JP2002212120A - Method for synthesizing oxygen-containing compound and device therefor - Google Patents

Abstract

PROBLEM TO BE SOLVED: To rationalize and simplify a process for synthesizing an oxygen- containing compound without using a harmful carbon monoxide. SOLUTION: This method for synthesizing the oxygen-containing compound comprises introducing a hydrocarbon resource, an oxidizing agent and water into a conversion zone 28 maintained at 600 to 1,000 deg.C in a reactor 11 maintained at 12 to 35 MPa to convert into the reaction product in the semi- critical or supercritical state of the water, introducing the product into a water- separating zone 30 maintained at 150 to 360 deg.C to liquidize and separate the contained water, introducing the product into a synthetic zone 35 maintained at 250 to 450 deg.C to synthesize the oxygen-containing compound and water, introducing the gas exhausted from the reactor into the first separator 12 to separate the oxygen-containing compound from the gas containing the unreacted hydrogen and the carbon dioxide, introducing the gas containing the separated hydrogen and carbon dioxide into the second separator 13 to separate the carbon dioxide from the gas containing the hydrogen and the carbon dioxide, and then introducing the separated hydrogen gas into the synthesis zone.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to the conversion of fossil-derived resources such as heavy oil or renewable resources such as waste plastics into subcritical water or supercritical water or supercritical carbon dioxide. The present invention relates to a method for synthesizing an oxygen-containing compound by using a generated reaction product as a raw material, and an apparatus for the same.

[0002]

2. Description of the Related Art Although the Asian region is blessed with coal resources, about half of it is estimated to be low-grade coal such as sub-bituminous coal and lignite. This low-grade coal is characterized by a low calorific value due to a high water content and a high oxygen content, and is easily fired spontaneously when dried due to its high activity. Therefore, it is not suitable for transportation or storage, and has been used only partially as a fuel for power generation and household fuel in the vicinity of the hill, and its use has been limited. From the viewpoint of effective use of limited coal resources, it has been important to develop utilization technologies according to the properties of low-grade coal.

[0003] On the other hand, the synthesis of methanol is based on natural gas and stone.
Using hydrocarbon resources such as oil and coal as raw materials,
Water gas (synthesis of carbon monoxide, hydrogen and carbon dioxide)
Gas) zinc oxide with copper or metal oxide added to heterogeneous catalyst
Synthesizes methanol by heating and pressurizing
The method has been established as an industrial method. Methanol
As shown in Fig. 3, the method of synthesis from fossil resources is
Temperature 1200 to 1700 ° C, pressure 3MPa
And gasify hydrocarbon resources. Then gas
The product gas obtained by the conversion is purified. In this purification process
More desulfurization is performed. Next, CO 2_TwoAbsorber
About CO_TwoTo absorb CO from the product gas_TwoIsolate
You. CO separated from product gas_TwoThe absorber that absorbed
Heat CO_TwoAnd absorbent. Separated CO_TwoIs
Released outside the system. CO _TwoFrom hydrogen and carbon monoxide
Gas containing hydrogen as the main component, the composition ratio of hydrogen and carbon monoxide
Is H_TwoThe gas composition is adjusted so that / CO = 2. set
The pressure of the adjusted gas is increased to 10
After adjusting the pressure to about 15 MPa, using a catalyst,
The methanol is represented by the following formula (1) at about 250 to 360 ° C.
It is synthesized by the following reaction.

[0004] CO + 2H ₂ → CH ₃ OH + 21.7 kcal (1) The obtained methanol is separated from the unreacted gas, cooled and recovered as crude methanol. Unreacted carbon monoxide and hydrogen are gas-conditioned and recycled.

[0005] Methanol is liquid at normal temperature and pressure, and can be treated in the same or similar manner as petroleum fuel in all handling of storage, transportation and dispensing. Similarly, dimethyl ether obtained by dehydrating methanol (DiMethyl Ethe
r, hereinafter referred to as DME. ) Is also easily liquefied in a pressurized state, so that almost the same treatment as with methanol is possible. Methanol and DME produce sulfur oxides (S
Ox) is not generated, and generation of nitrogen oxide (NOx) is small. Furthermore, it has been recognized internationally that it is very desirable as an environmentally friendly alternative fuel, since there is almost no generation of dust and unburned hydrocarbons and no pollutants such as heavy metals are contained in exhaust gas. In particular, methanol has attracted much attention as a fuel for fuel cells that are scheduled to be used in next-generation vehicles.

[0006]

However, the conventional process for synthesizing methanol using a gasification furnace has the following problems. That is, since the reaction pressure in gasification is largely different from the pressure required for methanol synthesis, a step of increasing the pressure of gas during the process is required. Further, the temperatures in the respective steps of gasification, gas purification, and methanol synthesis change drastically from high to low to medium. Since the product gas obtained in the gasification furnace is rich in CO with respect to the H ₂ / CO composition required for methanol synthesis, it is necessary to add H ₂ gas from outside the system. Since CO, a toxic gas, is used as a raw material for methanol synthesis, its handling is severe.
As shown in the chemical formula (1), the methanol synthesis reaction with the H ₂ / CO composition generates a large amount of heat, so it is necessary to effectively remove the heat. An object of the present invention is to provide a method for synthesizing an oxygen-containing compound and an apparatus therefor for streamlining and simplifying the process for synthesizing an oxygen-containing compound. An object of the present invention is to provide a method and an apparatus for synthesizing an oxygen-containing compound using a process that does not use harmful carbon monoxide.

[0007]

According to the first aspect of the present invention,
As shown in FIG. 1, the inside of the reactor 11 is 12 to 35 MPa.
And the temperature inside the reactor 11 is 600 to 1
Converting hydrocarbon resources into a reaction product containing hydrogen and carbon dioxide in a subcritical or supercritical state of water by introducing hydrocarbon resources together with an oxidizing agent and water into the conversion zone 28 maintained at 000 ° C. Introducing the reaction product converted in the region 28 into a water separation region 30 maintained at a temperature of 150 to 360 ° C. inside the reactor 11 to liquefy and separate water contained in the reaction product; A step of introducing oxygen-containing compound and water from hydrogen and carbon dioxide contained in the reaction product by introducing the compound into the synthesis zone 35 maintained at a temperature of 250 to 450 ° C. inside the reactor 11, Discharging a gas containing water, hydrogen and carbon dioxide, and converting the gas discharged from the reactor 11 to a temperature of 100 to 20.
First separator 12 maintained at 0 ° C. and pressure of 12 to 35 MPa
And separating the oxygen-containing compound and a gas containing unreacted hydrogen and carbon dioxide into a gas containing hydrogen and carbon dioxide at a temperature of −70 to 20 ° C. and a pressure of 12 to
Introducing carbon dioxide from a gas containing hydrogen and carbon dioxide by introducing the hydrogen into the second separator 13 maintained at 35 MPa, and introducing the separated hydrogen into the synthesis region 35 inside the reactor 11. Is a synthesis method. Claim 1
In the invention according to the invention, hydrocarbon resources are converted in a conversion region formed inside the reactor, water contained in a reaction product is separated in a water separation region, and an oxygen-containing compound is synthesized from the reaction product in a synthesis region. . In this way, since the process from conversion to synthesis is performed inside the reactor, the process for synthesizing the oxygen-containing compound can be rationalized and simplified. Hydrocarbon resources are converted into carbon dioxide and hydrogen by the subcritical or supercritical state of water, and the converted carbon dioxide and hydrogen are used as raw materials for methanol synthesis. Since the synthesis reaction using carbon dioxide and hydrogen gas has a lower calorific value than the synthesis reaction of, heat removal becomes easier.
Further, since harmful carbon monoxide is not used in the synthesis of the oxygen-containing compound, handling of toxic gas is not required, and further simplification can be achieved.

The invention according to claim 2 is the invention according to claim 1, which is a synthesis method in which a desulfurizing agent is added to the water separation region 30 inside the reactor 11. In the invention according to claim 2,
When the hydrocarbon resource contains sulfur, the sulfur can be easily removed from the system by adding a desulfurizing agent to the water separation region.

As shown in FIG. 2, the invention according to claim 3 is characterized in that the inside of the reactor 11 is brought to a pressure of 12 to 35 MPa and the hydrocarbon is contained in the conversion zone 28 in which the temperature inside the reactor 11 is maintained at 600 to 1000 ° C. Converting the hydrocarbon resources into a reaction product containing hydrogen and carbon dioxide in a supercritical state of carbon dioxide by introducing resources together with water, an oxidizing agent and carbon dioxide;
A step of introducing oxygen into the synthesis region 35 maintained at ~ 450 ° C to synthesize oxygenates and water from hydrogen and carbon dioxide contained in the reaction product;
Discharging a gas containing water, hydrogen and carbon dioxide;
The gas discharged from the reactor 11 has a temperature of 100 to 200.
C., a step of introducing into the first separator 12 maintained at a pressure of 12 to 35 MPa to separate the oxygen-containing compound and water into a gas containing unreacted hydrogen and carbon dioxide, including the separated hydrogen and carbon dioxide Gas at temperature -70 ~ 20 ° C, pressure 1
It is introduced into the second separator 13 maintained at 2 to 35 MPa to separate carbon dioxide from the gas containing hydrogen and carbon dioxide, and the separated hydrogen is introduced into the synthesis area 35 inside the reactor 11, and the separated carbon dioxide Is introduced into the conversion region 28 in the reactor 11. In the invention according to claim 3, since carbon dioxide is used as the supercritical fluid, this carbon dioxide can be used not only as a reaction medium but also as a reactant of a synthesis reaction.

The invention according to claim 4 is the invention according to claim 3, which is a synthesis method in which a desulfurizing agent is added to a region located between the conversion region 28 and the synthesis region 35 inside the reactor 11. In the invention according to claim 4, when the hydrocarbon resource contains sulfur, the sulfur is easily converted into hydrogen sulfide by adding a desulfurizing agent to a region located between the conversion region 28 and the synthesis region 35. Can be removed outside the system.

As shown in FIG. 4, the invention according to claim 5 has a vertical reactor 11 having both ends sealed and configured to be able to maintain a supercritical state of water, and a reactor discharged from the reactor 11. A first separator 12 that separates a gas containing oxygen and water and a gas containing hydrogen and carbon dioxide, and a second separator 13 that separates carbon dioxide from the separated gas containing hydrogen and carbon dioxide And as shown in FIG.
Is provided at one end thereof for introducing a hydrocarbon resource, water and an oxidizing agent into the inside of the reactor 11, and is provided with a hydrocarbon resource provided inside the reactor 11 in a subcritical or supercritical state of water. Conversion zone 28, which converts the reaction product into a reaction product containing hydrogen and carbon dioxide, and a reactor 11 above the conversion zone 28.
A cooler 29 provided inside to cool the reaction product generated by the conversion reaction to produce condensed water; and a condensed water provided inside the reactor 11 between the cooler 29 and the conversion area 28 and dripped from the cooler 29. Gas-liquid contactor 31 for bringing the gas into contact with the reaction product generated by the conversion reaction, a desulfurizing agent supply pipe 37 for supplying a desulfurizing agent to gas-liquid contactor 31, and a gas-liquid contactor 31
A drain valve 47 for extracting condensed water stored in the reactor; a synthesizer 32 provided inside the reactor 11 above the cooler 29 to synthesize an oxygen-containing compound from hydrogen and carbon dioxide contained in a reaction product; The apparatus for synthesizing an oxygen-containing compound is provided with a gas outlet 16 provided at the top of the chamber 11 for discharging a gas containing an oxygen-containing compound, water, hydrogen and carbon dioxide.
In the invention according to claim 5, a conversion reaction is performed in a conversion region formed inside the reactor, water is separated and removed from a reaction product by a cooler and a gas-liquid contactor, and hydrogen and carbon dioxide are contained in a synthesizer. In order to synthesize an oxygen-containing compound from the reaction product,
The apparatus can be simplified.

The invention according to claim 6 is the invention according to claim 5, wherein, as shown in FIG.
1. A multi-tube or coil-type cooler disposed in the vertical direction, wherein the flow control valve 33 is provided in the refrigerant inflow pipe 29a of the cooler 29 and adjusts the flow rate of the refrigerant;
A temperature sensor 34 for detecting the temperature between the internal cooler 29 and the synthesizer 32, and a first controller 36 for controlling the flow regulating valve 33 based on the detection output of the temperature sensor 34
And a synthesizing device comprising: In the invention according to claim 6,
Since the first controller controls the flow control valve by the temperature sensor to keep the cooling capacity of the cooler constant, the condensation of the reaction product in the supercritical water state by the cooler is reliably performed. Thereby, the product and the condensed water are separated, and the condensed water can be efficiently stored in the gas-liquid contactor. Further, since supercooling by the cooler is prevented, the reaction with the supercritical fluid can be appropriately performed.

The invention according to claim 7 is the invention according to claim 5 or 6, wherein, as shown in FIG. 5, a multi-tube type or coil in which a synthesizer 32 is disposed in the longitudinal direction of the reactor 11. A flow control valve 48 having a cooling means and provided in the refrigerant inflow pipe 32a of the cooling means for adjusting the flow rate of the refrigerant, a temperature sensor 49 for detecting a temperature near the inner top of the reactor 11,
Flow control valve 4 based on the detection output of temperature sensor 49
And a second controller 51 for controlling the control unit 8. In the invention according to claim 7, since the second controller controls the flow control valve by the temperature sensor to keep the cooling capacity of the cooling means constant at all times, the synthesis of the oxygen-containing compound by the synthesizer is reliably performed.

The invention according to claim 8 is the invention according to claims 5 to 7
In the invention according to any of the above, as shown in FIG. 5 or FIG. 6, the synthesizer 32 is a multiple tube type or a fluidized bed type synthesizer filled with a catalyst in which a plurality of the synthesizers 32 are vertically arranged and filled with a catalyst. There is a synthesizer.

[0015]

BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, the subcritical or supercritical state of water is defined as a temperature of 600 to 1000 ° C and a temperature of 12 to 12 ° C.
It means the state of water at a pressure of 35 MPa. The supercritical state of carbon dioxide of the present invention means a state of carbon dioxide at a temperature of 31 to 1000 ° C. and a pressure of 12 to 35 MPa. If the temperature and pressure conditions are below the lower limits, the conversion reaction is slow and the efficiency of hydrocarbon resource decomposition is poor. Exceeding the upper limits of the above temperature and pressure conditions is not efficient because the reactor is overloaded. As the oxygen-containing compound synthesized in the present invention, methanol,
DME and the like.

The hydrocarbon resources include coal, petroleum hydrocarbons, waste plastics, organic sludge, and organic waste. Examples of coal include lignite, subbituminous coal, bituminous coal, and the like. Petroleum hydrocarbons include heavy oil, ultra-heavy oil, and the like. Examples of heavy oil include crude oil, heavy A oil, heavy B oil, heavy C oil, atmospheric distillation residue, and vacuum distillation residue. Examples include natural bitumen, natural tar, and the like. Examples of the waste plastic include thermoplastic resins such as polyethylene, polypropylene, polyvinyl chloride, polystyrene, polyester, and vinylidene chloride. Examples of the organic waste include waste oil containing PCB and the like.

The hydrocarbon resources are preferably in the form of a slurry or an emulsion for suppressing the coking phenomenon. When the hydrocarbon resource is a solid such as coal, it is crushed and prepared into a slurry mixed with water, and when the hydrocarbon resource is a liquid such as heavy oil, the heavy oil and water are mixed. It is prepared into an emulsion. The concentration of hydrocarbon resources with respect to the water in the slurry is 1000 to 6000 kc in calorific value.
It is prepared to be al / kg. 1000kcal
/ Kg, it is difficult to maintain the reaction temperature.
If it exceeds al / kg, the undecomposed ratio increases.

The oxidizing agent includes oxygen, air, hydrogen peroxide and the like. Examples of the desulfurizing agent include ZnO, CuO, and FeO. The catalyst includes CuO.ZnO.La ₂ O ₃ , Cu
_{· ZnO · Al 2 O 3,} Cu · ZnO · ZrO 2, Cu · ZnO
_{· Cr 2 O 3, Cu ·} ZnO · MnO, Cu · ZnO · Al 2 O
₃ · ZrO ₂ , Cu · ZnO · Al ₂ O ₃ · Cr ₂ O ₃ , Cu · P
d.ZnO.Al ₂ O _{3 and the} like.

Next, an embodiment of the present invention will be described with reference to the drawings. As shown in FIG. 4, the synthesis device 10 of the present invention includes a reactor 11, a first separator 12 and a second separator 13. The reactor 11 is a vertical type, both ends of which are sealed, and is configured to be able to maintain a supercritical state of water. Around the reactor 11, a heater for keeping heat and preheating together with a heat insulating material not shown are provided. The reactor 11 has an inlet 14 on the side, a gas outlet 16 on the top, and an ash outlet 17 on the bottom.

The slurry mixed by the mixer 18 is supplied to the inlet 14 after the temperature of the slurry is increased by a pump 19 and a preheater 21. Water is supplied to the inlet 14 from the tank 22.
From the pump 23 and the preheater 24 to supply subcritical or supercritical water. Further introduction port 14
The oxidizing agent is supplied at a high pressure by a pump 27 and a preheater 28. Further, in this case, although not shown, the liquid to be treated and water or the water and the oxidizing agent are mixed together, and the pressure is increased by a pump and a preheater to be in a subcritical or supercritical state of water and supplied to the inlet 14. May be.

As shown in FIG. 5, the reactor 11 has therein a conversion area 28, a cooler 29, a gas-liquid contactor 31, and a synthesizer 32, respectively. In the conversion zone 28, hydrocarbon resources are converted to a reaction product containing hydrogen and carbon dioxide in a subcritical or supercritical state of water.

A cooler 29 is provided inside the reactor 11 above the conversion region 28, and condenses and separates water contained in the reaction product converted in the conversion region 28. The cooler 29 is a multi-tube or coil-type cooler disposed in the longitudinal direction of the reactor 11. A reaction product in a subcritical or supercritical state passes through a portion of the cooler 29, and a coolant (for example, water) flows around this. The reaction product in the supercritical water state is cooled below the temperature in the supercritical water state. Cooling temperature is 150 ~
Maintained in the range of 360 ° C. The refrigerant in the cooler 29 flows in from the upper inflow line 29a, and flows into the lower outflow line 29b.
It comes out of the. A flow control valve 33 for adjusting the flow rate of the refrigerant is provided in the refrigerant inflow pipe 29a. A temperature sensor 34 for detecting a temperature is provided between the cooler 29 and the synthesizer 32 inside the reactor 11. The detection output of the temperature sensor 34 is connected to the control input of the first controller 36, and the control output is connected to the flow control valve 33.

The gas-liquid contactor 31 includes a conversion area 28 and a cooler 2.
, The condensed water condensed in the cooler 29 is stored, and the condensed water and the conversion region 2 are condensed.
8. Contact with the reaction product converted in 8. Gas-liquid contactor 3
One end of a desulfurizing agent supply pipe 37 is provided on the upper part of 1.
The other end of the desulfurizing agent supply pipe 37 is connected to a desulfurizing agent supply port 38 provided on the side of the reactor 11. The desulfurizing agent is supplied to the desulfurizing agent supply port 38 by raising the temperature of the desulfurizing agent by the pump 59 and the preheater 61. As shown in an enlarged manner in FIG. 7, the gas-liquid contactor 31 is of a valve cap tray type, and an upper tray 39 and a lower tray 41 are provided at intervals. Each of the trays 39, 41 has a plurality of short tubes 39a, 41a.
Are erected through the trays 39, 41, and small caps 39b, 41b are provided on the upper ends of the short tubes 39a, 41a. Along the inner wall 11a of the reactor 11, a long tube 42 is provided at one end of each of the trays 39 and 41, and a long tube 43 is provided at the other end of the lower tray 41. The upper end of the long tube 42 penetrates the upper tray 39, and the lower end thereof is the lower tray 41.
To the vicinity of the upper surface of. The upper portion of the long tube 43 penetrates the lower tray 41, and a tray 43a is provided near the lower end thereof. The upper ends of the long tubes 42 and 43 are small caps 39.
b, 41b are provided at the same position as the upper surface. Saucer 43a
A drain port 44 is provided on the side of the reactor lower than the upper end of the reactor. A conduit 46 and a drain valve 47 are connected to the drain port 44.

Returning to FIG. 5, the synthesizer 32 is provided inside the reactor 11 above the cooler 29, and synthesizes an oxygen-containing compound from hydrogen and carbon dioxide contained in the reaction product from which water has been separated. The synthesizer 32 is a multi-tube type, which is arranged vertically and is filled with a catalyst, or a fluidized bed type synthesizer filled with a catalyst as shown in FIG. Multiple tube type synthesizer 3
Numeral 2 is composed of a plurality of multiple tubes arranged vertically, a dispersion plate and cooling means, and the inside of the multiple tubes is filled with a pellet-shaped catalyst formed into a small cylinder. This filling portion has pores through which a reaction product containing hydrogen and carbon dioxide can flow. The fluidized bed type synthesizer is configured by filling a powdery catalyst on a dispersion plate formed at the bottom. The cooling means is arranged at a position where the cooling means is covered with the filled powdery catalyst. In this fluidized bed type synthesizer, the flowing gas for flowing the powder fluid is a reaction product that has passed through the conversion region and the separation region.

The cooling means is of a multi-tube type or a coil type arranged in the vertical direction, and is selected according to the type of the synthesizer.
The reaction product passes through the portion of the cooling means, around which a coolant (eg, water) flows. The reaction product is maintained at 250 ° C. to 450 ° C., which is the synthesis temperature range of the oxygen-containing compound. The refrigerant of the cooling means flows in from the upper inflow line 32a and flows out from the lower outflow line 32b. A flow control valve 48 for controlling the flow rate of the refrigerant is provided in the refrigerant inflow pipe 32a. A temperature sensor 49 for detecting a temperature near the inner top inside the reactor 11 is provided. The detection output of the temperature sensor 49 is
, And its control output is connected to a flow control valve 48.

As shown in FIG. 4, the reactor 11 and the first separator 12 are connected via a pipe 52. A cooler 53 is provided in the middle of the pipe 52. The first separator 12 has a gas outlet 12a at the top and a liquid outlet 12b at the bottom. The first separator 12 and the second separator 13 are connected via a pipe 54. A cooler 56 is provided in the middle of the pipe 54. The second separator 13 has a gas outlet 13a at the top and a liquid outlet 13b at the bottom.
The second separator 13 and the reactor 11 are connected via a line 57. A pump 62 and a heater 58 are provided in the middle of the pipe 57.

A description will be given of a case where coal is used as a hydrocarbon resource with reference to FIG. (a) Conversion area Coal and water are supplied to a mixer to prepare a slurry, and the mixed fluid comprising the slurry, the oxidizing agent, and water, which has been pressurized and heated, is supplied from the inlet 14 to a pressure of 12 to 35 MPa. It is introduced into the conversion zone 28 of the kept reactor 11. In the conversion zone 28, the temperature is maintained at 600-1000 ° C., where the hydrocarbon resources are converted to a reaction product containing methane, hydrogen and carbon dioxide. Of the components contained in the converted reaction product, the ash is gravity-sedimented at the bottom of the reactor 11 and is extracted from the ash outlet 17.

(B) Separation zone Of the reaction products in the supercritical water state generated by the reaction,
The solid-free components pass through a water separation zone 30 consisting of a gas-liquid contactor 31 and a cooler 29, and
To the inner top of the reactor 11. The reaction product in the supercritical water state is cooled in the cooler 29 to a temperature in the range of 150 to 360 ° C., which is lower than the temperature of the supercritical water, and a part of the reaction product becomes a subcritical water state and becomes condensed water.
The remainder reaches the synthesizer 32 as a synthesis gas of an oxygen-containing compound. Thereby, the synthesis gas of the oxygen-containing compound and the condensed water are separated. The cooling temperature of the cooler 29 is determined by the temperature sensor 3
4. The temperature is maintained at a predetermined temperature by the flow control valve 33 and the first controller 36. By this control, the reaction product in the supercritical water state is simultaneously prevented from being discharged from the gas discharge port 16.

The condensed water dropped from the cooler 29 shown in FIG. 7 first falls on the upper tray 39 and is stored on the upper tray 39. Next, the level of condensed water on the upper tray 39 rises,
When this water level exceeds the upper end of the long pipe 42, the condensed water
2 to the lower tray 41 and is stored on the lower tray 41. Next, the level of condensed water on the lower tray 41 rises,
When this water level exceeds the upper end of the long pipe 43, the condensed water
3 and once stored in the tray 43a, the reactor 11
Through a drain valve 47 from a discharge port 44 provided on the side of the nozzle. A desulfurizing agent is supplied to the upper tray 39 via a desulfurizing agent supply pipe 37. In this state,
The reaction product excluding the solid generated by the reaction with the supercritical water first passes through the short pipe 41a, pushes up the small cap 41b by the atmospheric pressure, passes through the condensed water on the lower tray 41,
It reaches the area 40 between the lower tray 41 and the upper tray 39.
The reaction products reaching this region 40 are likewise short tubes 39
a, and push up the small cap 39b so that the upper tray 39
Through the above condensed water to cooler 29 (FIG. 5). As a result, the reaction product in the supercritical water state coming from the conversion region 28 toward the inner top of the reaction vessel 11 comes into contact with the condensed water temporarily stored in the gas-liquid contactor 31 and accompanies the reaction product. H ₂ S gas can be dissolved in condensed water and desulfurized with a desulfurizing agent to form inorganic salts. In this separation region, ash that could not be separated in the conversion region can also be separated.

(C) Synthesis zone The reaction product from which water has been separated in the separation zone has a temperature of 250-45.
It is introduced into the synthesis zone maintained at 0 ° C. Here, hydrogen and carbon dioxide contained in the reaction product pass through the catalyst filled in the synthesizer, whereby the reaction mainly represented by the following formula (2) proceeds. CO ₂ + 3H ₂ → CH ₃ OH + H ₂ O + 11.8 kcal (2)

This reaction has a smaller calorific value and is easier to remove heat than a conventional methanol synthesis reaction with a H ₂ / CO composition. According to the chemical formula (2), the higher the pressure, the more the reaction is promoted due to the difference in the number of moles before and after the reaction. For this reason, the pressure is preferably higher. When a dehydration catalyst is added to the synthesis catalyst, the obtained methanol causes a dehydration reaction represented by the following reaction formula (3) due to the pressure, and DME is also synthesized. 2CH ₃ OH → CH ₃ OCH ₃ + H ₂ O (3)

(D) First Separator The oxygen-containing compound synthesized in the synthesizing section 35, water and unreacted hydrogen and carbon dioxide are passed through the first separator at 100 to 200 ° C.
And separated into oxygenates and water, hydrogen and carbon dioxide. From the separated oxygen-containing compound and water, water is removed by a distillation device (not shown) to obtain the oxygen-containing compound as a purified product.

(E) Second separator The hydrogen and carbon dioxide separated in the first separator are introduced into the second separator, where they are cooled to -70 to 20 ° C and separated into hydrogen and carbon dioxide. You. The separated hydrogen is introduced into the synthesis area 35, and the carbon dioxide is recovered. By lowering the cooling temperature, the recovery rate of carbon dioxide can be increased. In the present embodiment, a valve cap tray type is used for the gas-liquid contactor. Alternatively, a demister blanket type may be used.

[0034]

Next, embodiments of the present invention will be described. Was prepared undecane (C ₁₁ H ₂₄₎ is a straight-chain hydrocarbons <Example 1> hydrocarbon resources feedstock. First, water is added to and mixed with the undecane so that the ratio of water to the raw material becomes water / raw material ratio = 2, and a slurry is prepared. Further, hydrogen peroxide is used as an oxidizing agent with oxygen and carbon contained in the raw material. Is O / C
Mixing was performed so that ratio = 0.8. This mixture was then introduced into the conversion zone maintained at a temperature of 800 ° C. inside the reactor maintained at a pressure of 25 MPa as shown in FIG. The raw material was introduced into the conversion zone and converted in a supercritical state of water to obtain a reaction product. The gas composition contained in the reaction product was examined with a gas analyzer. Table 1 shows the gas composition of the reaction product.

[0035]

[Table 1]

Next, the reaction product containing the gas having the above composition is introduced into a separation region comprising a cooler and a gas-liquid contactor maintained at a temperature of 100 ° C. to separate water from the reaction product. The reaction product was introduced into a synthesis zone composed of a synthesizer maintained at a temperature of 250 ° C. to synthesize methanol. As the catalyst, a mixture prepared by a coprecipitation method using a mixture of copper nitrate, zinc nitrate and aluminum nitrate was used.

<Example 2> A reactor was synthesized under the same conditions as in Example 1 except that the pressure of the reactor was set to 20 MPa. <Example 3> Synthesis was performed under the same conditions as in Example 1 except that the pressure of the reactor was set to 15 MPa. <Example 4> A reactor was synthesized under the same conditions as in Example 1 except that the temperature of the synthesizer was set to 300 ° C.

Example 5 Synthesis was performed under the same conditions as in Example 1 using the same reactor as in Example 1 except that the temperature of the synthesizer was set at 350 ° C. <Example 6> A reactor was synthesized in the same manner as in Example 1 except that the temperature of the synthesizer was set at 450 ° C. <Example 7> A reactor was synthesized under the same conditions as in Example 1 except that the pressure in the reactor was set to 35 MPa and the temperature of the synthesizer was set to 350 ° C.

<Evaluation 1> In the synthesizers of Examples 1 to 7, the reaction was completed without recycling unreacted hydrogen, and the ethanol obtained at this time was regarded as one cycle, and the synthesis rate of ethanol per cycle was examined. Was. Table 2 shows the 1-cycle synthesis rates. In addition, the synthesis rate of methanol is shown by the conversion rate of the generated hydrogen.

[0040]

[Table 2] As is clear from Table 2, it was confirmed that methanol could be produced from a reaction product containing hydrogen and carbon dioxide obtained by converting hydrocarbon resources in supercritical water. Further, it was confirmed from gas analysis that a small amount of DME was also produced by-product.

Example 8 Undecane (C ₁₁ H ₂₄ ) which is a linear hydrocarbon was prepared as a hydrocarbon resource material.
First, in this undecane, the ratio of water and raw material is water / raw material ratio =
The slurry was prepared by adding and mixing water so as to be 1, and further, a hydrogen peroxide solution was mixed as an oxidizing agent so that oxygen and carbon contained in the raw material had an O / C ratio of 0.7. This mixture was then combined with carbon dioxide at a pressure of 25M as shown in FIG.
It was introduced into a conversion zone maintained at a temperature of 800 ° C. inside the reactor maintained at Pa. The raw material was introduced into the conversion zone and converted in a supercritical state of carbon dioxide to obtain a reaction product. The gas composition contained in the reaction product was examined with a gas analyzer. Table 3 shows the gas composition of the reaction product.

[0042]

[Table 3]

Next, the reaction product containing the gas having the above composition was introduced into a synthesis zone composed of a synthesizer maintained at a temperature of 250 ° C. to synthesize methanol. The same catalyst as in Example 1 was used.

Example 9 A reactor was synthesized under the same conditions as in Example 8 except that the pressure of the reactor was set to 20 MPa. <Example 10> A reactor was synthesized under the same conditions as in Example 8 except that the pressure of the reactor was set to 15 MPa. <Example 11> A reactor was synthesized under the same conditions as in Example 8, except that the temperature of the synthesizer was set to 300 ° C.

Example 12 A reactor was synthesized under the same conditions as in Example 8 except that the temperature of the synthesizer was set at 350 ° C. <Example 13> A reactor was synthesized in the same manner as in Example 8, except that the temperature of the synthesizer was set to 450 ° C. <Example 14> Example 8 except that the pressure in the reactor was set to 35 MPa and the temperature of the synthesizer was set to 350 ° C.
Using the same reactor as in Example 8, synthesis was performed under the same conditions as in Example 8.

<Evaluation 2> The reaction was completed without recycling unreacted hydrogen in the synthesizers of Examples 8 to 14,
Using the ethanol obtained at this time as one cycle, the synthesis rate of ethanol per cycle was examined. Table 2 shows the 1-cycle synthesis rates. In addition, the synthesis rate of methanol is shown by the conversion rate of the generated hydrogen.

[0047]

[Table 4] As is clear from Table 4, it was confirmed that methanol could be produced from a reaction product containing hydrogen and carbon dioxide obtained by converting hydrocarbon resources in supercritical water. Further, it was confirmed from gas analysis that a small amount of DME was also produced by-product.

[0048]

As described above, according to the present invention, 1
Oxygenated compounds are formed from hydrogen and carbon dioxide obtained by converting hydrocarbon resources in the conversion zone, water separation zone and synthesis zone, which are formed inside the reactor maintained at 2 to 35 MPa and have different temperature ranges respectively. Therefore, an oxygen-containing compound synthesis process that does not use harmful carbon monoxide can be constructed, and the oxygen-containing compound synthesis process can be rationalized and simplified.

[Brief description of the drawings]

FIG. 1 is a diagram showing a method for synthesizing an oxygen-containing compound using a subcritical or supercritical state of water according to the present invention.

FIG. 2 is a diagram illustrating a method for synthesizing an oxygen-containing compound using a supercritical state of carbon dioxide according to the present invention.

FIG. 3 is a diagram showing a method for synthesizing methanol using a conventional gasification furnace.

FIG. 4 is an overall configuration diagram of a synthesis device according to the present invention.

FIG. 5 is a configuration diagram of a reactor.

FIG. 6 is another configuration diagram of a reactor.

FIG. 7 is an enlarged configuration diagram of a gas-liquid contactor.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 11 Reactor 12 1st separator 13 2nd separator 14 Inlet 16 Gas outlet 28 Conversion area 29 Cooler 29a Refrigerant inflow pipe 30 Water separation area 31 Gas-liquid contactor 32 Synthesizer 32a Refrigerant inflow pipe 33 Flow rate Adjusting valve 34 Temperature sensor 35 Synthesis area 36 First controller 37 Desulfurizing agent supply pipe 47 Drainage valve 48 Flow rate adjusting valve 49 Temperature sensor 51 Second controller

Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat II (reference) C07C 43/04 C07C 43/04 D // C07B 61/00 C07B 61/00 B 300 300 (72) Inventor Akira Tanaka Tokyo 1-3-25 Koishikawa, Bunkyo-ku, Tokyo Mitsubishi Materials Corporation System Business Center F-term (reference) 4G040 BA02 BB02 4G140 BA02 BB02 4H006 AA02 AC41 AC43 AD18 BA05 BA07 BA09 BA34 BB62 BC10 BC11 BC13 BC31 BC51 BC52 BD33 BD52 BD81 BD82 BE32 FE11 GN05 GP01 4H039 CA60 CC90

Claims (8)

[Claims] 1. A pressure inside the reactor (11) of 12 to 35 MPa and a temperature inside the reactor (11) of 600 to 1 MPa.
A step of introducing a hydrocarbon resource together with an oxidizing agent and water into a conversion zone (28) maintained at 000 ° C. to convert the hydrocarbon resource into a reaction product containing hydrogen and carbon dioxide in a subcritical or supercritical state of water And converting the reaction product converted in the conversion region (28) into the reactor (1).
1) The water separation area (3
0), liquefying and separating water contained in the reaction product, and separating the reaction product into a temperature of 250 to 4 inside the reactor (11).
A step of introducing an oxygen-containing compound and water from hydrogen and carbon dioxide contained in the reaction product by introducing the compound into the synthesis zone (35) maintained at 50 ° C .; Discharging a gas containing hydrogen and carbon dioxide; and discharging the gas discharged from the reactor (11) to a temperature of 100 to 20.
First separator (12) maintained at 0 ° C. and pressure of 12 to 35 MPa
And separating the oxygen-containing compound and a gas containing unreacted hydrogen and carbon dioxide into a gas containing hydrogen and carbon dioxide.
It is introduced into a second separator (13) maintained at 70 to 20 ° C. and a pressure of 12 to 35 MPa to separate carbon dioxide from the gas containing hydrogen and carbon dioxide, and the separated hydrogen is supplied to the reactor (11). Introducing an oxygen-containing compound into an internal synthesis region (35). 2. The method according to claim 1, wherein a desulfurizing agent is added to the water separation zone (30) inside the reactor (11). 3. A pressure inside the reactor (11) of 12 to 35 MPa and a temperature inside the reactor (11) of 600 to 1 MPa.
Hydrocarbon resources in the conversion zone (28) maintained at
Converting the hydrocarbon resource into a reaction product containing hydrogen and carbon dioxide in a supercritical state of carbon dioxide by introducing together with an oxidizing agent and carbon dioxide, and converting the reaction product to a temperature inside the reactor (11). 250-4
A step of introducing an oxygen-containing compound and water from hydrogen and carbon dioxide contained in the reaction product by introducing the compound into the synthesis zone (35) maintained at 50 ° C .; Discharging a gas containing hydrogen and carbon dioxide; and discharging the gas discharged from the reactor (11) to a temperature of 100 to 20.
First separator (12) maintained at 0 ° C. and pressure of 12 to 35 MPa
And separating the oxygen-containing compound and water into a gas containing unreacted hydrogen and carbon dioxide, and separating the separated gas containing hydrogen and carbon dioxide into a temperature −
It is introduced into a second separator (13) maintained at 70 to 20 ° C. and a pressure of 12 to 35 MPa to separate carbon dioxide from the gas containing hydrogen and carbon dioxide, and the separated hydrogen is supplied to the reactor (11). Introducing the separated carbon dioxide into the conversion region (28) inside the reactor (11). 4. A desulfurizing agent is added to a region located between the conversion region (28) and the synthesis region (35) inside the reactor (11).
The described synthesis method. 5. A vertical reactor (11) having both ends sealed and capable of maintaining a supercritical state of water; and a gas discharged from the reactor (11) containing an oxygen-containing compound and water. And a first separator (12) for separating into a gas containing hydrogen and carbon dioxide, and a second separator (12) for separating carbon dioxide from the separated gas containing hydrogen and carbon dioxide, The reactor (11) is provided at one end of the reactor (11)
An inlet (14) for introducing a hydrocarbon resource, water and an oxidizing agent therein, and the hydrocarbon resource provided inside the reactor (11) and allowing the hydrocarbon and hydrogen to reach a subcritical or supercritical state of water. A conversion region (28) for converting into a reaction product containing carbon, and a reaction product formed by the conversion reaction provided in the reactor (11) above the conversion region (28) to cool condensed water. A cooler (29) to be produced, and condensed water dropped from the cooler (29) provided inside the reactor (11) between the cooler (29) and the conversion area (28) and formed by the conversion reaction. Gas-liquid contactor (31) for bringing the reaction product into contact with the reaction product, a desulfurizing agent supply pipe (37) for supplying a desulfurizing agent to the gas-liquid contactor (31), and stored in the gas-liquid contactor (31). Drain valve (47) for draining condensed water
A synthesizer (32) provided inside the reactor (11) above the cooler (29) to synthesize an oxygen-containing compound from hydrogen and carbon dioxide contained in a reaction product; and A) a gas outlet (16) for discharging a gas containing an oxygen-containing compound, water, hydrogen and carbon dioxide, provided at the top of the oxygen-containing compound. 6. A cooler (29) is a multi-tube or coil-type cooler disposed in the longitudinal direction of the reactor (11), wherein the cooler (29) has a refrigerant inflow pipe (29a). A flow rate adjusting valve (33) provided in the reactor, and a temperature sensor (34) for detecting a temperature between the cooler (29) and the synthesizer (32) inside the reactor (11). And a first controller for controlling the flow rate regulating valve (33) based on a detection output of the temperature sensor (34).
The apparatus for synthesizing an oxygen-containing compound according to claim 5, comprising (36). 7. A synthesizer (32) has a multi-tube or coil-type cooling means arranged in the longitudinal direction of the reactor (11), and is provided in a refrigerant inflow line (32a) of the cooling means. A flow rate adjusting valve (48) for adjusting the flow rate of the refrigerant, a temperature sensor (49) for detecting a temperature near the inner top of the reactor (11), and the temperature sensor
A second controller (51) for controlling the flow regulating valve (48) based on the detection output of (49).
An apparatus for synthesizing the oxygen-containing compound according to the above. 8. The oxygen-containing apparatus according to claim 5, wherein the synthesizer (32) is a plurality of multitubular or catalyst-filled fluidized bed synthesizers each of which is vertically arranged and filled with a catalyst. Compound synthesis equipment.