JPH0552355B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an improvement in a city gas production method, and more specifically, to a city gas production process in which the unit reactions are a hydrodesulfurization process of raw material hydrocarbons and a low-temperature steam reforming process. Incorporating a methanol reforming process, the reaction heat required for the methanol reforming process is covered by the heat recovered from the city gas production process, and the hydrogen produced in the methanol reforming reaction is used in the hydrodesulfurization process of feedstock hydrocarbons. This relates to a method for producing city gas that has been improved so that it can be used for

In general, city gas can be produced through a series of operations, including hydrodesulfurization of feedstock hydrocarbons such as LPG or naphtha, followed by low-temperature steam reforming, and then removing carbon dioxide from the produced gas. Caloric city gas can be produced by interposing a methanation process between a low temperature steam reforming process and a decarboxylation process. In such city gas production processes, it is customary to use a portion of the reformed gas flowing out from the low-temperature steam reforming process as a hydrogen source for hydrodesulfurizing feedstock hydrocarbons. ing.

By the way, the performance of low-temperature steam reforming catalysts has improved dramatically in recent years, and with this, the low-temperature steam reforming process requires lower temperatures and lower steam ratios (relative to The situation is such that it can be implemented using hydrocarbon feedstock). Therefore, the advent of high-performance low-temperature steam reforming catalysts has made it possible to operate the city gas production process under more economical conditions. However, when a low-temperature steam reforming process is carried out at a low temperature and low steam ratio using a high-performance catalyst, the hydrogen concentration in the generated gas inevitably decreases, so a part of this gas is used as raw material. In the embodiment in which the hydrocarbon is circulated to the hydrodesulfurization step, there is a disadvantage that the raw material hydrocarbon cannot be sufficiently purified.

For this reason, in the conventional city gas production process,
In order to increase the hydrogen concentration of the gas that is circulated to the hydrodesulfurization process, the gas supplied from the low-temperature steam reforming process is subjected to a high-temperature steam reaction, and then subjected to a CO shift reaction before being recycled to the hydrodesulfurization process. Alternatively, there is a method in which the gas from the low-temperature steam reforming process is supplemented with steam to increase the steam ratio, and this gas is processed in a second low-temperature steam reforming reaction process and then circulated to the hydrodesulfurization process. has been adopted. However, the former method requires the installation of a high-temperature steam reforming reactor and a CO shift reactor, which is disadvantageous in terms of increased equipment costs. on the other hand,
In the latter method, since the second low-temperature steam reforming reaction is endothermic, a significant increase in hydrogen concentration cannot be expected because hydrogen production is suppressed in chemical equilibrium by lowering the reaction temperature.

In view of the current state of the prior art as described above, the present invention incorporates a methanol reforming process into a city gas production process in which the unit reactions are a hydrodesulfurization process of feedstock hydrocarbons and a low-temperature steam reforming process of desulfurized hydrocarbons. By incorporating this, we provide a city gas production method that can self-suffice high-concentration hydrogen gas for the hydrodesulfurization process of feedstock hydrocarbons even when using a high-performance low-temperature steam reforming catalyst.

CH ₃ OH + H ₂ O → CO ₂ + 3H ₂ ...(1) ΔH _R = 12Kcal/g・mole The methanol reforming reaction is an endothermic reaction as shown in equation (1) above, but the necessary reaction here is Heat can be provided by the retained heat of the product gas flowing out from the low temperature steam reforming process in the city gas production process.

Therefore, the first method according to the present invention includes hydrodesulfurizing feedstock hydrocarbons, mixing the desulfurized hydrocarbons with steam, and supplying the mixture to a low-temperature steam reforming reaction zone.
In a method for producing city gas in which city gas is produced by bringing hydrocarbons and steam into contact with a reforming catalyst under low-temperature steam reforming conditions in the reaction zone, the A methanol reforming reaction zone is provided which is indirectly heated by the gas effluent from the zone, and methanol and steam are supplied to this reaction zone to reform methanol in the presence of a methanol reforming catalyst, and the hydrogen produced is It is characterized in that it is used for hydrodesulfurization of the above-mentioned raw material hydrocarbon.

By the way, as seen in the conventional city gas production process, when obtaining so-called high-calorie gas, a methanation process is installed downstream of the low-temperature steam reforming process, and the reformed gas flowing out from the low-temperature steam reforming process is The method used is to send the gas to a methanation process to methanize the CO ₂ in the reformed gas and increase the methane concentration.

CO ₂ +4H ₂ → CH ₄ +2H ₂ O ...(2) ΔH _R = -40Kcal/g・mole However, since the methanation reaction of CO ₂ is an exothermic reaction as shown in equation (2) above, this If the reaction heat is exchanged between the reaction and the methanol reforming reaction mentioned above, the heat can be used effectively (1)
Equation (2) has the advantage that not only can hydrogen for hydrodesulfurization be generated, but also methane concentration can be increased using equation (2). Moreover,
Since the reaction heat of the methanation reaction of formula (2) is absorbed by the methanol reforming reaction of formula (1), the chemical equilibrium of formula (2) can also be maintained advantageously for methane production.

Therefore, the second method according to the present invention includes hydrodesulfurizing feedstock hydrocarbons, mixing the desulfurized hydrocarbons with steam, and supplying the mixture to a low-temperature steam reforming reaction zone.
In a method for producing city gas in which city gas is produced by bringing hydrocarbons and steam into contact with a reforming catalyst under low-temperature steam reforming conditions in the reaction zone, a methanation reaction zone is provided on the heated fluid passage side. A heat exchange reactor having a methanol reforming reaction zone on the heated fluid passage side is provided downstream of the low temperature steam reforming reaction zone, and city gas flowing out from the low temperature steam reforming reaction zone is supplied to the methanation reaction zone. , a methanation reaction is caused in the presence of a methanation catalyst to increase the methane concentration of city gas, and while the methanol reforming reaction zone is heated with the reaction heat released from this methanation reaction zone, this zone is heated. The present invention is characterized in that methanol and steam are supplied to reform methanol in the presence of a methanol reforming catalyst, and the generated hydrogen is used for the hydrodesulfurization of the feedstock hydrocarbons described above.

This second city gas production method differs from the first method in that it includes a methanation step, but it
As is clear from equation (2), the methanation reaction of CO ₂ is accompanied by considerable heat generation, so it is best to use a heat exchange reactor in which the methanation reaction zone and methanol reforming reaction zone are adjacent. It is also possible to provide both reaction zones separately and heat the methanol reforming reaction zone with the gas flowing out from the methanation reaction zone; It is also possible to heat the methanol reforming reaction zone with a gas which is then fed to the methanation reaction zone.

The methanol reforming reaction requires water vapor, as can be seen from equation (1) above. For this reason, the first
In the second method, methanol and steam were supplied to the methanol reforming reaction zone, but the steam necessary for methanol reforming was supplied by the steam remaining in the outlet gas of the low temperature steam reforming reaction zone, and the methanol reforming reaction zone was supplied with methanol and steam. The reaction heat required for this can be covered by the heat possessed by the gas.

Therefore, the third method of the present invention is to hydrodesulfurize feedstock hydrocarbons, mix the desulfurized hydrocarbons with steam, and supply the mixture to a low-temperature steam reforming reaction zone, where the hydrocarbons and In a method for producing city gas in which city gas is produced by contacting steam with an improved catalyst under low-temperature steam reforming conditions, a methanol reforming reaction zone is attached, and methanol and low-temperature steam reforming reaction zone are added to the reaction zone. The system is characterized by supplying a portion of city gas flowing out from the system to reform methanol in the presence of a methanol reforming catalyst, and using the generated hydrogen for hydrodesulfurization of feedstock hydrocarbons.

Furthermore, the fourth method of the present invention is the method in which a methanation step is added to the third method, and in this method, the remainder of the low temperature steam reforming reaction zone outlet gas is supplied to the methanol reforming reaction zone. By supplying methane to the methanation reaction zone, the methane concentration is increased. An alternative to this fourth method is to increase the methane concentration by supplying the low temperature steam reforming reaction zone outlet gas to the methanation reaction zone without diverting it to the methanol reforming reaction zone, and then increasing the methane concentration in the methanation reaction zone. A portion of the outlet gas is supplied to the methanol reforming reaction zone together with methanol.

Hereinafter, the present invention will be described in more detail with reference to the accompanying drawings. Prior to that, symbols used in the drawings will be explained as follows.

HDS = hydrodesulfurization process MRG = low temperature steam reforming process MET = methanation process REF = methanol reforming process CO ₂ Rem = CO ₂ removal process ST'M = steam Figure 1 shows the implementation of the second method of the present invention In this block diagram, feedstock hydrocarbons such as LPG or naphtha are fed from line 1 to HDS step 2 to undergo hydrodesulfurization. still,
Hydrogen-containing gas is recycled from line 3 to HDS step 2, which will be described later.
The raw material hydrocarbons refined in the HDS process are introduced into the MRG process 5 together with steam (ST'M) supplied to line 4, where they are reformed to contain methane, hydrogen, carbon monoxide, carbon dioxide, and unreacted steam. Converts to gas. This reformed gas is sent from line 6 to MET step 7, where carbon dioxide in the gas is converted into methane according to equation (2) above, resulting in an increase in methane concentration. The gas with increased methane concentration is sent to CO ₂ Rem from line 8 according to the standard method of city gas production.
It is sent to a process where it undergoes decarboxylation treatment and becomes what is called a high-calorie gas. Each process up to this point is a MET process.
There is no substantial difference from the previous city gas production process, which was established downstream of the MRG process, and the catalysts and reaction conditions used in each process are different from those in the previous city gas production process. The conditions can be adopted as they are.

However, two-stage reforming using conventional low-temperature steam reforming catalysts, such as nickel catalysts supported on alumina or diatomaceous earth, or using high-performance low-temperature steam reforming catalysts such as ruthenium catalysts, When Step 5 is operated at a low temperature and low steam ratio, the hydrogen concentration of the reformed gas flowing through Line 6 decreases, so even if some of this gas is recycled to HDS Step 2, the feedstock hydrocarbons cannot be sufficiently converted. Cannot be hydrodesulfurized.

Therefore, in the second method of the present invention, REF step 1
0 is provided in a state where it can exchange heat with the MET step 7, methanol and steam are supplied to this step 10, and methanol is reformed according to the above-mentioned equation (1). Although methanol reforming is an endothermic reaction, the reaction heat required for this is covered by the calorific value of the methanation reaction that occurs in MET step 7, so methanol is reformed into hydrogen and carbon dioxide. Methanol reformed gas is REF
It is taken out from process 10 to line 11, and heat exchanger 1
2 and gas-liquid separator 13, from line 3 as a hydrogen-containing gas for hydrodesulfurization of feedstock hydrocarbons.
Recycled to HDS process 2.

In addition, in Figure 1, a heat exchange type reactor is used.
Although the mode in which reaction heat is exchanged between REF step 10 and MET step 7 has been shown, REF step 10
The heat of reaction required for can be provided by indirect heat exchange with the gas flowing in line 6 or line 8. In the block diagram shown in Figure 1, the installation of the MET process 7 is omitted and the reformed gas flowing from the MRG process 5 to the line 6 is used in the REF process 1.
The mode of heating 0 corresponds to the first method of the present invention.

FIG. 2 is a block diagram when implementing the fourth method of the present invention, in which feedstock hydrocarbons supplied from line 1 are hydrodesulfurized in HDS step 2, and low-temperature steam reformed in MRG step 5. ,
The process of methanation in the MET step 7 and decarboxylation in the CO ₂ Rem step 9 to convert into a so-called high-calorie gas is the same as in the case of FIG. The difference between the method shown in FIG. 1 and the method shown in FIG. The reformed gas is divided into
The point is that methanol is reformed by being supplied to the REF step 10. In the latter case, unreacted steam in the reformed gas flowing through line 6' is used as the steam necessary for reforming methanol. Since methanol reforming catalysts generally do not have methanation activity, the methanol reforming reaction can proceed selectively in the REF step 10 of FIG. As a reminder, since methanol reforming is an endothermic reaction, the reaction temperature is lowered, but in the reaction zone, methanation activity is suppressed and shift activity is expressed, so in equilibrium, CO is reduced. , hydrogen production is not inhibited. The gas produced in the REF step 10 is taken out to the line 11, and as in the case of Fig. 1, it passes through the heat exchanger 12 and the gas-liquid separator 13, and is sent out from the line 3 as a hydrogen-containing gas for hydrodesulfurization.
Recycled to HDS process 2.

In Figure 2, the MET process 7 is installed downstream of the MRG process 5 to increase the methane concentration in city gas and obtain high-calorie gas, but the MET process is omitted when obtaining regular city gas. In the block diagram shown in Figure 2,
The embodiment in which MET step 7 is omitted corresponds to the third method of the present invention.

In the first to fourth methods described above, known catalysts and reaction conditions can be used for reforming methanol. For example, as methanol reforming catalysts, copper, copper-zinc , copper-chromium,
Platinum or the like may be used, and the reaction conditions may be a temperature of 150° C. to 500° C. and a pressure of 50 Kg/cm ² G or less. According to the method of the present invention, the quality deterioration of hydrogen for hydrodesulfurization that occurs when the low-temperature steam reforming step in the city gas production process is operated at low temperature and low steam ratio can be avoided in the process. This can be improved by adding a methanol reforming step, and in addition, the reaction heat required for methanol reforming can be self-sufficient within the city gas production process. Although not shown in Figures 1 and 2, in the general city gas production process, it is customary to pressurize recycled gas in a compressor and return it to the hydrodesulfurization process. In the method of the invention, by performing the REF step 10 at a higher pressure than the HDS step 2, a compressor for recycled gas can be made unnecessary.

Example 1 This example shows an example of producing city gas according to the block diagram shown in FIG.

Hydrodesulfurization reactor 2, which has a hydrogenation zone filled with a pre-sulfurized NiMoX catalyst and an adsorption desulfurization zone filled with ZnO, was charged with 147/hr raw material naphtha (IBP 35℃, EP 162℃, specific gravity 0.68, sulfur content 230wt.
ppm) and hydrogenation gas of 9.48Nm ³ /hr,
After hydrogenation under the conditions of 340° C., 25 Kg/cm ² G, and LHSV=2.0, hydrogen sulfide was removed. Thus the sulfur concentration
126.0 Kg/hr of steam was added to the raw material naphtha refined to 0.1 wt.ppm or less, and the mixture was fed to the low temperature steam reforming reactor 5 filled with a ruthenium catalyst, and heated at 490°C.
The modification reaction was carried out under the condition of 19 kg/cm ² G.

On the other hand, methanol 3.66Kg/hr and steam 2.06
After preheating the mixture with Kg/hr to 250°C, it is supplied to the methanol reforming reactor 10, which has a copper-based methanol reforming catalyst packed in the tube side of the heat exchange reactor. The reformed gas flowing out from the reactor 5 was supplied to the shell side, and the temperature was 300°C, 26 kg/cm ² G,
Methanol reforming was carried out under the condition of LHSV=0.2. The methanol reformed gas obtained from the reactor 10 was cooled to condense and remove excess steam, and then recycled to the hydrodesulfurization reactor 2 through the line 3 as a hydrogenation gas. The composition of this gas is shown in column a of Table 1.
Further, the composition of the reformed gas obtained from the reactor 5 as the product gas is shown in column b of Table 1.

Table 1 a b CH ₄ -vol% 67.1vol% H ₂ 73.4 〃 10.6 〃 CO 6.2 〃 0.9 〃 CO ₂ 20.4 〃 21.4 〃 Example 2 This example is based on the block diagram shown in Figure 1 (however, the decarboxylation process is This is an example of producing city gas according to the method (omitted).

Hydrodesulfurization reactor 2, which has a hydrogenation zone filled with a pre-sulfurized NiMoX catalyst and an adsorption desulfurization zone filled with ZnO, was charged with 147/hr raw material naphtha (IBP 35℃, EP 162℃, specific gravity 0.68, sulfur content 230wt.
ppm) and hydrogenation gas of 9.48Nm ³ /hr,
After hydrogenation under the conditions of 340° C., 25 Kg/cm ² G, and LHSV=2.0, hydrogen sulfide was removed. Thus the sulfur concentration
126.0 Kg/hr of steam was added to raw material naphtha refined to 0.1 wt.ppm or less, and the mixture was fed to a low-temperature steam reforming reactor 5 filled with a ruthenium catalyst, and heated at 500°C.
The modification reaction was carried out under the condition of 19 kg/cm ² G.

The obtained reformed gas was cooled to 280°C and fed to the shell side of a heat exchange reactor, which was filled with a nickel-based methanation catalyst in the shell side and a methanol reforming catalyst in the tube side. The reaction was carried out under the conditions of /cm ² G. On the other hand, methanol 3.66Kg/hr and steam 2.06
Kg/hr was preheated to 250°C and fed to the tube side of the heat exchange reactor, and the mixture was heated to 280°C and 26Kg/cm ² G.
The reaction was carried out under the following conditions. The methanol reformed gas obtained from this reaction is cooled and the steam is condensed and removed.
It was recycled to reactor 2 as a hydrogenation gas. Further, the gas flowing out from the shell side of the heat exchange type reactor was cooled and water vapor was separated, followed by product gas.

Column a of Table 2 shows the composition of the hydrogenation gas obtained from the methanol reformed gas, and column b shows the composition of the product gas.

Table-2 a b CH ₄ -vol% 66.2vol% H ₂ 73.7 〃 11.5 〃 CO 5.4 〃 1.1 〃 CO ₂ 20.9 〃 21.2 〃 Example 3 In this example, city gas is produced according to the block diagram shown in Figure 4. did.

Hydrodesulfurization reactor 2, which has a hydrogenation zone filled with a pre-sulfurized NiMoX catalyst and an adsorption desulfurization zone filled with ZnO, was charged with 147/hr raw material naphtha (IBP 35℃, EP 162℃, specific gravity 0.68, sulfur content 230wt.
ppm) and hydrogenation gas of 9.48Nm ³ /hr,
After hydrogenation under the conditions of 340° C., 25 Kg/cm ² G, and LHSV=2.0, hydrogen sulfide was removed. Thus the sulfur concentration
126.0 Kg/hr of steam was added to raw material naphtha refined to 0.1 wt.ppm or less, and the mixture was fed to a low-temperature steam reforming reactor 5 filled with a ruthenium catalyst, and heated at 500°C.
The modification reaction was carried out under the condition of 19 kg/cm ² G.

1/30 of the reformed gas thus obtained was separated, 3.66 kg/hr of methanol was added thereto, and the mixture was supplied to the methanol reforming reactor 10 filled with a copper-based methanol reforming catalyst, at 220°C and 17 kg/cm ² The reaction was carried out under the conditions of G.
In this case, the amount of steam supplied is approximately 60 kg due to the reaction of 147 kg/hr of naphtha with 126 kg/hr of steam.
Kg/hr of steam is consumed, and 66 Kg/hr of steam still remains in the reformed gas. This 1/
30 is used for methanol reforming, as in Examples 1 and 2, it is possible to supply approximately 2.06 Kg/hr, which is the required amount of steam for 3.66 Kg/hr of methanol. The methanol reformed gas flowing out from the reactor 10 is cooled to remove steam, and then pressurized in a recycle compressor and sent to the reactor 2 as a hydrogenation gas.
supplied. Further, the remaining portion 29/30 of the reformed gas was cooled to condense and remove steam, and was used as a product gas.

Columns a and b of Table 3 show the compositions of the hydrogenation gas and product gas, respectively.

Table-3 a b CH ₄ 25.4vol% 66.4vol% H ₂ 50.1 〃 11.3 〃 CO 2.3 〃 1.1 〃 CO ₂ 22.3 〃 21.2 〃

[Brief explanation of the drawing]

1 to 4 each show a block diagram for carrying out the method of the present invention. 2; Hydrodesulfurization process, 5; Low temperature steam reforming process, 7; Methanation process, 9; CO ₂ removal process, 1
0; methanol reforming step; 13; gas-liquid separator.

Claims (1)

[Claims] 1 Hydrodesulfurization of feedstock hydrocarbons, the desulfurized hydrocarbons mixed with steam and supplied to a low temperature steam reforming reaction zone, where the hydrocarbons and steam are subjected to low temperature steam reforming. In a method for producing city gas in which city gas is produced by bringing it into contact with a reforming catalyst under quality conditions, methanol is placed downstream of a low-temperature steam reforming reaction zone and is indirectly heated by the gas flowing out from the zone. A reforming reaction zone is provided, methanol and steam are supplied to this reaction zone to reform methanol in the presence of a methanol reforming catalyst, and the generated hydrogen is used for the hydrodesulfurization of the feedstock hydrocarbons described above. A method for producing city gas characterized by: 2. Hydrodesulfurize the feedstock hydrocarbons, mix the desulfurized hydrocarbons with steam, and supply the mixture to a low-temperature steam reforming reaction zone, where the hydrocarbons and steam are reformed under low-temperature steam reforming reaction conditions. In a method for producing city gas in which city gas is produced by bringing it into contact with a quality catalyst, a heat exchange reactor having a methanation reaction zone on the heated fluid passage side and a methanol reforming reaction zone on the heated fluid passage side is used. It is installed downstream of the low-temperature steam reforming reaction zone, and the city gas flowing out from the low-temperature steam reforming reaction zone is supplied to the methanation reaction zone, and the methanation reaction occurs in the presence of a methanation catalyst to convert city gas into the methanation reaction zone. While increasing the methane concentration and heating the methanol reforming reaction zone with the reaction heat released from this methanation reaction zone, methanol and steam are supplied to this zone to reform methanol in the presence of a methanol reforming catalyst. and the produced hydrogen is used for hydrodesulfurization of the above-mentioned feedstock hydrocarbon. 3 In the method according to claim 2, instead of using the heat exchange type reactor, a methanation reaction zone and a methanol reforming reaction zone are provided separately, and the methanation reaction zone and the methanol reforming reaction zone are provided separately. The city gas is supplied to the methanation reaction zone, the methanation reaction is caused in the presence of a methanation catalyst to increase the methane concentration of the city gas, and the city gas with increased methane concentration is supplied to the methanol reforming reaction zone. A method for producing city gas, characterized by supplying methanol and steam to this zone while indirectly heating it, reforming the methanol, and using the generated hydrogen for hydrodesulfurization of feedstock hydrocarbons. 4 In the method described in claim 2, instead of using the heat exchange type reactor, a methanation reaction zone and a methanol reforming reaction zone are provided separately, and the methanation reaction zone and the methanol reforming reaction zone are provided separately. Methanol is reformed by supplying methanol and steam to the methanol reforming reaction zone while indirectly heating the methanol reforming reaction zone with city gas, and the generated hydrogen is used for hydrodesulfurization of feedstock hydrocarbons. A method for producing city gas, which comprises supplying city gas whose temperature has been lowered by heating a quality reaction zone to a methanation reaction zone, causing a methanation reaction to increase the methane concentration of the city gas. 5. Hydrodesulfurize the feedstock hydrocarbons, mix the desulfurized hydrocarbons with steam, and supply the mixture to a low-temperature steam reforming reaction zone, where the hydrocarbons and steam are reformed under low-temperature steam reforming conditions. In a method for producing city gas in which city gas is produced through contact with a catalyst, a methanol reforming reaction zone is attached, and methanol and a portion of the city gas flowing out from the low-temperature steam reforming reaction zone are supplied to the reaction zone. A method for producing city gas, characterized in that methanol is reformed in the presence of a methanol reforming catalyst, and the generated hydrogen is used for hydrodesulfurization of feedstock hydrocarbons. 6. Hydrodesulfurize the feedstock hydrocarbons, mix the desulfurized hydrocarbons with steam, and supply the mixture to a low-temperature steam reforming reaction zone, where the hydrocarbons and steam are converted to a mouth improvement catalyst under low-temperature steam reforming conditions. In the method for producing city gas in which city gas is produced by contacting with the gas, a methanation reaction zone is provided downstream of the low-temperature steam reforming reaction zone, and a methanol reforming reaction zone is further attached to perform the low-temperature steam reforming reaction. Part of the city gas flowing out from the zone is diverted to a methanol reforming reaction zone, and methanol is supplied to the reaction zone to reform it, and the generated hydrogen is used for hydrodesulfurization of feedstock hydrocarbons, A city characterized by supplying the remainder of the city gas flowing out from the low-temperature steam reforming reaction zone to the methanation reaction zone and causing a methanation reaction in the presence of a methanation catalyst to increase the methane concentration of the city gas. Gas production method. 7 In the method described in claim 6, city gas flowing out from the low-temperature steam reforming reaction zone is supplied to the methanation reaction zone without being diverted to the methanol reforming reaction zone to cause the methanation reaction. to increase the methane concentration of city gas, and divert a part of the high methane concentration city gas flowing out from the methanation reaction zone to the methanol reforming reaction zone,
A method for producing city gas, comprising supplying methanol to the reaction zone, reforming it, and using the generated hydrogen for hydrodesulfurization of feedstock hydrocarbons.