JP2011092925A - Mixer of combustible gas and combustion supporting gas - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a mixer with higher safety than conventionally known which can effectively inhibit the expansion of a generated combustion reaction, even in the case that a combustible gas and a combustion supporting gas are mixed. <P>SOLUTION: The mixer (10) comprises a tubular mixing part (1) for mixing the combustible gas and the combustion supporting gas; a combustible gas feed throat formed at one end (1a) of the tubular mixing part (1); a combustible gas conveyer (3) which feeds the combustible gas into the tubular mixing part (1) from the combustible gas feed throat; a mixed gas outlet which is formed at one end (1b) of the tubular mixing part (1) and spews a mixture of the combustible gas and the combustion supporting gas; and a combustion supporting gas feeder tube (5) which is connected with the tubular mixing part (1) between the other end (1a) and one end (1b) of the tubular mixing part (1) and feeds the combustion supporting gas into the tubular mixing part (1) from a combustion supporting gas feed throat (5a). In addition, the combustible gas conveyor (3) can make an adjustment of the flow velocity of the combustible gas at the combustion supporting gas feed throat (5a) so as to control to be at least the combustion rate of the mixture of the combustible gas and the combustion supporting gas. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a mixing device that mixes a combustible gas and an auxiliary combustible gas.

  A mixed gas of combustible gas and auxiliary combustible gas is used in various reaction processes. For example, a mixed gas obtained by mixing a combustible gas such as oxygen with a hydrocarbon gas such as methane, which is a combustible gas, is used in a disproportionation reaction for producing carbon monoxide and hydrogen. A mixed gas obtained by mixing a combustible gas containing hydrogen and an auxiliary combustible gas containing oxygen is used for an oxidation reaction for producing hydrogen peroxide, and an epoxidation in which the hydrogen peroxide epoxidizes an olefin. It is known to be used for reaction.

  As a mixing device of the combustible gas and the auxiliary combustible gas, for example, a mixture container to which the combustible gas and the auxiliary combustible gas are supplied is filled with a filler to form a large number of narrow gas flow paths, and the mixing container There is known a mixing apparatus in which the flow velocity of the gas flowing inside is increased (see Patent Document 1).

JP 2009-29680 A

  When combustible gas and auxiliary combustible gas are mixed in a conventional mixing apparatus, a combustion reaction may occur during the mixing, and the combustion reaction may be expanded. In order to perform safer mixing, there is a need for a mixing device that does not have the risk of expansion even if such a combustion reaction occurs.

Under such circumstances, as a result of intensive studies on a mixing device for combustible gas and auxiliary combustible gas, the following invention was achieved.
[1] A mixing device for mixing a combustible gas and a supplementary combustible gas,
A tubular mixing section for mixing the combustible gas and the auxiliary combustible gas;
A combustible gas supply port provided at one end of the tubular mixing section;
A combustible gas transporter for supplying combustible gas into the tubular mixing section from the combustible gas supply port;
A mixed gas outlet of the combustible gas and the auxiliary combustible gas provided at the other end of the tubular mixing portion;
A combustible gas transport pipe connected to the tubular mixing portion between one end and the other end of the tubular mixing portion, and supplying an auxiliary combustion gas into the tubular mixing portion from the auxiliary combustion gas supply port; The mixing apparatus is a combustible gas transporter capable of adjusting the flow rate of the combustible gas at the auxiliary combustible gas supply port to be higher than the combustion speed of the mixed gas of the combustible gas and the auxiliary combustible gas.
[2] The tubular mixing section includes at least one mixing member selected from the group consisting of a static mixer and a dispersion mixing member between the auxiliary combustible gas supply port and the mixed gas outlet. Mixing device.
[3] The mixing apparatus according to [1] or [2], wherein the combustible gas contains hydrogen and the auxiliary combustible gas contains oxygen.
[4] The mixing apparatus according to [3], wherein the combustible gas further contains propylene.
[5] The mixing apparatus according to [3] or [4], wherein the combustible gas further includes an inert component.
[6] The mixing apparatus according to any one of [1] to [5],
A reactor connected to a mixed gas outlet of the mixing device.
[7] A control valve for adjusting the flow rate of the auxiliary combustion gas passing through the auxiliary combustion gas supply pipe;
A measuring device for measuring the concentration of the auxiliary combustion gas in the reactor;
The controller according to [6], further including a controller that controls the flow rate of the auxiliary combustion gas through the auxiliary combustion gas supply pipe using a control valve based on the concentration of the auxiliary combustion gas in the reactor measured by the measuring device. Reactor.
[8] The above-mentioned [7], wherein the controller can control the flow rate of the auxiliary combustion gas through the auxiliary combustion gas supply pipe using a control valve so that the concentration of the auxiliary combustion gas in the reactor is maintained substantially constant. Reactor.
[9] The reaction apparatus according to any one of [6] to [8], further including a circulation line for returning the gas in the reactor to the combustible gas transporter.
[10] supplying combustible gas into the tubular mixing section from one end of the tubular mixing section;
The auxiliary combustion gas is supplied into the tubular mixing section from the auxiliary combustion gas supply port between one end and the other end of the tubular mixing section, and the mixed gas of the combustible gas and the auxiliary combustion gas is discharged from the other end of the tubular mixing section. The combustible gas supplied from one end of the tubular mixing portion is mixed with the auxiliary combustion gas supplied from the auxiliary combustion gas supply port and flows in the tubular mixing portion, and combustible from the other end of the tubular mixing portion. A method for producing a mixed gas from which a mixed gas of gas and auxiliary combustible gas is obtained, wherein the flow rate of the combustible gas at the auxiliary combustible gas supply port is equal to or higher than the combustion rate of the mixed gas of the combustible gas and auxiliary combustible gas. The method for producing a mixed gas, characterized in that the flow rate of the combustible gas supplied to the tubular mixing section is adjusted.
[11] Supplying the mixed gas obtained by the mixed gas production method of [10] to the reactor,
Supplying a mixed gas comprising measuring the concentration of the auxiliary combustion gas in the reactor and controlling the supply of the auxiliary combustion gas to the tubular mixing section based on the measured concentration of the auxiliary combustion gas in the reactor Method.
[12] The mixed gas supply method according to [11], wherein the supply of the auxiliary combustion gas to the tubular mixing unit is controlled so as to maintain the concentration of the auxiliary combustion gas in the reactor substantially constant.
[13] The method for supplying a mixed gas according to the above [11] or [12], further comprising extracting the gas from the reactor and reusing it as a combustible gas supplied to the tubular mixing section.
[14] The method for producing a mixed gas according to [10], wherein the combustible gas contains hydrogen and the auxiliary combustible gas contains oxygen.
[15] The method for producing a mixed gas according to [14], wherein the combustible gas further contains propylene.
[16] The method for producing a mixed gas according to the above [14] or [15], wherein the combustible gas further contains an inert component.

  ADVANTAGE OF THE INVENTION According to this invention, even if it mixes combustible gas and auxiliary combustible gas, the mixing apparatus with higher safety | security which can prevent effectively the generation | occurrence | production of combustion reaction can be provided.

It is a schematic sectional drawing which shows the mixing apparatus in one embodiment of this invention. It is an equilateral triangle coordinate graph of 5 parts by weight of propylene and 1.7 parts by weight of hydrogen, combustible gas (propylene + H ₂ ), auxiliary combustible gas (oxygen, O ₂ ), and inert gas (nitrogen, N ₂ ). It is a schematic sectional drawing which shows the mixing apparatus in another embodiment of this invention. It is a schematic sectional drawing which shows one example of the mixing member which can be used for this invention. It is a schematic sectional drawing which shows another example of the mixing member which can be used for this invention. It is a schematic sectional drawing which shows the mixing apparatus in another embodiment of this invention. It is a schematic sectional drawing which shows the mixing apparatus in another embodiment of this invention. It is a schematic sectional drawing which shows the reaction apparatus in one embodiment of this invention. It is a schematic sectional drawing which shows the reaction apparatus in another embodiment of this invention. 1 is a schematic cross-sectional view of a tubular mixing portion of a mixing apparatus used in Example 1. FIG. It is a schematic sectional drawing of the tubular mixing part of the mixing apparatus used in Example 2. FIG.

(Embodiment 1)
A mixing apparatus and a method for producing a mixed gas in one embodiment of the present invention will be described with reference to FIG.

  The mixing apparatus 10 of this embodiment supplies the tubular mixing part 1, the combustible gas supply port provided in the end 1a of the tubular mixing part 1, and supplies combustible gas in the tubular mixing part 1 from a combustible gas supply port. Between the one end 1a and the other end 1b of the tubular mixing section 1 and the combustible gas and auxiliary combustion gas outlet provided at the other end 1b of the tubular mixing section 1 An auxiliary combustion gas supply pipe 5 connected to the mixing unit 1 and supplying the auxiliary combustion gas into the tubular mixing unit 1 from the auxiliary combustion gas supply port 5a is provided.

  The tubular mixing part 1 is for mixing the combustible gas and the auxiliary combustible gas inside thereof. The tubular mixing part 1 has only to have a combustible gas supply port and a mixed gas outlet at both ends 1a and 1b, respectively, and the both ends 1a and 1b are continuously connected. The tubular mixing portion 1 may have any cross-sectional shape and cross-sectional area, but in the illustrated embodiment, it has a substantially circular cross-section.

  The combustible gas transport machine 3 is not particularly limited as long as the combustible gas can be supplied at an appropriate flow rate as will be described later. Examples thereof include a centrifugal compressor, an axial flow compressor, a volume compressor, a fan, and a blower. Can do.

  The auxiliary combustion gas supply pipe 5 has an auxiliary combustion gas supply port 5 a that communicates with the inside of the tubular mixing unit 1. For example, as shown in FIG. 1, the auxiliary combustible gas supply pipe 5 is inserted into the tubular mixing portion 1 between one end 1a and the other end 1b of the tubular mixing portion 1, and the tip thereof is bent, The auxiliary combustible gas supply port 5a opens toward the downstream side (right side in FIG. 1) of the tubular mixing portion. The auxiliary combustible gas supply pipe 5 may have any appropriate cross-sectional shape and cross-sectional area, but in the illustrated embodiment, it has a substantially circular cross-section. The auxiliary combustible gas supply pipe 5 may generally be provided with a control valve (not shown in FIG. 1) that can adjust the flow rate of the auxiliary combustible gas passing through the inside, but this is not essential to the present embodiment.

  Using such a mixing device 10, the combustible gas and the auxiliary combustible gas are mixed. The combustible gas only needs to contain a component that can be burned by reacting with oxygen (hereinafter referred to as “combustible component”). For example, hydrogen, a hydrocarbon compound containing olefin, and two or more of these And the like. The combustible gas may further contain an inert component such as nitrogen or water vapor in addition to the combustible component. The auxiliary combustible gas only needs to contain oxygen, and examples thereof include oxygen gas and air.

  A combustible gas is supplied into the tubular mixing unit 1 from the combustible gas supply port at one end 1a by using the combustible gas transport device 3. Further, the auxiliary combustion gas is supplied into the tubular mixing portion 1 from the auxiliary combustion gas supply port 5 a through the auxiliary combustion gas supply pipe 5. Thus, the combustible gas supplied by the combustible gas transport machine 3 eventually passes through the auxiliary combustible gas supply port 5a of the auxiliary combustible gas supply pipe 5 and the auxiliary combustible gas supplied from the auxiliary combustible gas supply port 5a. The gas flows through the tubular mixing portion 1 together, and finally, a mixed gas of combustible gas and auxiliary combustion gas is obtained from the mixed gas outlet at the other end 1 b of the tubular mixing portion 1.

At this time, the tubular mixing section 1 is used by using the combustible gas transporter 3 so that the flow rate of the combustible gas at the auxiliary combustible gas supply port 5a is equal to or higher than the combustion speed of the mixed gas of the combustible gas and the auxiliary combustible gas. Adjust the flow rate of combustible gas to
When the mixing apparatus has a substantially cylindrical tubular mixing portion as shown in FIGS. 1 and 3 or a tubular mixing portion having a tapered portion 1c as shown in FIG. 6 (FIGS. 3 and 6 will be described later), the combustion promoting property is increased. The flow rate of the combustible gas at the gas supply port is approximately equal to or higher than the flow rate of the combustible gas at the combustible gas supply port of the tubular mixing portion.
By adjusting in this way, even if a combustion reaction occurs, since the combustible gas flows at a flow rate higher than the combustion speed, it is possible to effectively prevent the combustion reaction from expanding.

  When the “flow rate of the combustible gas at the auxiliary combustible gas supply port” is equal to or higher than the combustion speed of the mixed gas of the combustible gas and the auxiliary combustible gas, the auxiliary combustible gas supply port 5a considered to have a relatively high concentration of the auxiliary combustible gas. Even in the vicinity of, there is a tendency to suppress the occurrence and expansion of the combustion reaction. A lower auxiliary combustion gas concentration is preferred because it tends to be difficult to ignite. The flow rate of the combustible gas at the auxiliary combustible gas supply port 5a is determined by the size and shape of the tubular mixing portion 1 to be used, the position of the auxiliary combustible gas supply port 5a in the tubular mixing portion 1, and the like. It can be adjusted by changing the amount of flammable gas supplied from the unit.

  The burning rate of the mixed gas of combustible gas and auxiliary combustible gas is determined according to the composition of the mixed gas. The burning rate of the mixed gas of a predetermined composition is Tadao Takeno, Toshio Iijima, “Measurement of burning rate by the spherical vessel method”, Report of the Institute of Space and Aeronautics, University of Tokyo, 1980, Vol. 17, No. 1 (B), p. It can be measured according to the known spherical container method described in 261-272. Schematically, a mixed gas prepared to have a predetermined composition is put in a spherical container, ignited, a change with time in pressure is measured, and a combustion rate can be obtained from the measurement result.

  The composition of the mixed gas of combustible gas and auxiliary combustible gas is considered to be equal to the combined composition of the supplied combustible gas and auxiliary combustible gas at the mixed gas outlet at the other end 1 b of the tubular mixing portion 1. The composition of the gas in the tubular mixing part 1 is substantially equal to the composition of the supplied combustible gas on the upstream side (left side in FIG. 1) from the auxiliary combustible gas supply port 5a, and downstream from the auxiliary combustible gas supply port 5a. In the vicinity, when viewed microscopically, the composition may differ depending on the flow state (or mixed state).

  When the combustible gas does not contain an inert component, the “combustion rate of the mixed gas of combustible gas and auxiliary combustible gas” is the combustible component with respect to the two components combustible component of combustible gas and oxygen of auxiliary combustible gas. It is possible to apply a combustion rate of a mixed gas having a composition in which oxygen is present in a theoretical amount necessary for burning (hereinafter referred to as “stoichiometric composition”). When the combustible gas is gradually mixed with the combustible gas, the gas composition in the middle of mixing is changed from a composition equal to the combustible component of the supplied combustible gas to a composition equal to the oxygen amount of the supplied combustible gas. It is considered that when it changes and becomes a stoichiometric composition, there is no excess or deficiency in the amount of oxygen necessary for combustion of combustible components, so that the maximum combustion rate is given. It is considered that the expansion of the combustion reaction can be sufficiently prevented if the “flow rate of the reactive gas” is equal to or higher than the combustion rate at such a stoichiometric composition.

  When the flammable gas contains an inert component, the flammable component and the flammable component in the three-component equilateral triangle coordinate graph (vol%) of the flammable component of the flammable gas, the oxygen of the auxiliary flammable gas, and the inert component of the flammable gas A line connecting a stoichiometric composition line in which oxygen forms a stoichiometric composition, a point indicating the composition of the combustible component and the inert component of the combustible gas to be supplied, and a point indicating the oxygen amount of the auxiliary combustible gas to be supplied ( Hereinafter, the combustion rate of the mixed gas having the composition of the intersection with the “operation line” may be applied. When the combustible gas is gradually mixed with the combustible gas, from the point indicating the composition of the combustible component and the inert component of the supplied combustible gas, toward the point indicating the oxygen amount of the supplied combustible gas It is considered that the maximum combustion rate is given when moving on the operation line and when the stoichiometric composition is reached, and the “flow rate of the combustible gas at the auxiliary combustion gas supply port” is the combustion rate at the stoichiometric composition. If it is above, it is thought that expansion of a combustion reaction can fully be prevented.

  Hereinafter, the composition of the mixed gas for determining the “combustion rate of the mixed gas of combustible gas and auxiliary combustible gas” will be described more specifically with reference to FIG.

FIG. 2 is an equilateral triangular coordinate graph of 5 parts by weight of propylene and 1.7 parts by weight of hydrogen, combustible gas (propylene + H ₂ ), auxiliary combustible gas (oxygen, O ₂ ), and inert gas (nitrogen, N ₂ ). It is. At point X, propylene + H ₂ = 100 vol%, at point Y, O ₂ = 100 vol%, and at point Z, N ₂ = 100 vol%.

When a mixed gas of 5 parts by weight of propylene and 1.7 parts by weight of hydrogen is used as the combustible component of the combustible gas, the stoichiometric composition of the combustible component and oxygen is point A (propylene + H _{2 in} FIG. 2) without nitrogen. = _22.2vol%, the O 2 = 77.8vol%). When nitrogen is added as an inert component to this mixed gas, it moves on the straight line AZ from point A to point Z while maintaining the stoichiometric composition of the combustible component and oxygen, and the ratio of nitrogen is too small Explosion does not occur at higher temperatures. The oxygen concentration at this boundary is referred to as a critical oxygen concentration, and is represented by a point B (propylene + H ₂ = 2.3 vol%, O ₂ = 8.0 vol%) in FIG. The straight line AB forms a stoichiometric composition line. On the other hand, even in the absence of nitrogen, no explosion occurs if the oxygen concentration is too low or too high. The oxygen concentration at this boundary is defined as a lower explosion limit concentration (O ₂ ) and an upper explosion limit concentration (O ₂ ), and point C (propylene + H ₂ = 49.5 vol%, O ₂ = 50.5 vol%) and point D ( Propylene + H ₂ = 2.3 vol%, O ₂ = 97.7 vol%). The straight line BC and the straight line BD are explosion limits, and the region surrounded by the point BCD is the explosion range.

When the combustible gas is composed of a mixed gas of 5 parts by weight of propylene and 1.7 parts by weight of hydrogen as a combustible component and does not include an inert component, the stoichiometric composition of the combustible component and oxygen is represented by point A in FIG. Become. When oxygen gas (O ₂ = 100 vol%) is used as the auxiliary combustible gas, and this is gradually mixed with the above combustible gas, the gas composition in the middle of mixing is a straight line XY (from the point X to the point Y). N ₂ = 0 vol%) and is considered to give the maximum burning rate when it reaches the stoichiometric composition at point A. Therefore, the combustion rate of the mixed gas having the composition of point A is applied as the “combustion rate of the mixed gas of combustible gas and auxiliary combustible gas”.

When the combustible gas is composed of a mixed gas of 5 parts by weight of propylene and 1.7 parts by weight of hydrogen as a combustible component and nitrogen gas as an inert component, the composition of the combustible gas to be supplied is here for convenience. Point E (propylene + H ₂ = 6.9 vol%, O ₂ = 1.7 vol%, N ₂ = 91.4 vol%). When oxygen gas (O ₂ = 100 vol%) is used as the auxiliary combustible gas and is gradually mixed with the above combustible gas, the gas composition in the middle of mixing is on a straight line EY from point E to point Y. And is considered to give the maximum burning rate when the stoichiometric composition is reached at point H. Point H is the intersection of the straight line EY that is the operation line and the straight line AB that is the stoichiometric composition line, and points F and G are the intersections of the straight line EY that is the operation line and the straight lines BC and BD, respectively. And the limit concentration (the upper limit and the lower limit of the fuel concentration when the gas having the composition of point E and the gas having the composition of point Y (O ₂ = 100 vol%) are mixed). Therefore, the combustion rate of the mixed gas having the composition of point H is applied as the “combustion rate of the mixed gas of combustible gas and auxiliary combustible gas”.

  Even when other components are used as the combustible gas and the auxiliary combustible gas, the “combustion rate of the mixed gas of the combustible gas and the auxiliary combustible gas” can be obtained by referring to the above explanation, The flow rate of the combustible gas at the mouth may be adjusted using a combustible gas transporter so that it is equal to or higher than the “combustion rate of the mixed gas of combustible gas and auxiliary combustible gas”.

  As a result, even if a combustion reaction occurs, since the combustible gas flows at a flow rate higher than the combustion speed, it is possible to effectively prevent the combustion reaction from being blown out by the combustible gas and expanding. Since the effect of preventing the expansion of the combustion reaction is high, the content of the inert gas in the combustible gas and / or the auxiliary combustible gas can be reduced, and the production efficiency of the mixed gas per volume can be improved. In addition, since the filler can be used or reduced, the production efficiency of the mixed gas per volume is improved, and the pressure loss of the supply pressure of the combustible gas and / or the auxiliary combustion gas during the mixed gas production is reduced. Can be reduced. In addition, since the pressure loss is small, the power cost of the combustible gas transporter tends to be reduced.

(Embodiment 2)
A mixing apparatus and a mixed gas manufacturing method according to another embodiment of the present invention will be described with reference to FIG. The present embodiment is a modification of the above-described first embodiment, and is the same as the first embodiment unless otherwise specified.

  In the mixing apparatus 10 ′ of the present embodiment, the tubular mixing portion 1 ′ includes a mixing member 7 between the auxiliary combustible gas supply port 5 a and the other end 1 b of the tubular mixing portion. Thus, by inserting the mixing member 7 between the auxiliary combustible gas supply port 5a and the other end 1b of the tubular mixing portion, the combustible gas and the auxiliary combustible gas can be mixed more quickly, and the combustion reaction Can be more effectively prevented.

  For example, a static mixer (swivel mechanism), a dispersion mixing member, or the like can be used as the mixing member 7 (in FIG. 3, a static mixer is illustrated by way of example).

  The static mixer may have a structure such as, for example, the static mixer 7a shown in FIG. 4 (FIG. 4 is a partially enlarged view of the tubular mixing portion 1 ′, and the static mixer 7a may have any appropriate length and / or Combustible gas and auxiliary combustible gas can be swirled together. As the static mixer, for example, those commercially available from Noritake Company Limited can be used. When a static mixer is used, there is an advantage that pressure loss is relatively small. In addition, a uniform mixing effect can be obtained in the radial direction in the tubular mixing portion 1 ′.

  The dispersion mixing member may have a structure such as a dispersion mixing member 7b shown in FIG. 5 (FIG. 5 is a partially enlarged view inside the tubular mixing portion 1 ′, and the dispersion mixing member 7b has, for example, a drum-shaped hole. Are arranged in a staggered manner and may have any suitable length and / or number of elements), combustible gas and auxiliary combustible gas dispersed (or divided) and mixed together. As the dispersion mixing member, for example, “Dispersion-kun” commercially available from Fujikin Co., Ltd. can be used. When the dispersion mixing member is used, the contact area between the dispersion mixing member and the gas is relatively large. Therefore, if the dispersion mixing member is made of a material having a high thermal conductivity such as a metal, an unexplosive effect due to the cooling of the flame can be obtained. It is done. Moreover, it is preferable that the mixing zones of the dispersion mixing member are independent from each other.

(Embodiment 3)
A mixing apparatus and a mixed gas manufacturing method according to another embodiment of the present invention will be described with reference to FIG. The present embodiment is a modification of the above-described first embodiment, and is the same as the first embodiment unless otherwise specified.

  In the mixing apparatus 10 '' of the present embodiment, the cross-sectional area of the tubular mixing portion 1 '' at the position where the auxiliary combustible gas supply port 5a is present is such that the tubular mixing portion 1 '' near the one end 1a of the tubular mixing portion is cut off. A tapered portion 1c is provided between these positions so as to be smaller than the area.

  When the tubular mixing portion has a substantially circular cross section, the inner diameter D1 of the tubular mixing portion 1 '' in the vicinity of one end 1a of the tubular mixing portion is equal to the inner diameter of the tubular mixing portion 1 '' at the position where the auxiliary combustible gas supply port 5a exists. Greater than D2. As shown in FIG. 6, the substantially cylindrical portion on the upstream side (on the one end 1a side) from the tapered portion 1c and the substantially cylindrical portion on the downstream side (on the other end 1b side) from the tapered portion 1c are arranged substantially coaxially. The taper part 1c has a substantially truncated cone shape and continuously connects them.

  In the illustrated embodiment, the inner diameter D2 of the tubular mixing portion 1 '' at the position where the auxiliary combustible gas supply port 5a exists is equal to the inner diameter of the substantially cylindrical portion on the downstream side of the tapered portion 1c. Note that it is not limited to:

  According to this embodiment, since the combustible gas passes through a smaller cross-sectional area at the auxiliary combustible gas supply port 5a, the flow rate of the combustible gas can be further increased. As a result, the burden on the combustible gas transporter can be further reduced, and the flow rate of the combustible gas at the auxiliary combustible gas supply port 5a can be adjusted more efficiently than the combustion rate of the mixed gas of the combustible gas and the auxiliary combustible gas. can do. Or when maintaining the driving | running condition of a combustible gas transport machine, it can prevent more reliably that a combustion reaction expands by the flow velocity of combustible gas increasing.

(Embodiment 4)
A mixing apparatus and a mixed gas manufacturing method according to another embodiment of the present invention will be described with reference to FIG. The present embodiment is a modification of the above-described first embodiment, and is the same as the first embodiment unless otherwise specified.

  In the mixing apparatus 10 ′ ″ of the present embodiment, the auxiliary combustion gas supply pipe 5 ′ is formed on the wall of the tubular mixing portion 1 ′ ″ at the auxiliary combustion gas supply port 5a ′, for example, in a T shape as shown in the figure. It is connected.

  Preferably, a porous film 9 is provided in the auxiliary combustible gas supply port 5a '. The porous film 9 may be a film having air permeability, and for example, a ceramic, a wire mesh, a polymer film, a sintered metal film, or the like can be used. The presence of the porous membrane 9 suppresses the occurrence of combustion in the auxiliary combustible gas supply pipe 5 '.

  According to the present embodiment, the auxiliary gas is supplied from the auxiliary gas supply port 5a ′ connected to the wall of the tubular mixing portion 1 ′ ″, preferably through the porous membrane 9, into the tubular mixing portion 1 ′ ″. Therefore, the auxiliary combustible gas can be supplied while being dispersed, and thus can be quickly mixed with the combustible gas.

(Embodiment 5)
The reaction apparatus and mixed gas supply method according to one embodiment of the present invention will be described with reference to FIG. Unless otherwise specified, it is the same as any one of the first to fourth embodiments described above.

  The reaction apparatus 20 of the present embodiment further includes a reactor 11 connected to the mixed gas outlet of the mixing apparatus in addition to the mixing apparatus as described above in the first to fourth embodiments (for purposes of illustration in the figure). Thus, the mixing apparatus of the first embodiment is shown, and the same reference numerals are used for the same members as those of the first embodiment. The reactor 11 can be selected according to the target reaction.

  Using such a reactor 20, the combustible gas and the auxiliary combustible gas are mixed, and the obtained mixed gas of the combustible gas and the auxiliary combustible gas is reacted. Mixing is the same as in any of Embodiments 1 to 4, and a mixed gas of combustible gas and auxiliary combustible gas is obtained from the other end 1 b of the tubular mixing portion 1. The obtained mixed gas is supplied to the reactor 11 as it is, and is used for the reaction in the reactor 11 (FIG. 8 exemplarily shows a liquid phase reaction).

  According to this embodiment, the same effects as those of Embodiments 1 to 4 can be obtained, and furthermore, the combustible gas and the auxiliary combustible gas can be safely mixed immediately before being supplied to the reactor 11.

  Although this embodiment is not limited, olefin and hydrogen can be used for combustible gas, and oxygen can be used for auxiliary combustible gas. Hydrogen and oxygen produce hydrogen peroxide in reactor 11, which can lead to olefin epoxidation reactions. For example, when propylene is used as the olefin, propylene oxide can be produced. More details will be described later in Embodiments 7 and 8.

(Embodiment 6)
A reaction apparatus and a mixed gas supply method according to another embodiment of the present invention will be described with reference to FIG. The present embodiment is a modification of the above-described fifth embodiment, and is the same as the fifth embodiment unless otherwise specified.

  In addition to the apparatus configuration of the fifth embodiment, the reaction apparatus 20 ′ of the present embodiment includes a control valve 13 that adjusts the flow rate of the auxiliary combustion gas passing through the auxiliary combustion gas supply pipe 5, and the auxiliary combustion gas in the reactor 11. A measuring instrument 15 for measuring the concentration and a controller 17 electrically connected to the measuring instrument 15 and the control valve 13 are provided. Moreover, although not essential for the present embodiment, a circulation line 19 may be provided between the reactor 11 and the combustible gas transporter 3.

  The concentration of the auxiliary combustion gas in the reactor 11 can be measured by the measuring device 15, and a data signal of this measured concentration is input to the controller 17 to adjust the flow rate of the auxiliary combustion gas through the auxiliary combustion gas supply pipe 5. Thus, a control signal is output to the control valve 13. In this way, the flow rate of the auxiliary combustion gas passing through the auxiliary combustion gas supply pipe 5 can be controlled through the control valve 13 based on the concentration of the auxiliary combustion gas in the reactor 11 measured by the measuring device 15. As a result, the amount of the auxiliary combustion gas supplied to the tubular mixing portion 1 and, consequently, the amount of the auxiliary combustion gas sent into the reactor 11 can be feedback controlled as desired. The control can be performed, for example, so as to maintain the concentration of the auxiliary combustible gas in the reactor 11 to be substantially constant, and thus can be controlled to the extent that no combustion reaction is caused in the reactor 11.

  Most of the gas in the reactor 11 is a flammable gas, and includes a flammable component that is not consumed in the reaction, and an inert component in some cases. By extracting the gas in the reactor 11 and returning it to the combustible gas transporter 3 through the circulation line 19, the combustible gas, more specifically the combustible component and possibly the inert component can be efficiently reused. . Note that such a configuration is not essential to the present embodiment.

(Embodiment 7)
The present invention, more specifically, the mixing apparatus and mixed gas production method of Embodiments 1 to 4, and the reaction apparatus and mixed gas supply method of Embodiments 5 to 6 are described in JP 2010-159245 A. In particular, it can be used to carry out a method for producing such an oxide compound, particularly a method for producing an epoxy compound.

  First, olefin and hydrogen are used as the combustible gas, oxygen is used as the auxiliary combustible gas, these are mixed using the mixing apparatus of the present invention, for example, the mixing apparatus of Embodiments 1 to 4, and the resulting mixed gas is the reactor. To supply.

  As a reaction step, an epoxy compound is obtained by reacting olefin, oxygen, and hydrogen in the reactor in the presence of titanosilicate (I) or a silylated product thereof and a noble metal catalyst. Oxygen and hydrogen produce hydrogen peroxide in the presence of a noble metal catalyst, which acts as an oxidant on the olefin to produce an epoxy compound.

  Hereinafter, the titanosilicate (I) used in this embodiment or its silylated product, its preparation method, and the reaction process using this will be described in detail.

-Titanosilicate (I) or a silylated product thereof and preparation method thereof Titanosilicate (I) is obtained by contacting titanosilicate (II) having the following X-ray diffraction pattern with a structure-directing agent. .
X-ray diffraction pattern (lattice spacing d / Å)
12.4 ± 0.8
10.8 ± 0.3
9.0 ± 0.3
6.0 ± 0.3
3.9 ± 0.1
3.4 ± 0.1

Titanosilicate is a general term for silicates having tetracoordinate Ti (titanium). In the present specification, titanosilicate means a titanosilicate having substantially tetracoordinated Ti, and an ultraviolet-visible absorption spectrum in a wavelength region of 200 nm to 500 nm has a maximum absorption in a wavelength region of 210 nm to 230 nm. A peak appears (for example, see Chemical Communications 1026-1027, (2002) FIGS. 2D and 2E).
The ultraviolet-visible absorption spectrum can be measured by a diffuse reflection method using an ultraviolet-visible spectrophotometer equipped with a diffuse reflection device.
Ti-MWW means crystalline titanosilicate having an MWW structure. The MWW structure is a molecular sieve structure represented by a structure code defined by the International Zeolite Society (IZA), and has a super cage (0 .7 × 0.7 × 1.8 nm) and a half cup-shaped side pocket having an inlet made of a 12-membered oxygen ring.

Since the titanosilicate (I) is obtained by bringing the titanosilicate (II) into contact with the structure directing agent, the fine structure containing the structure directing agent in the porous structure based on the titanosilicate (II) is obtained. It is believed that the pores are present at a certain rate. It is confirmed from the X-ray diffraction pattern that the titanosilicate (I) has such a porous structure.
Furthermore, since the titanosilicate (I) is obtained without contacting the titanosilicate (II) and the structure directing agent without a firing step, the peak intensity ratio of the X-ray diffraction pattern is MWW structure. Is different. The titanosilicate (I) exhibits an excellent activity as a catalyst for an organic compound oxidation reaction (olefin epoxidation reaction in the present embodiment).

The titanosilicate (I) shows an absorption peak in a wavelength region of 210 nm to 230 nm in an ultraviolet-visible absorption spectrum measured by a diffuse reflection method (baseline reference material: Spectralone) using an ultraviolet-visible spectrophotometer. .
The titanosilicate (I) exhibits the following X-ray diffraction pattern.
(Lattice spacing d / Å)
12.4 ± 0.8
10.8 ± 0.3
9.0 ± 0.3
6.0 ± 0.3
3.9 ± 0.1
3.4 ± 0.1
In the lattice spacing, “d / Å” indicates that the unit of the lattice spacing d is angstrom.
Titanosilicate (I), in yet X-ray diffraction pattern, the peak intensity ^{X 1} in (9.0 ± 0.3), the intensity ratio of the peak intensity ^{X 2,} of (3.4 ± 0.1) A relationship in which X ¹ / X ² is more than 0 and 0.4 or less is shown.
The X-ray diffraction pattern can be measured using an X-ray diffractometer that irradiates copper K-alpha radiation.

In the titanosilicate (I), the molar ratio of silicon to nitrogen (Si / N ratio) is not particularly limited, but is preferably 5 or more and 50 or less.
The lower limit of the Si / N ratio is more preferably 8 or more, and even more preferably 10 or more. The upper limit of the Si / N ratio is more preferably 35 or less, still more preferably 18 or less, and particularly preferably 16 or less.
Titanosilicate (I) has good catalytic activity when the Si / N ratio is within the above range.
The Si / N ratio is obtained by elemental analysis of the sample to be measured. This elemental analysis can be performed by a general method as follows. The contents of Ti (titanium), Si (silicon) and B (boron) can be measured by alkali melting-nitric acid dissolution-ICP emission analysis. The content of N (nitrogen) can be measured by an oxygen circulating combustion / TCD detection method.

The titanosilicate (I) is a ratio (SH ₂ O / SN ₂ ) between a specific surface area value (SH ₂ O) measured by a water vapor adsorption method and a specific surface area value (SN ₂ ) measured by a nitrogen adsorption method. Is preferably 0.7 or more, and more preferably 0.8 or more. The upper limit of the SH ₂ O / SN ₂ is preferably 1.5 or less, and more preferably 1.3 or less.
The SN ₂ is calculated by the BET method after measuring the sample to be measured at 150 ° C., then measuring by the nitrogen adsorption method. The SH ₂ O is calculated by the BET method after the sample to be measured is deaerated at 150 ° C., measured by the water vapor adsorption method at an adsorption temperature of 298K.

  The silylated product of the titanosilicate (I) can be obtained, for example, by silylating the titanosilicate (I) with a silylating agent such as 1,1,1,3,3,3-hexamethyldisilazane. .

In the present specification, the structure directing agent means an organic compound used for forming a zeolite structure. The above structure-directing agent can form a precursor of a zeolite structure by organizing polysilicate ions or polymetallosilicate ions around it (see Zeolite Science and Engineering, pages 33-34, 2000, Kodansha Scientific) .
The structure directing agent is preferably a nitrogen-containing compound capable of forming a zeolite having an MWW structure. For example, organic amines such as piperidine and hexamethyleneimine; N, N, N-trimethyl-1-adamantanammonium salt ( Octyltrimethylammonium salt (octyltrimethylammonium salt) described in Chemistry Letters 916-917 (2007), N, N, N-trimethyl-1-adamantanammonium hydroxide, N, N, N-trimethyl-1-adamantanammonium iodide, etc.) Quaternary ammonium salts such as hydroxide and octyltrimethylammonium bromide). These compounds may be used singly or in combination of two or more at any ratio.
Particularly preferred structure directing agents are piperidine or hexamethyleneimine, and these may be used in combination.

  In the production of the titanosilicate (I), the amount of the structure-directing agent is preferably 0.01 parts by mass or more, more preferably 0.1 parts by mass or more with respect to 1 part by mass of the titanosilicate (II). 1 part by mass or more is more preferable, and 2 parts by mass or more is particularly preferable. The amount of the structure directing agent is preferably 100 parts by mass or less, more preferably 50 parts by mass or less, still more preferably 20 parts by mass or less, and more preferably 15 parts by mass or less with respect to 1 part by mass of the titanosilicate (II). More preferred is 10 parts by mass or less.

  When the amount of the structure-directing agent is within the above range, titanosilicate (I) can be easily prepared.

Contact between the titanosilicate (II) and the structure directing agent is carried out by placing the titanosilicate (II) and the structure directing agent in a closed container such as an autoclave and applying pressure while heating. Alternatively, the titanosilicate (II) and the structure directing agent may be mixed in a container such as a glass flask in the air with or without stirring.
The lower limit of the contact temperature is preferably 0 ° C. or higher, more preferably 20 ° C. or higher, further preferably 50 ° C. or higher, and particularly preferably 100 ° C. or higher. The upper limit of the temperature is about 250 ° C, preferably 200 ° C or lower, more preferably 180 ° C or lower.
The pressure at the time of such contact is not particularly limited, but is preferably about 0 to 10 MPa as a gauge pressure. The titanosilicate (I) obtained by contact is separated, for example, by filtration. If necessary, the separated titanosilicate (I) may be subjected to post-treatment such as washing and drying. The amount of the structure-directing agent in the obtained titanosilicate (I) can also be adjusted by this post-treatment operation.

The titanosilicate (I) is preferably obtained by further washing after the contact. By performing such washing, not only the purity of the obtained titanosilicate (I) is increased, but the amount of the structure-directing agent present in the titanosilicate (I) is considered to be adjusted. The above-described cleaning may be performed by appropriately adjusting the amount of cleaning liquid, pH and the like as necessary. The washing is preferably performed using water as the washing liquid, and more preferably performed until the pH of the washing liquid becomes 7 to 11. When drying after the contact, conditions such as temperature can be appropriately set as long as the characteristics of the following titanosilicate (I) are not impaired.
In addition, since titanosilicate (I) is converted into an MWW structure by firing, it is classified as a Ti-MWW precursor.

Examples of the titanosilicate (II) include crystalline titanosilicate having an MWW structure or MSE structure, Ti-MWW precursor (a), and Ti-YNU-1.
As said Ti-YNU-1, Ti-YNU-1 etc. which were described in Angewante Chemie International Edition 43,236-240, (2004) etc. are mentioned, for example.
Examples of the crystalline titanosilicate having the MWW structure include Ti-MWW described in JP-A No. 2003-327425.
Examples of the crystalline titanosilicate having the MSE structure include Ti-MCM-68 described in JP-A-2008-50186.

In the present specification, the Ti-MWW precursor means a titanosilicate having a layered structure. Such a Ti-MWW precursor exhibits the property of becoming Ti-MWW when fired.
The Ti-MWW precursor (a) is a layered titanosilicate that is converted into Ti-MWW by firing. The Ti-MWW precursor (a) preferably has a molar ratio of silicon to nitrogen (Si / N ratio) of 21 or more. As the Ti-MWW precursor (a), titanosilicate (I) can also be used.
Examples of the Ti-MWW precursor (a) include a Ti-MWW precursor described in JP-A-2005-262164.
As the titanosilicate (II), a crystalline titanosilicate having an MWW structure or an MSE structure, or a Ti-MWW precursor (a) is preferable, and a Ti-MWW or Ti-MWW precursor having an MWW structure ( a) is more preferred.

  The titanosilicate (II) can be produced by a known method such as the method described in the above-mentioned literature. The crystalline titanosilicate having an MWW structure can also be produced, for example, by firing a Ti-MWW precursor (a).

Reaction Step The titanosilicate (I) or a silylated product thereof is used as a catalyst in the olefin epoxidation reaction (reaction in which an olefin compound is converted into a corresponding epoxy compound) of this embodiment. In this embodiment, hydrogen peroxide as an oxidant for the olefin epoxidation reaction is supplied by being produced in the same reaction system as the oxidation reaction, and more specifically, oxygen in the presence of a noble metal catalyst. And hydrogen. Such a reaction step is preferably performed in a liquid phase containing a solvent.

In this embodiment, titanosilicate (I) can be subjected to a reaction after previously contacting with hydrogen peroxide.
A hydrogen peroxide solution can be used as the hydrogen peroxide in the contact. The concentration of the hydrogen peroxide solution is preferably in the range of 0.0001% by mass to 50% by mass. The hydrogen peroxide solution may be an aqueous solution or a solution of a solvent other than water. As the solvent other than water, a suitable solvent can be selected from among solvents for oxidation reaction and the like. The contact temperature is preferably in the range of 0 to 100 ° C, and more preferably in the range of 0 to 60 ° C.

Examples of the olefin (or olefin compound) include a substituted or unsubstituted hydrocarbyl group or a compound in which hydrogen is bonded to a carbon atom constituting an olefin double bond.
Examples of the substituent of the hydrocarbyl group include a hydroxyl group, a halogen atom, a carbonyl group, an alkoxycarbonyl group, a cyano group, and a nitro group. Examples of the hydrocarbyl group include saturated hydrocarbyl groups, and examples of the saturated hydrocarbyl group include alkyl groups.
Specific examples of the olefin include alkene having 2 to 10 carbon atoms and cycloalkene having 4 to 10 carbon atoms.
Examples of the alkene having 2 to 10 carbon atoms include ethylene, propylene, butene, pentene, hexene, heptene, octene, nonene, decene, 2-butene, isobutene, 2-pentene, 3-pentene, 2-hexene, 3-hexene, Examples include 4-methyl-1-pentene, 2-heptene, 3-heptene, 2-octene, 3-octene, 2-nonene, 3-nonene, 2-decene and 3-decene.
Examples of the cycloalkene having 4 to 10 carbon atoms include cyclobutene, cyclopentene, cyclohexene, cycloheptene, cyclooctene, cyclononene, and cyclodecene.
In the present embodiment, the olefin is more preferably an alkene having 2 to 10 carbon atoms, more preferably an alkene having 2 to 5 carbon atoms, and particularly preferably propylene.

  Examples of the noble metal catalyst include noble metals such as palladium, platinum, ruthenium, rhodium, iridium, osmium and gold, or alloys or mixtures thereof. Preferable noble metals include palladium, platinum, and gold. A more preferred noble metal is palladium. As palladium, for example, a palladium colloid may be used (see, for example, JP-A-2002-294301, Example 1). As the noble metal catalyst, a noble metal compound that is converted into a noble metal by reduction in an oxidation reaction system may be used, and a preferred noble metal compound is a palladium compound. In addition, when using palladium as this noble metal catalyst, metals other than palladium, such as platinum, gold | metal | money, rhodium, iridium, and osmium, can also be added and mixed and used. A preferable metal other than palladium is platinum.

  Examples of the palladium compound include tetravalent palladium compounds such as sodium hexachloropalladium (IV) tetrahydrate and potassium hexachloropalladium (IV); palladium (II) chloride, palladium (II) bromide, palladium acetate (II), palladium acetylacetonate (II), dichlorobis (benzonitrile) palladium (II), dichlorobis (acetonitrile) palladium (II), dichloro (bis (diphenylphosphino) ethane) palladium (II), dichlorobis (triphenyl) Phosphine) palladium (II), dichlorotetraammine palladium (II), dibromotetraammine palladium (II), dichloro (cycloocta-1,5-diene) palladium (II), palladium trifluoroacetate (II) 2-valent palladium compounds such as are exemplified.

  The noble metal is preferably used by being supported on a carrier. The noble metal can be used by being supported on titanosilicate (I), and oxides such as silica, alumina, titania, zirconia and niobium; hydrates such as niobic acid, zirconium acid, tungstic acid and titanic acid; Carbon; or a mixture thereof can also be used. When a noble metal is supported in addition to titanosilicate (I), the carrier supporting the noble metal can be mixed with titanosilicate (I), and the mixture can be used as a catalyst. Among carriers other than titanosilicate (I), carbon is a preferred carrier. Known carbon carriers include activated carbon, carbon black, graphite, carbon nanotubes and the like.

As a method for preparing a noble metal-supported catalyst, for example, a method in which a noble metal compound is supported on a support and then reduced is known. For supporting the noble metal compound, a conventionally known method such as an impregnation method can be used.
As a reduction method, reduction may be performed using a reducing agent such as hydrogen, or reduction may be performed with ammonia gas generated during thermal decomposition in an inert gas atmosphere. The reduction temperature varies depending on the kind of the noble metal compound and the like, but when dichlorotetraamminepalladium (II) is used as the noble metal compound, the range of 100 to 500 ° C is preferable, and the range of 200 to 350 ° C is more preferable.
The noble metal-supported catalyst contains a noble metal in a range of 0.01 to 20% by mass, preferably in a range of 0.1 to 5% by mass.
The amount of the precious metal used may be 0.00001 parts by mass or more, preferably 0.0001 parts by mass or more, and more preferably 0.001 parts by mass or more with respect to 1 part by mass of titanosilicate (I). The amount of the precious metal used may be 100 parts by mass or less, preferably 20 parts by mass or less, and more preferably 5 parts by mass or less with respect to 1 part by mass of titanosilicate (I).

Examples of the solvent used in the reaction system include water, an organic solvent, a mixture of both, and the like.
Examples of the organic solvent include alcohol solvents, ketone solvents, nitrile solvents, ether solvents, aliphatic hydrocarbon solvents, aromatic hydrocarbon solvents, halogenated hydrocarbon solvents, ester solvents, and mixtures thereof.
Examples of the aliphatic hydrocarbon solvent include aliphatic hydrocarbons having 5 to 10 carbon atoms such as hexane and heptane. As an aromatic hydrocarbon solvent, C6-C15 aromatic hydrocarbons, such as benzene, toluene, xylene, are mentioned.
As said alcohol solvent, C1-C6 monohydric alcohol, C2-C8 glycol, etc. are mentioned. The alcohol solvent is preferably an aliphatic alcohol having 1 to 8 carbon atoms, more preferably a monohydric alcohol having 1 to 4 carbon atoms such as methanol, ethanol, isopropanol and tert-butanol, more preferably tert-butanol.
As said nitrile solvent, C2-C4 alkyl nitriles and benzonitrile, such as acetonitrile, propionitrile, isobutyronitrile, butyronitrile, are preferable, and acetonitrile is especially preferable.
The organic solvent is preferably an alcohol solvent and / or a nitrile solvent from the viewpoint of catalytic activity and selectivity.

In this reaction step, when a buffering agent is present in the reaction system, the catalyst activity can be prevented from decreasing or the catalyst activity can be further increased, and the utilization efficiency of the raw material gas can be improved.
The buffer is typically present in the reaction system by dissolving in a liquid phase, but may be included in a part of the noble metal complex in advance. For example, there is a method in which an ammine complex such as palladium (Pd) tetraammine chloride is supported on a support by an impregnation method or the like and then reduced to leave ammonium ions and generate a buffer during the epoxidation reaction. The addition amount of the buffering agent is preferably 0.001 to 100 mmol / kg per kg of the liquid phase solvent.
As the buffer,
1) Sulfate ion, hydrogen sulfate ion, carbonate ion, hydrogen carbonate ion, phosphate ion, hydrogen phosphate ion, dihydrogen phosphate ion, hydrogen pyrophosphate ion, pyrophosphate ion, halogen ion, nitrate ion, hydroxide ion An anion selected from the group consisting of carboxylate ions having 1 to 10 carbon atoms;
2) a cation selected from the group consisting of ammonium, alkylammonium having 1 to 20 carbon atoms, alkylarylammonium having 7 to 20 carbon atoms, alkali metal, and alkaline earth metal;
The buffer agent which consists of is illustrated.
Here, as a C1-C10 carboxylate ion, acetate ion, formate ion, acetate ion, propionate ion, butyrate ion, valerate ion, caproate ion, caprylate ion, caprate ion, and benzoic acid An ion etc. are illustrated.
Examples of the alkyl ammonium having 1 to 20 carbon atoms include tetramethylammonium, tetraethylammonium, tetra-n-propylammonium, tetra-n-butylammonium, and cetyltrimethylammonium.
Examples of alkali metal and alkaline earth metal cations include lithium cation, sodium cation, potassium cation, rubidium cation, cesium cation, magnesium cation, calcium cation, strontium cation, and barium cation.

  Preferred buffering agents include ammonium sulfate, ammonium hydrogen sulfate, ammonium carbonate, ammonium hydrogen carbonate, ammonium dihydrogen phosphate, ammonium dihydrogen phosphate, ammonium phosphate, ammonium hydrogen pyrophosphate, ammonium pyrophosphate, ammonium chloride, ammonium nitrate, etc. An ammonium salt of an inorganic acid; and an ammonium salt of a carboxylic acid having 1 to 10 carbon atoms such as ammonium acetate; and preferred ammonium salts include ammonium dihydrogen phosphate.

  As in this embodiment, when hydrogen peroxide is synthesized from oxygen and hydrogen in the same reaction system as the oxidation reaction, the selectivity of the oxidized compound is further increased by allowing the quinoid compound to be present in the reaction system. Can be made.

（式中、Ｒ^１、Ｒ^２、Ｒ^３及びＲ^４は、水素原子を表すかあるいは、Ｒ^１とＲ^２、あるいはＲ^３とＲ^４は、それぞれ独立に、その末端で結合し、それぞれが結合している炭素原子と一緒になって、置換基を有していてもよいナフタレン環を表し、Ｘ及びＹはそれぞれ独立に、酸素原子もしくはＮＨ基を表す。） Examples of the quinoid compound include a ρ-quinoid compound and a phenanthraquinone compound represented by the following formula (1).

(Wherein R ¹ , R ² , R ³ and R ⁴ represent a hydrogen atom, or R ¹ and R ² , or R ³ and R ⁴ are each independently bonded at their ends, (It represents a naphthalene ring which may have a substituent together with the carbon atoms to which it is bonded, and X and Y each independently represents an oxygen atom or an NH group.)

As a compound of Formula (1),
1) A quinone compound (1A) in which in formula (1), R ¹ , R ² , R ³ and R ⁴ are all hydrogen atoms, and X and Y are both oxygen atoms,
2) A quinoneimine compound (1B) in which R ¹ , R ² , R ³ and R ⁴ are all hydrogen atoms, X is an oxygen atom, and Y is an NH group in formula (1),
3) In Formula (1), R ¹ , R ² , R ³ and R ⁴ are all hydrogen atoms, and quinonediimine compound (1C) in which X and Y are NH groups is exemplified.

（式中、Ｘ及びＹは式（１）において定義されたとおりであり、Ｒ^５、Ｒ^６、Ｒ^７及びＲ^８はそれぞれ独立に、水素原子、ヒドロキシル基もしくはアルキル基（例えば、メチル基、エチル基、プロピル基、ブチル基、及びペンチル基等の炭素数１〜５のアルキル基）を表す。）。
式（１）及び式（２）において、Ｘ及びＹは好ましくは、酸素原子を表す。 The quinoid compound of the formula (1) includes the following anthraquinone compound (2).

(Wherein X and Y are as defined in formula (1), R ⁵ , R ⁶ , R ⁷ and R ⁸ are each independently a hydrogen atom, a hydroxyl group or an alkyl group (for example, a methyl group, Represents an alkyl group having 1 to 5 carbon atoms such as an ethyl group, a propyl group, a butyl group, and a pentyl group).
In formula (1) and formula (2), X and Y preferably represent an oxygen atom.

  The quinoid compound can be a dihydro form of a partially hydrogenated quinoid compound depending on the reaction conditions, but these compounds may be used.

Examples of the quinoid compound include benzoquinone, naphthoquinone, anthraquinone, alkylanthraquinone compound, polyhydroxyanthraquinone, ρ-quinoid compound, o-quinoid compound, and the like.
Examples of the alkylanthraquinone compound include 2-ethylanthraquinone, 2-tert-butylanthraquinone, 2-amylanthraquinone, 2-methylanthraquinone, 2-butylanthraquinone, 2-tert-amylanthraquinone, 2-isopropylanthraquinone, 2-s. 2-alkylanthraquinone compounds such as butylanthraquinone and 2-s-amylanthraquinone; polyalkylanthraquinones such as 1,3-diethylanthraquinone, 2,3-dimethylanthraquinone, 1,4-dimethylanthraquinone and 2,7-dimethylanthraquinone Compounds. Examples of the polyhydroxyanthraquinone include 2,6-dihydroxyanthraquinone. Examples of the ρ-quinoid compound include naphthoquinone and 1,4-phenanthraquinone. Examples of the o-quinoid compound include 1,2-, 3,4- and 9,10-phenanthraquinone.
Preferred quinoid compounds include anthraquinone and 2-alkylanthraquinone compounds (in the formula (2), X and Y are oxygen atoms, R ⁵ is an alkyl group substituted at the 2-position, R ⁶ represents hydrogen, R ⁷ and R ⁸ represent a hydrogen atom.).

  The amount of the quinoid compound to be used is in the range of 0.001 to 500 mmol / kg, more preferably 0.01 to 50 mmol / kg, per 1 kg of the liquid phase solvent.

  Furthermore, in this embodiment, it is also possible to add an ammonium salt, an alkyl ammonium salt or an alkylaryl ammonium salt and a quinoid compound simultaneously to the reaction system.

  The quinoid compound can also be prepared by oxidizing a dihydro form of the quinoid compound using oxygen or the like in the reaction system. For example, hydroquinone or a compound in which a quinoid compound such as 9,10-anthracenediol is hydrogenated may be added to the liquid phase and oxidized with oxygen in a reactor to generate the quinoid compound.

（式中、Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４、Ｘ及びＹは、前記式（１）に関して定義されたとおりである。）

（式中、Ｘ、Ｙ、Ｒ^５、Ｒ^６、Ｒ^７及びＲ^８は前記式（２）に関して定義されたとおりである。）
式（３）及び式（４）において、Ｘ及びＹは、好ましくは酸素原子を表す。
好ましいキノイド化合物のジヒドロ体としては、上述の好ましいキノイド化合物に対応するジヒドロ体が挙げられる。 Examples of the dihydro form of the quinoid compound include compounds of the following formulas (3) and (4) which are dihydro forms of the compounds of the formulas (1) and (2).

(In the formula, R ¹ , R ² , R ³ , R ⁴ , X and Y are as defined for the formula (1).)

(Wherein X, Y, R ⁵ , R ⁶ , R ⁷ and R ⁸ are as defined for formula (2) above).
In formula (3) and formula (4), X and Y preferably represent an oxygen atom.
Preferred dihydro forms of quinoid compounds include dihydro forms corresponding to the above-mentioned preferred quinoid compounds.

  The reaction formats include fixed bed reaction, stirred tank reaction, fluidized bed reaction, moving bed reaction, bubble column reaction, tube reaction, circulation reaction, etc., in particular, circulation type fixed bed reaction, circulation type slurry complete mixing reaction. Etc.

In the present embodiment, there is no limitation on the reaction gas atmosphere.
When hydrogen peroxide is produced from oxygen and hydrogen in the presence of a noble metal in the same reaction system as in this embodiment, the partial pressure ratio of oxygen and hydrogen supplied to the reactor is oxygen: hydrogen = 1. : The range of 50 to 50: 1. A preferable partial pressure ratio of oxygen and hydrogen is oxygen: hydrogen = 1: 2 to 10: 1. If the partial pressure ratio between oxygen and hydrogen is too high, the production rate of the epoxy compound may decrease. On the other hand, if the partial pressure ratio of oxygen and hydrogen is too low, the selectivity of the epoxy compound may decrease due to an increase in by-product of the alkane compound.
In this embodiment, oxygen and hydrogen may be diluted with other gases. Other gases used for dilution include nitrogen, argon, carbon dioxide, methane, ethane and propane. Although there is no restriction | limiting in the density | concentration of the gas for dilution, Reaction is performed by diluting oxygen or hydrogen as needed.

  As the source gas, oxygen may be oxygen gas itself or air. As the oxygen gas, oxygen gas produced by an inexpensive pressure swing method can be used, and high-purity oxygen gas produced by cryogenic separation or the like can be used as necessary.

The reaction temperature is preferably 0 ° C. or higher, more preferably 40 ° C. or higher, and particularly preferably 50 ° C. or higher. On the other hand, the upper limit of the reaction temperature is preferably 200 ° C. or lower, more preferably 150 ° C. or lower, and particularly preferably 120 ° C. or lower.
If the reaction temperature is too low, the reaction rate tends to be slow, and if the reaction temperature is too high, there is a tendency for by-products due to side reactions to increase.

The reaction pressure is preferably in the range of 0.1 MPa to 20 MPa in gauge pressure, and more preferably in the range of 1 MPa to 10 MPa.
After the reaction, the reaction product can be collected by a known method such as distillation separation.

  In the present embodiment, the amount of titanosilicate (I) or silylated product can be appropriately selected according to the type of reaction, particularly the type of olefin used, etc., but with respect to the total amount of solvent in the liquid phase, The lower limit is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, and particularly preferably 0.5% by mass or more. On the other hand, the upper limit is preferably 20% by mass or less, more preferably 10% by mass or less, and particularly preferably 8% by mass or less.

  In the present embodiment, the amount of the olefin compound can be appropriately selected according to the type and reaction conditions, but the lower limit is 0.01 parts by mass or more with respect to 100 parts by mass of the total amount of the solvent in the liquid phase. Is preferable, 0.1 part by mass or more is more preferable, and 1 part by mass or more is particularly preferable. On the other hand, the upper limit is preferably 1000 parts by mass or less, more preferably 100 parts by mass or less, and particularly preferably 50 parts by mass or less.

  The amount of the oxidizing agent can be arbitrarily selected according to the type of olefin compound, reaction conditions, and the like, but is preferably 0.1 parts by mass or more, more preferably 1 part by mass with respect to 100 parts by mass of the olefin compound. That's it. As for the quantity of the said oxidizing agent, a preferable upper limit is 100 mass parts or less with respect to 100 mass parts of olefin compounds, and a more preferable upper limit is 50 mass parts or less.

  According to the present embodiment, olefin epoxidation can be carried out more safely.

(Embodiment 8)
The present invention, more specifically, the mixing apparatus and mixed gas production method of Embodiments 1 to 4, and the reaction apparatus and mixed gas supply method of Embodiments 5 to 6 are described in JP-A-2008-106030. Can be used to carry out such a method for producing an epoxy compound.

  First, olefin and hydrogen are used as the combustible gas, oxygen is used as the auxiliary combustible gas, these are mixed using the mixing apparatus of the present invention, for example, the mixing apparatus of Embodiments 1 to 4, and the resulting mixed gas is the reactor. To supply.

  Then, as a reaction step, olefin, oxygen, and hydrogen in a reactor, crystalline titanosilicate, mesoporous titanosilicate having a MEL structure, MTW structure, BEA structure, MWW structure, or DON structure in a liquid phase. An epoxy compound is obtained by reacting in the presence of titanosilicate (X) selected from the group consisting of layered titanosilicates, noble metal catalysts, and quinoid compounds or dihydro forms of quinoid compounds. Also in this embodiment, oxygen and hydrogen produce hydrogen peroxide in the presence of a noble metal catalyst, and hydrogen peroxide acts as an oxidizing agent for olefins to produce an epoxy compound.

  Hereinafter, the titanosilicate (X) used in this embodiment and the reaction process using this will be described in detail. In the present embodiment, unless otherwise specified, the same as in the seventh embodiment.

・ Titanosilicate (X)
The titanosilicate (X) is selected from the group consisting of a crystalline titanosilicate having a MEL structure, MTW structure, BEA structure, MWW structure or DON structure, mesoporous titanosilicate and layered titanosilicate.

Examples of the titanosilicate (X) used in the present embodiment include the following.
TS-2 having MEL structure and Ti-ZSM-12 having MTW structure (for example, those described in Zeolites 15, 236-242, (1995)), which are structural codes defined by the International Zeolite Society (IZA). Ti-Beta having a BEA structure (for example, one described in Journal of Catalysis 199, 41-47, (2001)), Ti-MWW having an MWW structure (for example, Chemistry Letters 774-775, (2000)) And crystalline titanosilicates such as Ti-UTD-1 having a DON structure (for example, those described in Zeolites 15, 519-525, (1995)).
Examples of layered titanosilicates include Ti-MWW precursors (for example, those described in JP-A-2003-32745) and Ti-YNU-1 (for example, Angewandte Chemie International Edition 43, 236-240, (2004)). And titanosilicate having a structure in which the layers of the MWW structure spread as shown in FIG.
Mesoporous titanosilicate is generally a titanosilicate having regular pores of 2 to 10 nm, and Ti-MCM-41 (for example, one described in Microporous Materials 10, 259-271, (1997)), Ti-MCM-48 (for example, described in Chemical Communications 145-146, (1996)), Ti-SBA-15 (for example, described in Chemistry of Materials 14, 1657-1664, (2002)) Etc. are exemplified. In addition, titanosilicate having characteristics of both mesoporous titanosilicate and titanosilicate zeolite such as Ti-MMM-1 (for example, those described in Microporous and Mesoporous Materials 52, 11-18, (2002)). Are also illustrated.

Of these titanosilicates (X), crystalline titanosilicate or lamellar titanosilicate having pores with 12 or more oxygen rings is preferable.
Examples of the crystalline titanosilicate having pores with 12 or more oxygen rings include Ti-ZSM-12, Ti-Beta, Ti-MWW, and Ti-UTD-1.
Examples of the layered titanosilicate having pores having an oxygen 12-membered ring or more include Ti-MWW precursor and Ti-YNU-1. More preferred titanosilicates include Ti-MWW and Ti-MWW precursors.

  The titanosilicate (X) used in this embodiment usually uses a surfactant as a mold agent or structure directing agent, hydrolyzes a titanium compound and a silicon compound, and crystallizes by hydrothermal synthesis or the like as necessary. It is synthesized by a method in which the surfactant is removed by calcination or extraction after improving the crystallization or pore regularity.

  A crystalline titanosilicate having an MWW structure is usually prepared as follows. That is, a gel is prepared by hydrolyzing a silicon compound and a titanium compound in the presence of a structure-directing agent. Next, the obtained gel is heated in the presence of water by hydrothermal synthesis or the like to prepare a layered crystal precursor. Further, the obtained layered crystal precursor is crystallized by firing to prepare crystalline titanosilicate having an MWW structure.

  The titanosilicate (X) used in this embodiment includes those silylated using a silylating agent such as 1,1,1,3,3,3-hexamethyldisilazane. Silylated titanosilicate is also a preferable titanosilicate (for example, silylated Ti-MWW, etc.) because silylation can further increase the activity or selectivity.

-Reaction process The said titanosilicate (X) is used as a catalyst in the epoxidation reaction of the olefin of this embodiment (reaction in which an olefin compound is converted into a corresponding epoxy compound). In this embodiment, hydrogen peroxide as an oxidant for the olefin epoxidation reaction is supplied by being produced in the same reaction system as the oxidation reaction, and more specifically, oxygen in the presence of a noble metal catalyst. And hydrogen. Such a reaction step is performed in a liquid phase containing a solvent in the presence of a quinoid compound or a dihydro form of a quinoid compound.

  As the noble metal catalyst used in the present embodiment, the same noble metal catalyst as in the seventh embodiment can be used.

  In the present embodiment, titanosilicate (X) can be activated and used by treatment with a hydrogen peroxide solution having an appropriate concentration. Usually, the concentration of the hydrogen peroxide solution can be in the range of 0.0001 to 50% by mass. The solvent of the hydrogen peroxide solution is not particularly limited, but water or a solvent used for the propylene oxide synthesis reaction is industrially simple and preferable.

  The olefin used in the present embodiment, the noble metal catalyst, and the solvent used in the reaction system may be the same as those described in the seventh embodiment. Further, the quinoid compound or dihydro form of the quinoid compound used in the present embodiment can be the same as that described in the seventh embodiment.

  In the present embodiment, the noble metal catalyst can be used by being supported on titanosilicate (X). The mass ratio of the noble metal catalyst to the titanosilicate (X) (the mass of the noble metal / the mass of the titanosilicate) is preferably 0.01 to 100% by mass, more preferably 0.1 to 20% by mass.

  The reaction step is usually carried out in a liquid phase consisting of water, an organic solvent or a mixture of both, and a quinoid compound or a dihydro form of the quinoid compound or a mixture of both is added to the quinoid compound derivative. It is preferably used after being dissolved in the liquid phase. Since the liquid phase contains an organic solvent, the quinoid compound derivative tends to work efficiently, so the amount of quinoid compound derivative used can be reduced compared to when the liquid phase does not contain an organic solvent. An epoxy compound can be obtained with good selectivity.

  When a mixture of water and an organic solvent is used, the ratio of water to the organic solvent is usually 90:10 to 0.01: 99.99, preferably 50:50 to 0.01: 99, by mass ratio. .99. When the ratio of water becomes too large, the epoxy compound may easily react with water to cause ring-opening deterioration, and the selectivity of the epoxy compound may be lowered. On the other hand, when the ratio of the organic solvent becomes too large, the recovery cost of the solvent increases.

  Examples of the reaction format include a fixed bed reaction, a stirred tank reaction, a fluidized bed reaction, a moving bed reaction, a bubble column reaction, a tube reaction, and a circulation reaction.

  In the present embodiment, the amount of titanosilicate (X) can also be appropriately selected according to the type of reaction, particularly the type of olefin used, and can be the same as in the seventh embodiment. Other reaction conditions are the same as in the seventh embodiment.

  Also according to this embodiment, olefin epoxidation can be carried out more safely.

  While several embodiments of the present invention have been described above, various modifications can be made to these embodiments. For example, also in Embodiment 5, as described in Embodiment 6, a circulation line for returning the gas in the reactor to the combustible gas transporter may be provided.

  The mixed gas obtained in Embodiments 1 to 4 can be used in any reaction apparatus in addition to the reaction apparatuses in Embodiments 5 and 6. In addition to the methods described in the seventh and eighth embodiments, the mixing device and the mixed gas manufacturing method according to the first to fourth embodiments and the reaction device and the mixed gas supplying method according to the fifth to sixth embodiments are optional. Appropriate methods can be used, for example as described in the following documents: WO 99/52884 (JP 2002-511454 A), WO 99/52885 (JP Table 2002-511455), International Publication No. 2001/023370 (Special Table No. 2003-510314 Publication), International Publication No. 2001/062380, International Publication No. 2002/008214, International Publication No. 2002/066841, International Publication No. 2002/057245, International Publication No. 2003/031423 (Japanese translations of PCT publication No. 2005-511524) International Publication No. 2003/044001 (Japanese Patent Publication No. 2005-514364), International Publication No. 2003/035631 (Special Publication No. 2005-510502 Publication), International Publication No. 2003/035630, International Publication No. 2003/035632. International Publication No. 2003/048143, International Publication No. 2004/026852, International Publication No. 2005/077531, International Publication No. 2005/082533, International Publication No. 2005/092524, International Publication No. 2005/092874, US Patent Application Publication No. 2005/0282699, United States Patent Application Publication No. 2005/0277542, International Publication No. 2006/065311, International Publication No. 2007/018864, United States Patent Application Publication No. 2007/0027347, international No. 2007/046958, International Publication No. 2007/050193, US Patent Application Publication No. 2007/0142651, US Patent Application Publication No. 2007/0093668, US Patent Application Publication No. 2008/0003175 US Patent Application Publication No. 2008/0015372, US Patent Application Publication No. 2008/0021230, US Pat. No. 7,387,981, US Patent Application Publication No. 2008/0146825, US Patent Application Publication No. No. 2008/0146826, U.S. Patent Application Publication No. 2008/0255379, U.S. Pat. No. 7,470,801, U.S. Patent Application Publication No. 2009/0112006, U.S. Pat. No. 7,501,532.

Example 1
According to Embodiment 2, the combustible gas and the auxiliary combustible gas were mixed under various conditions.

  A schematic cross-sectional view of the tubular mixing portion of the mixing apparatus used is shown in FIG. A SUS straight pipe having an inner diameter of 20 mm and a length of 300 mm was used as the tubular mixing portion 1 ′. As the auxiliary combustible gas supply pipe 5, the tip of a SUS circular pipe having an inner diameter of 5 mm is bent substantially coaxially with the tubular mixing section 1 ′, and the opening surface of the auxiliary combustion gas supply port 5a is one end 1a of the tubular mixing section ( It was arranged to be located about 50 mm downstream from the combustible gas supply port). As the mixing member 7, a commercially available static mixer 7a (TAH Industories Inc. (Mercury Supply Systems Co., Ltd.), manufactured by SUS, model number: 090-612) was used. In addition, the ignition devices E-01 to E-03 and the temperature sensors TI-01 to TI-03 are connected to the vicinity of the downstream side of the auxiliary combustion gas supply port 5a, the auxiliary combustion gas supply port 5a, and the other end 1b as shown in the figure. (Mixed gas outlet) between each other in the vicinity of the upstream side of the other end 1b. Specifically, E-01 is 55 mm, E-02 is 135 mm, and E-03 is 215 mm downstream from one end 1a. Moreover, each thermometer (TI-01-TI-03) shall be located 10 mm downstream from the ignition device (E-01-E-03), respectively. In addition, the static mixer with a length of 45.5 mm is an upstream spark plug at three locations between E-01 and E-02, between E-02 and E-03, and between E-03 and 1b. It was installed 21 mm away. The temperature rise due to the spark of the ignition device was about 10 to 20 ° C. (measured by flowing only nitrogen gas at 15 m / s so as not to cause a combustion reaction).

  As the combustible gas, a gas composed of 10 vol% of a mixed gas of 6 parts by weight of propylene and 4 parts by weight of hydrogen and 90 vol% of nitrogen gas was used. 100 vol% of oxygen gas was used as the auxiliary combustion gas. The burning rate of the mixed gas of combustible gas and auxiliary combustion gas is the burning rate of the mixed gas having the composition of point H in FIG. 2, and the flame stability limit of propane having a molecular structure similar to that of propylene used in this example. From about 30 m / s.

  Combustible gas and auxiliary combustible gas were tested under the condition No. 1 shown in Table 1. 01-No. Measure the maximum temperature at TI-01 to TI-03 when ignited with E-01, ignited with E-02, and ignited with E-03 while supplying at each supply amount of 08 Then, it was determined whether any one of TI-01 to TI-03 ignited. The results are shown in Tables 2-9. In these tables, the temperature is the highest temperature rise, and the judgment is “X” when no ignition occurs, “O” when ignition occurs but temperature rise is less than 100 ° C., ignition occurs, and temperature rise 100 ° C. The case where it was above was designated as “◎”.

As is clear from Table 1, the flow rate of the outlet mixed gas was equal to the sum of the combustible gas supply amount and the auxiliary combustion gas supply amount.
In addition, referring to Table 1, the condition No. 1 in which the flow rate of the combustible gas at the auxiliary combustible gas supply port is 30 m / s or more is obtained. 01, 02, 05-08 are examples of the present invention. 03 and 04 are comparative examples. As understood from Tables 2 to 9, ignition was not recognized in the examples of the present invention. As described above, according to the present invention, it was confirmed that the expansion of the combustion reaction can be effectively prevented.

(Example 2)
According to Embodiment 4, the combustible gas and the auxiliary combustible gas were mixed under various conditions.

  A schematic cross-sectional view of the tubular mixing portion of the used mixing apparatus is shown in FIG. A SUS straight pipe having an inner diameter of 20 mm and a length of 300 mm was used as the tubular mixing portion 1 ″ ″. As the auxiliary combustible gas supply pipe 5 ′, the tip of the SUS circular pipe having an inner diameter of 5 mm is connected to the tubular mixing part 1 ′ ″ in a T shape, and the central part of the opening of the auxiliary combustible gas supply port 5a is tubular mixed. It arrange | positioned so that it might be located about 50 mm downstream from the one end 1a (flammable gas supply port) of a part. In this example, no porous membrane was used. The positions of the ignition devices E-01 to E-03 and the temperature sensors TI-01 to TI-03 were the same as those in Example 1. As the combustible gas and the auxiliary combustible gas, the same ones as in Example 1 were used. Therefore, the combustion speed of the mixed gas of combustible gas and auxiliary combustible gas was set to about 30 m / s as in the case of Example 1.

  Combustible gas and auxiliary combustible gas were measured under the conditions No. 1 shown in Table 10. 11-No. The maximum temperature was measured at TI-01 to TI-03 when ignited at E-01, ignited at E-02, and ignited at E-03 while being supplied at each supply amount of 21. Then, it was determined whether any one of TI-01 to TI-03 ignited. The results are shown in Tables 11-21. The symbols in these tables are the same as in Example 1.

As is clear from Table 10, the flow rate of the outlet mixed gas was equal to the sum of the combustible gas supply amount and the auxiliary combustible gas supply amount.
Further, with reference to Table 10, the condition No. 1 in which the flow rate of the combustible gas at the auxiliary combustible gas supply port is 30 m / s or more is obtained. 11, 12, 18-21 are examples of the present invention. 13 to 17 are comparative examples. As understood from Tables 11 to 21, ignition was not recognized in the examples of the present invention. As described above, according to the present invention, it was confirmed that the expansion of the combustion reaction can be effectively prevented.

  ADVANTAGE OF THE INVENTION According to this invention, even if it mixes combustible gas and auxiliary combustible gas, the mixing apparatus with higher safety | security which can prevent effectively the generation | occurrence | production of combustion reaction can be provided.

1, 1 ', 1'',1''' Tubular mixing part 1a One end (combustible gas supply port)
1b The other end (mixed gas outlet)
DESCRIPTION OF SYMBOLS 1c Tapered part 3 Flammable gas transport machine 5 Auxiliary gas supply pipe 5a Auxiliary gas supply port 7 Mixing member 7a Static mixer 7b Dispersion mixing member 9 Porous membrane 10, 10 ', 10'',10''' Mixing device 11 Reactor 13 Control valve 15 (Combustible gas concentration) measuring device 17 Controller 19 Circulating line 20, 20 ′ Reactor D1, D2 Inner diameter X Propylene + H ₂ (Combustible component of combustible gas) 100 vol%
Y O ₂ (combustion supporting gas) 100 vol%
Z N ₂ (inert components of the combustible gas) 100 vol%
A Stoichiometric composition B Limit oxygen concentration Line AB Stoichiometric composition line C Explosive lower limit concentration (O ₂ )
D Explosive upper limit concentration (O ₂ )
Line BC, Line BD Explosion limit E Composition of flammable gas to be supplied Line EY Operation line F, G Limit concentration H Intersection of stoichiometric composition line and operation line

Claims (16)

A mixing device for mixing combustible gas and auxiliary combustible gas,
A tubular mixing section for mixing the combustible gas and the auxiliary combustible gas;
A combustible gas supply port provided at one end of the tubular mixing section;
A combustible gas transporter for supplying combustible gas into the tubular mixing section from the combustible gas supply port;
A mixed gas outlet of the combustible gas and the auxiliary combustible gas provided at the other end of the tubular mixing portion;
A combustible gas transport pipe connected to the tubular mixing portion between one end and the other end of the tubular mixing portion, and supplying an auxiliary combustion gas into the tubular mixing portion from the auxiliary combustion gas supply port; The mixing apparatus is a combustible gas transporter capable of adjusting the flow rate of the combustible gas at the auxiliary combustible gas supply port to be higher than the combustion speed of the mixed gas of the combustible gas and the auxiliary combustible gas.   The mixing device according to claim 1, wherein the tubular mixing unit includes at least one mixing member selected from the group consisting of a static mixer and a dispersion mixing member between the auxiliary combustible gas supply port and the mixed gas outlet.   The mixing apparatus according to claim 1 or 2, wherein the combustible gas contains hydrogen and the auxiliary combustible gas contains oxygen.   The mixing apparatus of claim 3, wherein the combustible gas further comprises propylene.   The mixing device according to claim 3 or 4, wherein the combustible gas further contains an inert component. A mixing apparatus according to any one of claims 1 to 5,
A reactor connected to a mixed gas outlet of the mixing device. A control valve for adjusting the flow rate of the auxiliary combustion gas passing through the auxiliary combustion gas supply pipe;
A measuring device for measuring the concentration of the auxiliary combustion gas in the reactor;
7. The reaction according to claim 6, further comprising a controller for controlling the flow rate of the auxiliary combustion gas through the auxiliary combustion gas supply pipe by a control valve based on the concentration of the auxiliary combustion gas in the reactor measured by the measuring device. apparatus.   The reaction device according to claim 7, wherein the controller can control the flow rate of the auxiliary combustion gas through the auxiliary combustion gas supply pipe using a control valve so as to maintain the concentration of the auxiliary combustion gas in the reactor substantially constant.   The reaction apparatus according to any one of claims 6 to 8, further comprising a circulation line for returning the gas in the reactor to the combustible gas transporter. Supplying combustible gas into the tubular mixing section from one end of the tubular mixing section;
The auxiliary combustion gas is supplied into the tubular mixing section from the auxiliary combustion gas supply port between one end and the other end of the tubular mixing section, and the mixed gas of the combustible gas and the auxiliary combustion gas is discharged from the other end of the tubular mixing section. The combustible gas supplied from one end of the tubular mixing portion is mixed with the auxiliary combustion gas supplied from the auxiliary combustion gas supply port and flows in the tubular mixing portion, and combustible from the other end of the tubular mixing portion. A method for producing a mixed gas from which a mixed gas of gas and auxiliary combustible gas is obtained, wherein the flow rate of the combustible gas at the auxiliary combustible gas supply port is equal to or higher than the combustion rate of the mixed gas of the combustible gas and auxiliary combustible gas. The method for producing a mixed gas, characterized in that the flow rate of the combustible gas supplied to the tubular mixing section is adjusted. A mixed gas obtained by the method for producing a mixed gas according to claim 10 is supplied to a reactor,
Supplying a mixed gas comprising measuring the concentration of the auxiliary combustion gas in the reactor and controlling the supply of the auxiliary combustion gas to the tubular mixing section based on the measured concentration of the auxiliary combustion gas in the reactor Method.   The method for supplying a mixed gas according to claim 11, wherein the supply of the auxiliary combustion gas to the tubular mixing portion is controlled so as to maintain the concentration of the auxiliary combustion gas in the reactor substantially constant.   The method for supplying a mixed gas according to claim 11 or 12, further comprising extracting the gas from the reactor and reusing it as a combustible gas supplied to the tubular mixing section.   The method for producing a mixed gas according to claim 10, wherein the combustible gas contains hydrogen and the auxiliary combustible gas contains oxygen.   The method for producing a mixed gas according to claim 14, wherein the combustible gas further contains propylene.   The method for producing a mixed gas according to claim 14 or 15, wherein the combustible gas further contains an inert component.

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