, manufactured by Sumitomo Chemical Co., Ltd. aluminum Niumu content _{_{(A 1 2 0 3) 99.}} 7 wt%, silicon content (S i 0 ₂₎ 0. 02 wt%, sodium © beam content _{(N a 2 0) 0.} 2 7 wt%, iron content _{_{(F e 2 0 3) 0}} . 0 2 wt%] 5 0 0 g of Yore, reaction tube of ^ and the heat medium The reaction was carried out in the same manner as in Example 1 except that the temperature of each was set at 250 ° C. When the filler was taken out and the mass was measured, there was no change in the filler mass.

Example 3

A reaction tube similar to that of Example 1 was prepared except that a nickel thermometer sheath and a tube having an outer diameter of 6 were installed on the reaction tube so that the gas temperature in the reaction tube could be measured in the axial direction of the reaction tube. The gas inlet side of the reaction tube was filled with a supported catalyst obtained by extrusion molding (1% by weight of ruthenium oxide supported on titania and alumina), and the gas outlet side was the same as that used in Example 1. The same filler was filled. Using the same heat medium as that used in Example 1, the heat medium was introduced into the jacket covering the reaction tube with the nucleus being 3oo :, while the heat medium was introduced from the gas inlet side of the reaction tube to 300 ”, 0.00”. Hydrogen chloride gas and oxygen gas were mixed and introduced at a flow rate of 300 Nm ³ Z (O: atmospheric pressure) and a flow rate of 0.014 Nm ³ (0, atmospheric pressure). The gas introduced into the reaction tube reacts and generates heat when it comes into contact with the catalyst layer, and the generated reaction gas reaches 350 at the gas outlet of the catalyst layer, but then comes into contact with the filler layer. However, the heat is removed by the heat transfer between the filler and the heating medium. As a result, at a distance of 20 cm from the gas inlet side of the filler, the temperature of the reaction gas drops to 300, the same as the heating medium. The temperature power of the reaction gas ¾ decreased slightly, indicating that the heat removal was good.

Example 4

A reaction tube was prepared in the same manner as in Example 1 except that a nickel thermometer sheath and a tube having an outer diameter of 6 were installed in the reaction tube so that the gas temperature in the reaction tube could be measured in the axial direction of the reaction tube. The gas inlet side of the reaction tube was filled with a supported catalyst obtained by extrusion molding (1% by weight of ruthenium oxide supported on titania and alumina), and the gas outlet side was the same as that used in Example 2. The same filler was filled. Using the same heat medium as that used in Example 1, the temperature was set to 300, and the heat medium was introduced into a jacket covering the reaction tube. Hydrogen chloride gas was introduced at a flow rate of 300 Nm ³ Z (0, converted to atmospheric pressure) and oxygen was introduced at a flow rate of 0.014 Nm ³ / min (0 ° C, converted to atmospheric pressure). The gas introduced into the reaction tube reacts and generates heat when it comes into contact with the catalyst layer, and the generated reaction gas reaches 35 Ot: at the gas outlet of the catalyst layer. The heat is removed by heat transfer between the filler and the heating medium, so that at a distance of 20 cm from the gas inlet side of the filler, the temperature of the reaction gas drops to 310 ° C and a temperature of 45 cm At this point, the reaction gas had decreased to 300, the same as the heat medium. The rapid reduction in the temperature of the reaction gas indicated that the heat removal was good.

Claims

The scope of the claims

1. Filler for gas phase reaction consisting of alumina with aluminum content of about 90% by weight or more in terms of aluminum oxide

2. The packing material for a gas phase reaction according to claim 1, which has a specific surface area of 1 m ² / g or less.

3. The filler for a gas phase reaction according to claim 1, wherein the filler is a sintered body made of a-alumina.

4. A gas phase reaction reactor filled with the filler according to any one of claims 1 to 3.

5. A gas phase reactor comprising a reaction tube and a jacket covering the reaction tube, wherein the reaction medium is cooled or heated by a heating medium flowing in the jacket, and the heating medium is provided near the reaction tube in the jacket. 4. A reactor for a gas phase reaction, comprising: a partition plate for rectifying the flow rate; and a filler near the partition plate in the reaction tube, which is filled with the filler for a gas phase reactor according to any one of claims 1 to 3.

6. Multi-tube reactor for gas phase reaction, comprising a plurality of reaction tubes, a jacket covering the reaction tubes, and a partition plate supporting the reaction tubes, fixed to the jacket (21), and regulating the flow of the heat medium in the jacket. The filler according to any one of claims 1 to 3, wherein the filler according to any one of claims 1 to 3 is filled in the reaction tube (20) near a portion where the reaction tube (20) and the partition plate (4) are in contact with each other. Reactor for phase reaction.

7. A gas phase reaction method for a compound, wherein a gaseous raw material compound is introduced into a reactor filled with the filler according to any one of claims 1 to 3 and reacted.

8. A method comprising providing a reaction tube and a jacket covering the reaction tube, and introducing or reacting a gaseous raw material compound into the reaction tube while cooling or heating the reaction tube with a heat medium flowing in the jacket. A partition plate for rectifying the heat medium is provided near the reaction tube in the jacket, and near the partition plate in the reaction tube, the filler for a gas phase reactor according to any one of claims 1 to 3. A method for reacting a compound, wherein

9. Multi-tube reactor for gas phase reaction, comprising a plurality of reaction tubes, a jacket covering the reaction tubes, and a partition plate supporting the reaction tubes, fixed to the jacket (21), and adjusting the flow of the heat medium in the jacket. Wherein the reaction is carried out by introducing a gaseous raw material compound into the reaction tube, wherein the reaction tube (20) is in the vicinity of a portion where the reaction tube (20) and the partition plate (4) are in contact with each other. A method for reacting a compound, the method comprising:

10. The reaction method according to any one of claims 7 to 9, wherein the compound is reacted at 200 ° C or higher.

11. The reaction method according to any one of claims 7 to 10, wherein the raw material compound contains hydrogen chloride and oxygen.

12. A method for producing chlorine, comprising reacting hydrogen chloride and oxygen by the reaction method according to claim 11.