JP2555265B2 - Medium pressure continuous gasifier - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION The present invention is to convert a raw material such as butane (C ₄ H ₁₀ ) or naphtha into a gas containing hydrogen gas as a main component with a nickel-based reforming catalyst by mixing with steam. Quality medium pressure continuous gasifier.

[0002]

2. Description of the Related Art Conventionally, as an intermediate pressure continuous gasifier for producing an intermediate pressure gas having a calorific value of around 4500 kcal / Nm ³ from a raw material such as butane (C ₄ H ₁₀ ) and naphtha, for example, FIG.
The ICI (Imperial) consists of four departments, desulfurization, reforming, CO conversion (carbon monoxide conversion), and heat recovery
Chemical Industries) formula is known.

The ICI type medium-pressure continuous gasifier shown in FIG. 3 uses a raw material 61a pressurized to about 10 kgf / cm ³ and a recycled gas 61b, which is a part of the produced gas, for hydrogenation. Mix as a source and heat to about 350 ° C. in heater 62.
Then, the heated gas 61d flows into the desulfurizer 64 filled with the ZnO (zinc oxide) adsorbent 63a and adsorbs and removes hydrogen sulfide (H ₂ S) in the raw material 61a. Furthermore, a cobalt-molybdenum (Co-Mo) -based hydrogenation catalyst (COMO
X) 65a flows into the desulfurizer 66 filled on the upstream side, and the hydrogen (H ₂ ) of the recycle gas 61b causes the organic sulfur compound in the raw material 61a to be saturated hydrocarbon (C _n H _{2n + 2} ) and H ₂ S.
Reacting with the above, hydrogen sulfide is adsorbed and removed by the ZnO-based adsorbent 63a on the downstream side of the desulfurizer 66, and the raw material 61a is desulfurized.

Next, the desulfurized raw material 61a is mixed with heated steam (H ₂ O) 61c at a predetermined ratio to obtain nickel (N 2
i) It flows into the reaction tube 68 filled with the system reforming catalyst 67a.
Since the steam reforming reaction by the nickel-based reforming catalyst 67a is a large endothermic reaction, the outside of the reaction tube 68 is
The raw material 61a is heated with a burner or the like (not shown) that uses a part of naphtha and butane as fuel.

The raw material 61a flowing into the reaction tube 68 is
C _n H _{2n + 2} reacts with carbon monoxide (CO) and H ₂ with H ₂ O, and the generated CO, CO and carbon dioxide (CO _{2 in the} raw material 61a and the recycled gas 61b) ) Reacts with methane (CH ₄ ) and CO ₂ with H ₂ and H ₂ O of steam 61 c. The amount of these reactions produced is determined by the temperature, pressure, steam ratio, and the like. Then, CH ₄ and C containing H ₂ as a main component
It is reformed into a gas 61e having a predetermined composition containing O ₂ and CO.

After that, the reformed gas 61e is cooled to about 350 ° C. in the waste heat boiler 69, and iron-chromium (Fe-C) is used.
r) Flows into the CO shift converter 71 filled with the catalyst 70a, and the Fe-Cr catalyst 70a reacts with CO ₂ and H ₂ by the steam 61c remaining in the gas 61e to reduce CO. Let

Then, the modified gas 61f is separated into steam and water, diluted with air, and the gas 61f becomes about 4500 kcal / Nm ^3.
61 g of the supply gas is manufactured by adjusting the heat generation amount of the above, cooled by the cooler 72, depressurized to about 7 kgf / cm ² by the pressure adjusting valve 73, and stored in the storage tank.

[0008]

However, in the above-mentioned conventional medium-pressure continuous gasifier, the raw material 61a is once produced by pressurizing it to a high pressure, and the gas is depressurized to supply 61 g of gas. There is a problem of reduced efficiency.

Further, in order to efficiently and surely carry out the catalytic reaction according to the purpose, it is necessary to heat the raw material 61a to a predetermined temperature range. Therefore, various catalysts 63a, 65a, 67a,
It is necessary to provide a plurality of equipment such as desulfurizers 64 and 66 and reaction tubes 68, each of which is filled with 70a, and the apparatus becomes large-sized, and the structure of equipment such as heating means and heat recovery means (not shown) is also provided. There is a problem that the device becomes complicated and the device becomes large.

On the other hand, CO is converted into CH with H ₂ and H ₂ O.
_The methanation reaction with ₄ and CO ₂ is an exothermic reaction, and C _n H _{2n + 2} is converted into CO and H ₂ with H ₂ O.
The steam reforming reaction that is reacted with is an endothermic reaction. Then, the methanation reaction proceeds in a temperature range slightly lower than the steam reforming reaction. However, since the methanation reaction and the steam reforming reaction are performed in parallel in the reaction tube for reforming, there is a problem that the thermal efficiency of heating the reaction tube by the burner is reduced and the reaction efficiency is also reduced. .

The present invention has been made in view of the above-mentioned conventional problems, and an object of the present invention is to provide a medium-pressure continuous gasifier which is simple and compact in structure, and which can efficiently and inexpensively gasify.

[0012]

The medium-pressure continuous gasifier according to the present invention desulfurizes a raw material, mixes it with steam, and reforms it into a gas containing hydrogen gas as a main component with a nickel-based reforming catalyst. In the medium-pressure continuous gasifier equipped with a reaction tube whose outer periphery is heated, and a converter for converting carbon dioxide gas in the gas from the reaction tube, the reaction tube has an inlet through which a raw material flows. , A desulfurization chamber having a catalyst for desulfurizing the raw material flowing from the inlet, a methanation chamber having a catalyst for reacting the raw material flowing from the desulfurizing chamber with methane, and the raw materials flowing from the methanation chamber were mixed. a reforming chamber with a reforming catalyst for steam reformed to hydrogen in a steam, the reforming chamber and a flow outlet communicating with steam reformed gas flows out to the front Kiaratame quality room the meta Perimeter of the nation chamber
And it is formed on at least the double pipe structure disposed coaxially located on the side.

[0013]

[Action] pressure continuous gasifier in the present invention, the desulfurization chamber desulfurizing material, methanation chamber for methanation of the raw material, raw material reforming chamber for steam reforming, the temperature range order of the catalytic reaction
Methanation that is installed to perform methanation, which is an exothermic reaction
It is located on the outer peripheral side where it is heated from the chamber and is coaxial with the endothermic reaction
A reforming chamber for performing certain steam reforming is installed to form a multi-tube structure.
Therefore, the heat generated during methanation is converted into the heat required for steam reforming.
It can be used to improve thermal efficiency and reduce gasification cost, and can perform desulfurization, methanation, and steam reforming in one reaction tube, which simplifies and downsizes the device.

[0014]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS An embodiment of the medium pressure continuous gasifier of the present invention will be described with reference to the drawings.

In FIG. 1, reference numeral 1 denotes a raw material tank. In the raw material tank 1, a raw material 1a such as butane (C ₄ H ₁₀ ) and naphtha is stored as a liquid at a medium pressure of, for example, about 7 kgf / cm ^2. There is. The raw material tank 1 is connected to a heat exchanging device 4 having a double pipe structure in which an inner pipe 3 through which a liquid raw material 1a is circulated is connected in the pipe body 2, and the inner pipe 3 of the heat exchanging device 4 is connected to the heat exchanging device 4. The liquid raw material 1a flows through and is vaporized.

A raw material mixing device 5 is connected to the inner pipe 3 of the heat exchanging device 4, and by the raw material mixing device 5,
For the raw material 1a, steam (H ₂ O) 1c and the recycled gas 1b which is a hydrogen source for hydrogenation, which is a part of the produced gas, are used, for example, the raw material 1a, steam (H ₂ O) 1c, and hydrogen in the recycled gas 1b. Mix so that the ratio with (H ₂ ) is 10: 30: 1. As the recycled gas 1b, a part of the gas produced in the carrier gas tank 6 connected to the raw material mixing device 5 is stored as the recycled gas 1b at a medium pressure of, for example, about 7 kgf / cm ² . Further, a reaction tower 7 is connected to the raw material mixing device 5.

The reaction tower 7 is shown in FIG. 1 and FIG.
As shown in FIG. 2, it is composed of a hollow kiln 11 having a heating chamber 10 in which a refractory material 9 is provided on the inner wall, and a reaction tube 12 arranged in the heating chamber 10 in the kiln 11. .

Further, the kiln 11 is provided with a burner (not shown) at a kiln opening 14 provided at the outer peripheral edge of the lower end, and combustion gas 15 from the burner passes from the kiln opening 14 to the outer peripheral edge of the upper end through the heating chamber 10. It is formed in a cylindrical shape so as to flow out from the exhaust port 16 provided,
It is installed along the vertical direction in the axial direction. Further, a construction window 17 in which the reaction tube 12 is inserted and installed is opened at the upper end of the kiln body 11 and is always closed by a lid body 18. Further, a mounting port 19 into which one end of the reaction tube 12 is fitted is formed at the lower end of the kiln 11.

On the other hand, the reaction tube 12 is composed of a hollow outer tube body 21 having a substantially columnar shape, and a cylindrical inner tube body 22 coaxially arranged in the outer tube body 21. A cylindrical mounting portion 24 is formed at the lower end of the outer tube body 21 so as to project coaxially downward and to be fitted into the mounting opening 19 of the kiln body 11 and to open the outlet 23 downward. Further, on the outer peripheral surface of the outer tube body 21, a wind control wall 25 is formed in a spiral shape so that the reaction tube 12 is uniformly heated by the combustion gas 15 from the burner. Further, a through hole 27 is formed in the substantially lower center near the inner lower portion of the outer tubular body 21, and a breathable support plate 28 for mounting and supporting the inner tubular body 22 is provided.
Is provided. Furthermore, at the lower end of this mounting part 24,
A T-shaped tubular joint portion 29 is attached so as to open downward and sideways.

Further, at the lower end of the inner pipe body 22, an inflow pipe 32, which opens an inflow port 31 into which the mixed gas 1d from the raw material mixing device 5 flows, is provided coaxially so as to project downward.
32 is inserted into the through hole 27 of the support plate 28 of the outer tubular body 21,
The lower end surface of 22 comes into contact with and is supported by the upper surface of the support plate 28. In the vicinity of the lower end of the inflow pipe 32, an annular closing plate 33 whose peripheral edge is attached to the opening edge of the lower end of the joint portion 29 is attached to close the lower end opening of the joint portion 29.

Further, inside the inner tube body 22, there are provided three disc-shaped catalyst receivers 35 which are permeable to air and which are partitioned in the axial direction.
From the lower end side where the inflow pipe 32 is provided, an inflow chamber 36, a sulfide alteration chamber 37, a desulfurization chamber 38, and a methanation chamber 39 are defined.

The inflow chamber 36 is formed in a hollow state so that the mixed gas 1d flowing in from the inflow pipe 32 passes through the inner pipe body 22 substantially uniformly in the cross section of the inner pipe body 22.

Further, in the sulfide alteration chamber 37, a cobalt-molybdenum (Co-Mo) type hydrogenation catalyst (COMOX) 37a is used.
The unsaturated hydrocarbons in the raw material 1a are reacted with H ₂ of the recycle gas 1b into saturated hydrocarbons (C _n H _{2n + 2} ) by the COMOX 37a, and the organic sulfur compounds in the raw material 1a are converted into C _n H 2 React with _{2n + 2} and H ₂ S.

Further, the desulfurization chamber 38 is filled with a zinc oxide ( ZnO ) adsorbent 38a for adsorbing and removing hydrogen sulfide (H ₂ S) in the mixed gas 1d.

Then, the methanation chamber 39 is filled with a nickel (Ni) -based catalyst 39a, and C _n H in the raw material 1a is filled.
_{2n + 2} is converted to methane (CH ₄ ) by H ₂ of recycled gas 1b
Decomposes into raw material 1a and recycled gas 1b
Carbon monoxide (CO) and carbon dioxide (CO ₂ ) in
However, with H ₂ and H ₂ O containing 1 c of steam, methane (C
H ₄ ) and CO ₂ .

A reforming chamber 40 filled with a nickel (Ni) -based catalyst 40a is formed between the outer peripheral surface of the inner tubular body 22 and the inner peripheral surface of the outer tubular body 21. _n H _{2n + 2} and CH
CO and H ₂ with H ₂ O of steam 1 c mixed with ₄
Be reacted to.

Then, at the side opening of the joint portion 29 communicating with the outlet 23 of the reaction tube 12, the tube body 2 of the heat exchange device 4 is provided.
The mixed gas 1d that is connected to the lower part and flows out from the reaction tube 12,
The liquid raw material 1a flowing through the inner pipe 3 is cooled by heat exchange for vaporization.

Further, a cylindrical transformer 42 is connected to the heat exchange device 4. Then, in the transformer 42, a first shift chamber 43, a cooling chamber 44, and a second shift chamber 45 are partitioned from the upper end in the axial direction. Further, the first shift chamber 43 is filled with an iron-chromium (Fe-Cr) -based catalyst 43a,
CO in the mixed gas 1d is reacted with CO ₂ and H ₂ by the residual water vapor 1c in the Fe-Cr catalyst 43a, and C
O is reduced. The cooling chamber 44 is provided with an inner pipe 47 through which the cooling water 46 flows, and the mixed gas 1d is cooled by heat exchange with the cooling water 46. Further, the second transformer chamber 45, copper - zinc (Cu-Zn) catalyst 45a is filled, the CO remaining in the mixed gas 1d reacted to CO ₂ and H ₂ by steam, to further reduce the CO .

The transformer 42 is connected to a cooler 49 having an inner pipe 48 through which the cooling water 46 flows, and the mixed gas 1d is cooled by heat exchange with the cooling water 46.

Further, the cooler 49 includes a storage tank 50.
And the mixed gas 1d cooled by the cooler 49 is stored at a medium pressure of, for example, about 7 kgf / cm ² .

Further, between the cooler 49 and the storage tank 50, a control means 51 for controlling the heat generation amount of the mixed gas 1d flowing out from the cooler 49 is provided. And this control means
51 is a calorimeter 52 for detecting the heat generation amount of the mixed gas 1d
And a mixer 53 for vaporizing the raw material 1a from the raw material tank 1 by the calorimeter 52 and mixing the mixed gas 1d by a predetermined amount.
It consists of and.

On the other hand, 55 is a boiler, and this boiler 55
Uses a part of the raw material 1a of the raw material tank 1 as a fuel to evaporate water into water vapor 1c and supply it at a medium pressure of about 7 kgf / cm ² .

Further, 56 is an exhaust gas heat exchange device, which is formed in a cylindrical shape and has one end connected to the exhaust port 16 of the kiln 11 of the reaction tower 7 and the other end connected to the boiler 55. The exhaust gas of the combustion gas 15 from the reaction tower 7 is connected and used as secondary air for burning the raw material of the boiler. Further, in the exhaust gas heat exchange device 56, an inner pipe 57 is arranged similarly to the heat exchange device 4, the inner pipe 57 is connected to the boiler 55, and the steam 1c of the boiler 55 and the like can flow. .
Then, the water vapor 1c flowing through the inner pipe 57 is heat-exchanged from the exhaust gas from the reaction tower 7 and heated. Further, the inner pipe 57 of the exhaust gas heat exchange device 56 is connected to the raw material mixing device 5 so as to mix the steam 1c with the raw material 1a.

Next, the gasification operation of the above embodiment will be described.

About 7 kgf / cm ² of liquid raw material 1a, butane (C ₄ H ₁₀ ) in the raw material tank 1 is caused to flow into the inner pipe 3 of the heat exchange device 4, and the inside of the tubular body 2 of the heat exchange device 4 Is vaporized and heated by heat exchange with the mixed gas 1d flowing through. Meanwhile, at the boiler 55, medium pressure steam (H ₂ O) 1c of about 7 kgf / cm ²
Is generated, and this H ₂ O 1c is further added to the exhaust gas heat exchange device 4
Heat at.

Then, the vaporized and heated C ₄ H ₁₀ gas 1a is caused to flow into the raw material mixing apparatus 5, and the C ₄ H ₁₀ gas 1a is supplied.
In the carrier gas tank 6, about 7 kgf / cm ² of recycled gas 1b and H ₂ O 1c from the boiler 55 are added to C ₄ H ₁₀
1a, H ₂ O 1c, and hydrogen (H ₂ ) in the recycled gas 1b are mixed in a ratio of 10: 30: 1.

Next, the mixed gas 1d is caused to flow into the inflow chamber 36 in the inner pipe body 22 from the inflow port 31 of the reaction tube 12 of the reaction tower 7 through the inflow pipe 32. The reaction tower 7 is the raw material tank 1
Kiln body of C ₄ H ₁₀ 1a at a burner (not shown) and fuel
The inside of 11 heating chambers 10 is heated to about 880 ° C.

The burner combustion gas 15 is used in the heating chamber 10
After through the exhaust port 16 flows into the exhaust gas heat exchanger 56, the H ₂ O1c generated the inner tube 57 of the exhaust gas heat exchanging device 56 from the boiler 55 flowing past and heated by heat exchange from the boiler 55
The exhaust gas of the boiler 55 is reused as the secondary air and the secondary air of the burner, and is exhausted after being processed by an exhaust gas processing device (not shown).

Then, the mixed gas flowing into the inflow chamber 36
1d flows into the sulfide alteration chamber 37 above the inflow chamber 36 while being heated to about 350 to 400 ° C., and the cobalt-molybdenum (Co—Mo) based hydrogenation catalyst ( (COMOX) 37a causes unsaturated hydrocarbons in the mixed gas 1d to react with saturated hydrocarbons (C _n H _{2n + 2} ) by H _{2 in the} recycle gas 1b, and organic sulfur compounds to C _n H _{2n + 2} and sulfide. A hydrogenation reaction of reacting with hydrogen (H ₂ S) is performed.

Further, the mixed gas 1d which has passed through the sulphide alteration chamber 37 flows into the upper desulfurization chamber 38 and is heated to about 400 to 500 ° C.
The sulfur (S) of H ₂ S in the mixed gas 1d is adsorbed with Zn of the ZnO-based adsorbent 38a by the ZnO (zinc oxide) -based adsorbent 38a filled in the desulfurization chamber 38 while being heated to (ZnS) next, H ₂ S in H ₂ is the ZnO-based adsorbent 38a
Oxygen combine with (O) to generate the H ₂ O, desulfurization reactions shown in the following _{formula, ZnO + H 2 S → ZnS} + H 2 O is produced.

The desulfurized mixed gas 1d flows into the upper methanation chamber 39, and the nickel (Ni) catalyst 39a filled in the methanation chamber 39 causes the mixed gas 1d.
A part of C _n H _{2n + 2} in 1d is decomposed into methane (CH ₄ ) by H ₂ of the recycled gas 1b, and carbon monoxide (CO) and carbon dioxide (CO) in the mixed gas 1d and the recycled gas 1b ( CO ₂ ) is reacted with methane (CH ₄ ) and CO ₂ with H ₂ and H ₂ O, the decomposition and methane synthesis reaction (methanation) represented by the formula below, C _n H _{2n + 2} + (n _{-1) H 2 → nCH 4 CO} + 3H 2 → CH 4 + H 2 O CO + H 2 O → CO 2 + H 2 CO 2 + 4H 2 → CH 4 + 2H 2 O proceeds.

The methane synthesis reaction is an exothermic reaction, and the temperature of the mixed gas 1d rises to about 550 to 600 ° C. due to the exothermic reaction with the heating from the burner.

Next, the mixed gas 1d flowing through the methanation chamber 39 and flowing from the upper end of the inner pipe body 22 to the upper portion of the outer pipe body 21.
Flows into the reforming chamber 40 between the inner pipe body 22 and the outer pipe body 21.
Then, the mixed gas 1d is mixed with the Ni-based catalyst 40 filled in the reforming chamber 40 while being heated by the burner.
C _n H _{2n + 2} and CH ₄ in the H ₂ O of water vapor 1c
A steam reforming reaction represented by the following formula, which is reacted with O and H ₂ , C _n H _{2n + 2} + nH ₂ O → nCO + (2n +
1) H ₂ CH ₄ + H ₂ O → CO + 3H ₂ progresses.

After this, the mixed gas 1d flowing through the reforming chamber 40
Is heated to about 750 ° C. by heating from the burner and flows into the heat exchange device 4 from the outlet 23 of the reaction tube 12 via the joint 29. Then, the mixed gas 1d vaporizes C ₄ H ₁₀ of the liquid raw material 1a flowing through the inner pipe 3 of the heat exchange device 4, and the temperature of the mixed gas 1d is about 400 by this heat exchange.
Cool to ~ 450 ° C.

Further, the cooled mixed gas 1d is transferred to the transformer.
It flows into the transformer 42, and iron-chromium (Fe-C
r) Flow through the first shift chamber 43 filled with the system catalyst 43a.
During this flow-through, the mixed gas 1d was mixed with the Fe-Cr catalyst 43a.
CO in the inside is reacted with CO ₂ and H ₂ by H ₂ O of residual water vapor 1c, a CO shift reaction shown by the following formula, CO + H ₂ O → CO ₂ + H ₂ , occurs, and the CO concentration is reduced. Next, the mixed gas 1d flows from the first shift conversion chamber 43 into the cooling chamber 44, and exchanges heat with the cooling water 46 flowing through the inner pipe 47 arranged in the cooling chamber 44 to about 20%.
Cooled to 0 ° C, copper-zinc (Cu-Zn) -based catalyst 45
It flows into the second shift conversion chamber 45 filled with a. Then, the mixed gas 1d is CO-converted by the Cu—Zn-based catalyst 45a, and the residual CO is converted into H ₂ O of the remaining steam 1c by C ₂ C.
By reacting with O ₂ and H ₂ , CO concentration is further reduced.

The CO-transformed mixed gas 1d flows into the cooler 49 and is further cooled by heat exchange with the cooling water 46 flowing through the inner pipe 48 arranged in the cooler 49. .

Thereafter, the calorific value of the mixed gas 1d is detected by the calorimeter 52 of the control means 51, and the calorific value is about 450.
Raw material tank 1 in mixer 49 so that it becomes 0 kcal / Nm ^3.
The mixed gas 1d in which the gas and the gas obtained by vaporizing C ₄ H ₁₀ 1a from the above is mixed with the mixed gas 1d in a predetermined amount and the calorific value is controlled is
It is stored in the storage tank 50 at a medium pressure of about 7 kgf / cm ² as a production gas containing CH ₄ , CO ₂ , and CO containing H ₂ as a main component and having a predetermined composition.

The cooling chamber 44 and the cooling device 49 of the transformer 42
The cooling water 46 that has been heat-exchanged at is used as a water source of steam (H ₂ O) 1c generated in the boiler 55.

Next, the operation of the above embodiment will be described.

In the reaction tower 7, C in the sulfide alteration chamber 37
The hydrogenation reaction with OMOX47a is efficiently carried out at about 350 to 400 ° C. In addition, the ZnO-based adsorbent in the desulfurization chamber 38
The desulfurization reaction by 38a is efficiently performed at about 400 to 500 ° C. Furthermore, the Ni-based catalyst in the methanation chamber 39
Degradation and methane synthesis reaction to C _n H _{2n + 2} of CH ₄ by 39a, is efficiently performed at about 500 to 600 ° C.. Further, the steam reforming reaction by the Ni-based catalyst 40a in the reforming chamber 40 is efficiently performed at about 600 to 750 ° C.

In the above embodiment , the reaction tube 12 is replaced by the inner tube body.
22 and the outer tubular body 21 are coaxially formed into a double tubular structure, and the sulfide alteration chamber 37, the desulfurization chamber 38, the methanation chamber 39, and the mixed gas 1d in the inner tubular body 22 are located below the kiln 11. In order to efficiently heat with the burner installed in the
The reforming chamber 40 that is formed by partitioning in the axial direction of, and further performs a steam reforming reaction that is an endothermic reaction that requires a large reaction heat,
Formed between the outer tube body 21 and the inner tube body 22 heated by the burner, from the inlet 31 side to the outlet 23, the sulfide alteration chamber 37, the desulfurization chamber 38, the methanation chamber 39, the reforming chamber Since 40 are sequentially formed, each catalytic reaction according to the purpose can be efficiently and reliably progressed.

[0052] Further, in one reaction column 7, hydrogenation, desulfurization, material degradation and methane synthesis reaction, steam reforming reaction can be carried out, with the heat loss suppressed manufacturing cost can be reduced, the catalyst It is not necessary to provide a plurality of individual reaction towers 7 for individually performing the reactions, and the device can be simplified and downsized, and the device can be installed easily.

Further, the outer periphery of the methanation chamber 39 is modified.
The chamber 40 is provided coaxially, and before the steam reforming reaction is performed in the reforming chamber 40, CH ₄ of C _n H _{2n + 2} is decomposed in the methanation chamber 39, and the methane synthesis reaction is an exothermic reaction. Is being done. For this reason, steam reforming from lower methane is easier than steam reforming from higher saturated hydrocarbons, and the reaction heat required for the steam reforming reaction of the endothermic reaction can be reduced and the exothermic reaction Due to the heat generation from the methane synthesis reaction, the combustion amount of the burner supplying reaction heat to the steam reforming of the mixed gas 1d can be reduced, and the manufacturing cost can be reduced.

Further, since the spiral wind control wall 25 is provided on the outer peripheral surface of the outer tube body 21 of the reaction tube 12, the combustion gas of the burner is kilned in a spiral shape around the reaction tube 12 by the wind control wall 25. Since it flows over the heating chamber 10 of the body 11, the reaction tube 12
The heating can be performed substantially uniformly, and the desired catalytic reaction can be efficiently and reliably progressed.

Further, unlike the conventional case, the raw material 1a is once pressurized to a high pressure to produce a gas, and the mixed gas 1d is decompressed and the pressure is not increased or decreased. Therefore, equipment for pressure operation is not required. Manufacturing efficiency can be improved and manufacturing cost can be reduced.

Then, the raw material mixing apparatus 5 is provided, and the reaction tube 12
In order to correspond to the calorific value produced in C ₄ H ₁₀ of the raw material 1a flowing into the reactor, H ₂ O and H ₂ are mixed in a predetermined amount, and the reaction is carried out without pressure up / down operation. Even if they are different, it is possible to easily deal with them, and it is possible to easily produce a production gas having a composition with a desired calorific value, and it is possible to facilitate the production operation.

Further, a mounting port 19 is formed at the lower end of the kiln 11, a construction window 17 is formed at the upper end, and the reaction tube 12 is inserted through the construction window 17, and one end of the reaction tube 12 is fitted into the mounting port 19. Since the reaction tube 12 is installed by inserting it, maintenance and management of the reaction tube 12 such as exchange of various catalysts filled in the reaction tube 12, cleaning of the heating chamber 10 of the furnace 11 and repair of the refractory 9 Maintenance of the body 11 can be easily performed.

Although the reaction tube 12 is formed in a double tube structure in the above embodiment, a multi-tube structure, for example, the sulfide alteration chamber 37 and the desulfurization chamber 38 are formed in the inner tube body 22, and this inner tube is formed. A methanation chamber 39 is formed between the inner tubular body and the inner tubular body that coaxially encloses the body 22, and the outer peripheral side of the methanation chamber 39 is further formed.
Medium tube to be positioned in a triple pipe structure formed reformed chamber 40 between the outer tube member 21 and the middle tube body enclosing coaxially, the same effect can Ru obtained.

[0059]

According to the medium-pressure continuous gasifier of the present invention, a desulfurization chamber for desulfurizing the raw material, a methanation chamber for methanizing the raw material, and a reforming chamber for steam reforming the raw material are provided for each catalytic reaction. Methane that performs methanation, which is an exothermic reaction, in order of temperature range
Located on the outer peripheral side that is heated from the
Since the reforming chamber for performing steam reforming, which is a thermal reaction, is installed and has a multi-tube structure , the heat generated during methanization is required for steam reforming.
It can be used for necessary heat , heat efficiency can be improved, gasification can be made inexpensive, and desulfurization, methanation, and steam reforming can be performed in one reaction tube, and the apparatus can be simplified and downsized.

[Brief description of drawings]

FIG. 1 is a system explanatory view showing an embodiment of a medium-pressure continuous gasifier of the present invention.

FIG. 2 is a cross-sectional view showing the same reaction tower.

FIG. 3 is a system diagram showing an example of a conventional medium-pressure continuous gasifier.

[Explanation of symbols]

 1a Raw material 12 Reaction tube 23 Outlet 31 Inlet 38 Desulfurization chamber 39 Methanation chamber 40 Reforming chamber 42 Transformer

Claims (1)

(57) [Claims] 1. A reaction tube whose outer periphery is heated after desulfurization of a raw material, steam is mixed, and reformed into a gas containing hydrogen gas as a main component by a nickel-based reforming catalyst, and a gas from this reaction tube. In a medium-pressure continuous gasifier equipped with a shifter for transforming the carbon dioxide gas inside, the reaction tube is a desulfurization chamber having an inlet into which a raw material flows and a catalyst for desulfurizing the raw material flowing from the inlet. A methanation chamber having a catalyst for reacting the raw material flowing from the desulfurization chamber with methane; and a reforming catalyst having a reforming catalyst for steam reforming the raw material flowing from the methanation chamber into hydrogen by the mixed steam. and quality chamber, this communicates with the reforming chamber steam reformed gas and a flow outlet exiting, prior Kiaratame quality chamber located on the outer peripheral side of the methanation chamber <br/> coaxially the formation of which disposed the at least double-pipe structure A medium-pressure continuous gasifier characterized by the following features.