JP2008239443A - Method and system for producing synthesis gas - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for producing a synthesis gas by which, for example, lower hydrocarbons and aromatic hydrocarbons remaining in low concentration in a source gas refined by a conventional method such as coke oven gas can be efficiently removed. <P>SOLUTION: The system includes: a refining device not shown in the figure, for removing impurities in a source gas 11 containing hydrocarbons as the main component by a conventional method; a lower hydrocarbon removing device 12 for removing lower hydrocarbons remaining in low concentration in the source gas by a hydrogenation catalyst; a desulfurizing device 14 for desulfurizing a sulfur compound in the highly refined gas 13 from which lower hydrocarbons are removed; a device 17 for removing lower hydrocarbons and aromatic hydrocarbons, for adding steam 16 to preliminarily reform the source gas containing residual lower hydrocarbons and aromatic hydrocarbons to thereby remove the remaining lower hydrocarbons and aromatic hydrocarbons; and a reforming device 19 generating a modified gas 18 as the synthesis gas comprising CO<SB>2</SB>, CO and hydrogen. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

The present invention, for example, after purifying a raw material gas such as coke oven gas by a conventional method, further removes remaining lower hydrocarbons and aromatic hydrocarbons, and desulfurization step for desulfurization of sulfur compounds in the raw material gas and steam The present invention relates to a synthesis gas production method and system that can be added to prolong the life of a reforming process that generates CO ₂ , CO, and hydrogen.

At present, for example, a process such as a methanol plant uses natural gas mainly composed of CH ₄ as a raw material. In recent years, the use of gas originating from coal, petroleum, biomass, and the like has been increasing due to the increased raw material sources (heavy oil, tar).

  By the way, when a methanol synthesis plant is constructed from a gas originating from the coal, petroleum, biomass or the like based on the current natural gas process, there are the following problems.

If the temperature rises to 300 ° C or higher due to the presence of lower hydrocarbons that are not included in natural gas but are included in gas originating from coal, petroleum, biomass, etc., carbon (C ) A so-called coking phenomenon occurs due to precipitation.
Occurrence of this caulking may cause clogging of piping and the like, which may occur when plant operation cannot be maintained.

By the way, coke oven gas (COG), which has been produced as a by-product when producing coke by dry distillation of coal, has been used as a fuel for city gas and raw materials for chemical synthesis, and unrefined coke oven gas is an impurity. In order to remove (H ₂ S, COS, aromatic hydrocarbons, tar, dust, etc.), purification by a conventional method is performed (see, for example, Patent Document 1).

JP 2000-248286 A

However, since the lower hydrocarbons still remain at a low concentration in the raw gas obtained by refining a general ordinary method, as described above, in order to actually apply to natural gas facilities, lower carbons are still used. Hydrogen must be completely removed.
In addition, aromatic hydrocarbons cause poisoning of the catalyst of the reformer that reforms the synthesis gas, so it is also necessary to remove them.

The present invention has been made in view of the above circumstances, and its object is to remove lower hydrocarbons and aromatic hydrocarbons remaining in low concentrations in a raw material gas purified by a conventional method such as coke oven gas. To provide a synthesis gas production method and system capable of extending the life of a desulfurization step for desulfurization of a sulfur compound in a raw material gas and a reforming step for generating CO ₂ , CO and hydrogen by adding steam It is in.

A first invention of the present invention for solving the above-described problems includes a purification step for removing impurities in a raw material gas containing hydrocarbon as a main component, and a low-concentration lower hydrocarbon remaining in the raw material gas. A lower hydrocarbon removal step to remove, a desulfurization step to desulfurize sulfur compounds in the raw material gas, a lower hydrocarbon and aromatic hydrocarbon removal step to remove residual lower hydrocarbons and aromatic hydrocarbons, and CO _2. A synthesis gas production method comprising a reforming step for producing CO and hydrogen.

  According to a second invention, in the first invention, the lower hydrocarbon is removed by any of hydrogenation / cracking catalyst removal, absorption removal, adsorption removal, condensation removal, or a combination thereof, and the lower hydrocarbon is removed. Removal of hydrocarbons and aromatic hydrocarbons is performed by any one or a combination of hydrogenation / cracking catalyst removal, absorption removal, adsorption removal, condensation removal, or pre-reforming removal, or a combination thereof It is in.

A third invention is the synthesis gas production method according to the first or second invention, further comprising a hydrogen addition step of adding hydrogen to the source gas so that the hydrogen concentration is 60% or more.
According to a fourth aspect of the present invention, in any of the purification step for removing impurities in the raw material gas containing hydrocarbon as a main component, the desulfurization step for desulfurization of the sulfur compound in the raw material gas, and before or after the desulfurization step A lower hydrocarbon and aromatic hydrocarbon removing step for absorbing and removing residual low-concentration lower hydrocarbons and aromatic hydrocarbons, and a reforming step for producing CO ₂ , CO, and hydrogen In the synthesis gas production method.

According to a fifth aspect of the present invention, there is provided a purification step for removing impurities in a raw material gas containing hydrocarbon as a main component, a hydrogen addition step for adding hydrogen to the raw material gas to make the hydrogen concentration 60% or more, and the raw material gas A desulfurization step for desulfurization of the sulfur compound therein, and a lower hydrocarbon and aromatic hydrocarbon removal step for removing residual low-concentration lower hydrocarbons and aromatic hydrocarbons either before or after the desulfurization step; And a reforming step for producing CO ₂ , CO, and hydrogen.

  According to a sixth invention, in the fourth or fifth invention, the removal of the lower hydrocarbon and the aromatic hydrocarbon is one of hydrogenation / cracking catalyst removal, absorption removal, adsorption removal, condensation removal, or pre-reforming removal or The synthesis gas production method is characterized by being performed by a combination thereof.

  A seventh invention is characterized in that, in any one of the first to sixth inventions, the concentration of the remaining lower hydrocarbon is 1.5 vol% or less and the concentration of the aromatic hydrocarbon is 300 ppm or less. In the manufacturing method.

  An eighth invention is the synthesis gas production method according to any one of the first to seventh inventions, wherein a hydrogen concentration in the raw material gas is 30% or more.

  According to a ninth invention, in any one of the first to eighth inventions, the raw material gas containing hydrocarbon is coke oven gas, coal gasification gas, blast furnace gas, converter gas, petroleum coke gasification gas, The synthesis gas production method is characterized by being any one of biomass-derived gases or a combination thereof.

  A tenth invention is the synthesis gas according to any one of the first to ninth inventions, wherein the concentration of the remaining lower hydrocarbon is 0.5 vol% or less and the concentration of the aromatic hydrocarbon is 100 ppm or less. In the manufacturing method.

An eleventh invention includes a purification step for removing impurities in a raw material gas containing hydrocarbon as a main component, a hydrogen addition step for adding hydrogen to the raw material gas to make the hydrogen concentration 70% or more, and the raw material gas A desulfurization step for desulfurization of the sulfur compound therein, and a lower hydrocarbon and aromatic hydrocarbon removal step for removing residual low-concentration lower hydrocarbons and aromatic hydrocarbons either before or after the desulfurization step; And a reforming step for producing CO ₂ , CO, and hydrogen.

A twelfth aspect of the invention is a purifier for removing impurities in a raw material gas containing hydrocarbon as a main component, a lower hydrocarbon removing device for removing low-concentration lower hydrocarbons remaining in the raw material gas, A desulfurization apparatus for desulfurization of sulfur compounds in the raw material gas, a lower hydrocarbon and aromatic hydrocarbon removal apparatus for removing residual lower hydrocarbons and aromatic hydrocarbons, CO ₂ , CO and A synthesis gas production system comprising a reformer that generates hydrogen.

  In a thirteenth aspect based on the twelfth aspect, the lower hydrocarbon is removed by any one or a combination of hydrogenation / cracking catalyst removal, absorption removal, adsorption removal, and condensation removal, and the lower hydrocarbon. Removal of hydrocarbons and aromatic hydrocarbons by any of hydrogenation / cracking catalyst removal, absorption removal, adsorption removal, condensation removal, pre-reforming removal, or a combination thereof, In the system.

  A fourteenth invention is the synthesis gas production system according to the twelfth or thirteenth invention, wherein hydrogen is added to the raw material gas so that the hydrogen concentration is 60% or more.

According to a fifteenth aspect of the present invention, there is provided a refining device for removing impurities in a raw material gas containing hydrocarbon as a main component, a desulfurizing device for desulfurizing a sulfur compound in the raw material gas, and any one before or after the desulfurizing device. And a lower hydrocarbon and aromatic hydrocarbon removing device that absorbs and removes residual low-concentration lower hydrocarbon and aromatic hydrocarbon, and a reformer that generates CO ₂ , CO, and hydrogen. In the synthesis gas production system.

According to a sixteenth aspect of the present invention, there is provided a refining device for removing impurities in a raw material gas containing hydrocarbon as a main component, a hydrogen adding device for adding hydrogen to the raw material gas to make the hydrogen concentration 60% or more, and the raw material gas A desulfurization apparatus for desulfurization of sulfur compounds therein, and a lower hydrocarbon and aromatic hydrocarbon removal apparatus for removing residual low-concentration lower hydrocarbons and aromatic hydrocarbons provided either before or after the desulfurization step And a reformer that generates CO ₂ , CO, and hydrogen.

  According to a seventeenth aspect, in the fifteenth or sixteenth aspect, the removal of lower hydrocarbons and aromatic hydrocarbons is any one of hydrogenation / cracking catalyst removal, absorption removal, adsorption removal, condensation removal, or pre-reforming removal or The synthesis gas production system is characterized by being performed by a combination thereof.

  The eighteenth invention is the synthesis gas according to any one of the twelfth to seventeenth inventions, wherein the concentration of the remaining lower hydrocarbon is 1.5 vol% or less and the concentration of the aromatic hydrocarbon is 300 ppm or less. In the manufacturing system.

  A nineteenth invention is the synthesis gas production system according to any one of the twelfth to eighteenth inventions, wherein the hydrogen concentration in the raw material gas is 30% or more.

  In a twentieth aspect of the invention according to any one of the twelfth to nineteenth aspects, the raw material gas containing hydrocarbon is coke oven gas, coal gasification gas, blast furnace gas, converter gas, petroleum coke gasification gas, The synthesis gas production system is any one of biomass-derived gases or a combination thereof.

  A twenty-first aspect of the present invention is the synthesis gas according to any one of the twelfth to twentieth aspects, wherein the concentration of the remaining lower hydrocarbon is 0.5 vol% or less and the concentration of the aromatic hydrocarbon is 100 ppm or less. In the manufacturing system.

According to a twenty-second aspect of the present invention, there is provided a refining device for removing impurities in a raw material gas containing hydrocarbon as a main component, a hydrogen adding device for adding hydrogen to the raw material gas so that the hydrogen concentration is 70% or more, and the raw material gas A desulfurization apparatus for desulfurization of sulfur compounds therein, and a lower hydrocarbon and aromatic hydrocarbon removal apparatus for removing residual low-concentration lower hydrocarbons and aromatic hydrocarbons provided either before or after the desulfurization step And a reformer that generates CO ₂ , CO, and hydrogen.

  According to the present invention having the above-described configuration, it is possible to suppress the occurrence of coking in the raw material gas piping and the like by removing and suppressing the lower hydrocarbons remaining in the raw material gas purified by a conventional method. Moreover, since the remaining aromatic hydrocarbons can also be removed, poisoning of the reformer with the reforming catalyst can be prevented. As a result, it is possible to extend the operating time of the system.

  Hereinafter, the present invention will be described in detail with reference to the drawings. Note that the present invention is not limited to the embodiments. In addition, constituent elements in the following embodiments include those that can be easily assumed by those skilled in the art or those that are substantially the same.

[First Embodiment]
A method for purifying a source gas according to a first embodiment of the present invention will be described with reference to the drawings. FIG. 1 is a conceptual diagram illustrating a synthesis gas production system according to an embodiment. As shown in FIG. 1, a synthesis gas production system 10-1A according to the present embodiment removes impurities in a raw material gas 11 containing hydrocarbon (for example, methane) as a main component by a conventional method. A lower hydrocarbon removing device 12A for removing low-concentration lower hydrocarbons remaining in the raw material gas, and a desulfurizing device 14 for desulfurizing sulfur compounds in the highly purified gas 13 from which the lower hydrocarbons have been removed, Lower hydrocarbon and aromatic hydrocarbon removing device 17 for removing residual lower hydrocarbon and aromatic hydrocarbon in the raw material gas containing residual lower hydrocarbon and aromatic hydrocarbon, and synthesis comprising CO ₂ , CO and hydrogen And a reformer 19 that generates a reformed gas 18 that is a gas. Reference numeral 15 shows the purified gas (excluding sulfur compound) from which the sulfur compound has been removed.

  Here, as the raw material gas 11 in the present invention, any one of a coke oven gas, a coal gasification gas, a blast furnace gas, a converter gas, a petroleum coke gasification gas, a biomass origin gas, or a mixed gas thereof is exemplified. be able to.

Examples of low-concentration lower hydrocarbons remaining in the raw material gas 11 include olefins and paraffins such as C ₂ or more (for example, ethane, propane, butane, ethylene, propylene, 1-butene, 2-butene, isobutylene, acetylene). Etc.).

  Further, the concentration of the low-concentration lower hydrocarbon remaining in the raw material gas 11 is not particularly limited, but the highly purified gas (excluded: lower hydrocarbon) 13 is removed by the lower hydrocarbon removal apparatus 12A of the present invention. And the outlet concentration after the treatment is 1.5 vol% or less, preferably 0.5 vol%, more preferably 100 ppm or less, in the pipe to which the raw material gas is supplied and in the desulfurization apparatus 14 The occurrence of coking can be prevented.

  Here, the lower hydrocarbon removing device 12A removes lower hydrocarbons in the raw material gas by any one of hydrogenation / cracking catalyst removal, absorption removal, adsorption removal, condensation removal, or a combination thereof.

[Test example]
As the hydrogenation / cracking catalyst usable at a low temperature, a catalyst containing Pd, Pt, Ni or the like as an active metal is preferable. For example, trade names “G-68”, “SC13”, “SC53” manufactured by Zude Chemie Co., Ltd. , “G74”, “G75” and the like.
However, considering the influence of catalyst poisoning by sulfur compounds in the raw material gas, a Pd-based catalyst having high sulfur poisoning resistance is particularly preferable. In addition, as operating conditions, the lower hydrocarbon is charged by filling the catalyst into a lower hydrocarbon removing device and supplying the raw material gas 11 at 40 to 350 ° C., GHSV = 150 to 30000, 0.3 to 10.0 MPaG. At the outlet of the removing device 12A, the concentration of olefin and paraffin in the raw material gas 11 can be 1.5 vol% or less.

  In this way, as a result of removing lower hydrocarbons remaining in a low concentration in the raw material gas 11 purified by a conventional method by the lower hydrocarbon removal device, the amount of precipitated C becomes 0.0035 g / h or less. The system life of the gas purification system has been improved over 3000 hours.

  Further, as the lower hydrocarbon and aromatic hydrocarbon removing device 17 interposed between the desulfurization device 14 and the reforming device 19, the aromatic hydrocarbon remaining in the purified gas 15 by, for example, a pre-reforming catalyst. The thing which removes can be illustrated. As a result, it is possible to prevent deterioration of the reforming catalyst used in the reformer 19 provided downstream.

  As this pre-reforming catalyst, for example, a Ni-based pre-reforming catalyst can be used.

[Test example]
An aromatic hydrocarbon was removed at a temperature of 400 to 600 ° C., a pressure of ^{1 to 2} MPaG, and a GHSV = 1000 h ⁻¹ using a Ni-based pre-reforming catalyst (“SC11PR (trade name)” manufactured by Zude Chemie) as the pre-reforming catalyst.
In the pre-reforming device 17, the concentration of olefin was 1.5 vol% or less and the aromatic hydrocarbon was 300 ppm or less.
As described above, the lower hydrocarbons and aromatic hydrocarbons remaining at a low concentration in the highly refined purified gas 15 are removed by the lower hydrocarbons and aromatic hydrocarbon removing device 17, and as a result, the amount of deposited C is 0. The system life of the raw material gas purification system was improved by 3000 hours or more.

  Further, the relationship between the methane conversion rate at the outlet of the reformer and the time depending on the presence or absence of the pre-reforming catalyst shown in FIG. 11 was obtained. As shown in FIG. 11, the difference in performance deterioration can be confirmed by the presence or absence of the pre-reforming catalyst, and it has been found that the system time is improved by providing the pre-reforming catalyst.

  In the present embodiment, the lower hydrocarbon removal device 12A in which the lower hydrocarbon is saturated hydrocarbon by a hydrogenation catalyst is used as the raw material gas advanced purification device. Instead of this lower hydrocarbon removal device, FIG. As shown in FIG. 3, either a lower hydrocarbon absorption / removal device 12B that absorbs and removes the lower hydrocarbon, or a hydrogen addition device 12C that adds hydrogen to the raw material gas to make the hydrogen concentration 60% or more as shown in FIG. The synthesis gas production systems 10-1B and 10-1C using one chemical processing apparatus may be used.

  Here, the lower hydrocarbon absorption / removal device 12B that absorbs and removes the lower hydrocarbons shown in FIG. 2 uses, for example, kerosene, light oil, heavy oil, crude benzene, coal-based cleaning oil, etc. as the absorbing liquid. The lower hydrocarbon remaining in a low concentration in the raw material gas 11 is absorbed and removed by gas-liquid contact by a scrubber method, a packed bed method, and a tray method.

Moreover, it is preferable that processing temperature shall be the range of 10-70 degreeC.
This is because the absorption temperature in the absorption liquid is lower if the temperature is lower, and higher absorption efficiency can be obtained. However, due to the problem of coagulation of the aromatic compound remaining in the raw material gas 11 at a low concentration, it is 10 ° C. or higher. This is because it is desirable. On the other hand, when the temperature is set to 70 ° C. or higher, the outlet aromatic concentration may be higher than the inlet due to vaporization from the absorbing solution, which is not preferable.

The absorption pressure of the lower hydrocarbon absorption / removal device is preferably 0.3 to 1.5 MPaG. The higher the pressure, the better.
Here, the L (liquid) / G (gas) ratio is preferably 0.2 to 0.5 kg / kg. This is because even if the L / G ratio is too high, the aromatics in the gas are almost absorbed near L / G = 0.5, so that the absorption efficiency is not further improved.

[Test example]
Examples of the absorbent used in the lower hydrocarbon absorption / removal device include kerosene, light oil, heavy oil, crude benzene, and coal-based cleaning oil. And it was made to gas-liquid contact with the source gas 11 in the range whose absorption temperature is 10-70 degreeC.
In this way, as a result of removing lower hydrocarbons remaining in a low concentration in the raw material gas 11 purified by a conventional method by the lower hydrocarbon removal device, the amount of precipitated C becomes 0.0035 g / h or less. The system life of the gas purification system has been improved over 3000 hours.

Further, a hydrogen addition apparatus 12C for adding hydrogen to the source gas shown in FIG. 3 to make the hydrogen concentration 60% or more injects hydrogen into the source gas 11 from a hydrogen source supply apparatus such as a hydrogen cylinder, for example. By setting the H ₂ concentration to 60% or higher, the decomposition temperature of C _{2 to} C ₄ is raised for equilibrium, and coking in the piping through which the source gas 11 flows is suppressed.

[Test example]
When the temperature of the raw material gas is 250 to 350 ° C. and the pressure is about 1 to 2 MPaG, hydrogen is supplied into the raw material gas 11 from, for example, a hydrogen cylinder using a hydrogenation device, and the H ₂ concentration is set to 70% or more. If the amount of C precipitation is reduced by 10 to 40%, preferably 80% or more, the occurrence of coking can be reduced to 40% or more, and if the H ₂ concentration is 90% or more, C precipitation is completely eliminated. I was able to suppress it.

  Thus, as a result of increasing the decomposition temperature on the equilibrium of the lower hydrocarbons remaining in a low concentration in the raw material gas 11 refined by a conventional method and suppressing coking in the raw material gas pipe, the amount of precipitated C is 0.0035 g. / H or less, and the system life of the raw material gas purification system was improved by 3000 hours or more.

[Second Embodiment]
A method for purifying a source gas according to a second embodiment of the present invention will be described with reference to the drawings. FIG. 4 is a conceptual diagram illustrating a synthesis gas production system according to an embodiment. As shown in FIG. 4, the synthesis gas production system 10-2A according to the present embodiment removes impurities in the raw material gas 11 containing hydrocarbons (for example, methane, ethane, etc.) as a main component by a conventional method (not shown). Refining device, lower hydrocarbon removing device 12A for removing low-concentration lower hydrocarbons remaining in the raw material gas with a hydrogenation catalyst, and desulfurization of sulfur compounds in highly purified gas 13 from which lower hydrocarbons have been removed A desulfurization apparatus 14 that performs the above-described process, and a lower hydrocarbon that absorbs and removes remaining low-concentration lower hydrocarbons and aromatic hydrocarbons by bringing the highly purified gas 13 into contact with an absorption liquid on the upstream side of the desulfurization apparatus 14 and The apparatus includes an aromatic hydrocarbon absorption / removal device 31 and a reforming device 19 that generates a reformed gas 18 that is a synthesis gas composed of CO ₂ , CO, and hydrogen. The lower hydrocarbon and aromatic hydrocarbon absorption / removal device 31 may be provided on the downstream side of the desulfurization device 14.

  Here, the lower hydrocarbon and aromatic hydrocarbon absorption / removal device 31 is the same as the lower hydrocarbon absorption / removal device 12B for absorbing and removing the lower hydrocarbon shown in FIG. Gas oil, heavy oil, crude benzene, coal-based cleaning oil, etc., for example, by a scrubber method, a packed bed method, a tray method, gas-liquid contact, lower hydrocarbons remaining in a low concentration in the raw material gas 11 and Aromatic hydrocarbons are absorbed and removed.

  Moreover, as shown in FIG. 5, it is good also as the synthesis gas manufacturing system 10-2B which removes a lower hydrocarbon and an aromatic hydrocarbon using the hydrogenation apparatus 12C instead of the lower hydrocarbon removal apparatus 12A.

Further, as shown in FIG. 6, a lower hydrocarbon and aromatic hydrocarbon absorption / removal device without using a raw material gas advanced purification device such as the lower hydrocarbon removal device 12A of FIG. 4 and the hydrogenation device 12C of FIG. Only 31 may be used as the synthesis gas production system 10-2C for removing lower hydrocarbons and aromatic hydrocarbons in the raw material gas 11.
Also in the synthesis gas production system according to the present embodiment, the lower hydrocarbon and aromatic hydrocarbon removal apparatus 17 for removing residual lower hydrocarbons and aromatic hydrocarbons according to the first embodiment is further reformed. It may be provided on the upstream side of the device 18.

[Third Embodiment]
A method for purifying a source gas according to a third embodiment of the present invention will be described with reference to the drawings. FIG. 7 is a conceptual diagram illustrating a synthesis gas production system according to an embodiment. As shown in FIG. 7, the synthesis gas production system 10-2D according to the present embodiment removes impurities in the raw material gas 11 containing hydrocarbons (for example, methane, ethane, etc.) as a main component by a conventional method (not shown). Refining device, lower hydrocarbon removing device 12A for removing low-concentration lower hydrocarbons remaining in the raw material gas with a hydrogenation catalyst, and desulfurization of sulfur compounds in highly purified gas 13 from which lower hydrocarbons have been removed In the desulfurization apparatus 14 that performs the desulfurization process, either before or after the desulfurization step, the lower hydrocarbon and aromatic hydrocarbon adsorption is performed by contacting the raw material gas containing the residual lower hydrocarbon and aromatic hydrocarbon with the adsorbent and removing it by adsorption. The apparatus includes a removing device 32 and a reforming device 19 that generates a reformed gas 18 that is a synthesis gas composed of CO ₂ , CO, and hydrogen.

The lower hydrocarbon and aromatic hydrocarbon adsorption / removal device 32 adsorbs and removes lower hydrocarbon and aromatic hydrocarbon in the gas by physical adsorption.
Here, examples of the adsorbent to be removed by adsorption include known adsorbents such as activated carbon, silica gel, alumina gel, and zeolite.
The operating temperature is preferably 10 to 100 ° C. or less, more preferably 60 ° C. or less.
This is because the lower the temperature, the more advantageous for the adsorption, but considering the precipitation of the high boiling point aromatic compound, it is not preferable to set the temperature to 10 ° C. or lower. Moreover, if the temperature is high, the amount of adsorbent increases, which is not preferable. The operating pressure is preferably as high as possible.
The superficial velocity is preferably 0.3 m / s or less, and the space velocity is preferably 400 to 5000 h ⁻¹ .

As described above, lower hydrocarbons and aromatic hydrocarbons remaining at a lower concentration in the highly purified purified gas 15 are physically adsorbed and removed by the lower hydrocarbon and aromatic hydrocarbon adsorption / removal device 32. The amount of C deposited was 0.0035 g / h or less, and the system life of the raw material gas purification system was improved by 3000 hours or more.
Also in the synthesis gas production system according to the present embodiment, the lower hydrocarbon and aromatic hydrocarbon removal apparatus 17 for removing residual lower hydrocarbons and aromatic hydrocarbons according to the first embodiment is further reformed. It may be provided on the upstream side of the device 18.

[Fourth Embodiment]
In the present embodiment, lower hydrocarbons are not chemically removed, and the generation of coking is suppressed by preventing the raw material gas from staying in the piping as much as possible.

  First, as a means for suppressing coking by adjusting the gas flow rate of the source gas, the source gas 11 has a gas flow rate of 1 m / s or higher, 350 ° C. or lower, and a pressure of 1 MPaG or lower. The occurrence of coking in the circulating piping facility can be suppressed.

  By setting it as the said operating conditions, a system lifetime will be 3000H or more, and as C precipitation amount, it will be 0.0035 g / h or less.

  Next, a description will be given of a means for suppressing C precipitation by not forming a gas retention portion when supplying the raw material gas 11 to the desulfurizer 14.

8A and 8B are schematic views of the layout of the first gas supply pipe according to the second embodiment. FIG. 8-1 is a layout diagram of piping at the time of start-up, and FIG. 8-2 is a layout diagram of piping at a normal time.
As shown in FIG. 8A, the first gas supply pipe 31-1 is provided with a first heater 32-1 to keep the source gas 11 at a predetermined temperature, and the first valve 33-1 is interposed. A branch point X is provided in front of the first valve 33-1, and a second gas supply pipe 31-2 is connected to the desulfurization device 14 from here. The second gas supply pipe 31-2 branched from the branch point X is provided with a second heater 32-2 so as to keep the source gas 11 at a predetermined temperature. -2 is installed.

Here, at the time of start-up when the raw material gas is desulfurized, the second valve 33-2 is closed and the first valve 33-1 is opened so that the raw material gas 11 is not supplied to the desulfurizer 14. To. In this case, the raw material gas stays between the branch point X and the second valve 33-2.
Thereafter, when the predetermined desulfurization temperature is reached, as shown in FIG. 8-2, the second valve 33-2 is opened, and then the first valve 33-1 is closed.
During the normal operation, since the second valve 33-2 is opened and the first valve 33-1 is closed, the source gas 11 stays between the branch point X and the first valve 33-1.

With this piping layout, the system system life can be increased to 1000 hours or more.
Note that the amount of precipitated C was 0.0035 g / h or less.

FIGS. 9A and 9B show the layout of the second pipe.
As shown in FIG. 9-1, the first gas supply pipe 31-1 is provided with a first heater 32-1 to keep the source gas 11 at a predetermined temperature, and the first valve 33-1 is interposed. A branch point X is provided in front of the first valve 33-1, and a second gas supply pipe 31-2 is connected to the desulfurization device 14 from here. A second valve 33-2 is interposed in the second gas supply pipe 31-2 branched from the branch point X on the front side of the second heater 32-2.

  Therefore, since the first valve 33-1 and the second valve 33-2 are closer to the branch point X than the first piping layout in the case shown in FIGS. As a result, the volume of staying is reduced and coking is further suppressed.

With this piping layout, the system system life can be increased to 3000 hours or more.
Note that the amount of precipitated C was 0.0035 g / h or less.

[Fifth Embodiment]
Next, a case where methanol is synthesized using unrefined coke oven gas from coke oven gas from coke oven will be described. FIG. 10 is a schematic diagram of a system for synthesizing methanol using coke oven gas.
As shown in FIG. 10, the methanol synthesis system 20 using the coke oven gas according to the present embodiment uses a coke oven 21 to obtain an unrefined coke oven gas 22 from coal by dry distillation, and a conventional method. The coke oven gas refining apparatus 23 that obtains the raw material gas 11 by processing the desulfurization, detarring, deammonification, and deoiling processes in accordance with the above, the lower hydrocarbon remaining in the raw material gas 11 is removed, and the highly purified gas 13 The lower hydrocarbon removing device 12A, the desulfurizing device 14 for removing the sulfur compounds remaining in the highly purified gas 13, and the steam 16 are added, and the raw material gas containing residual lower hydrocarbons and aromatic hydrocarbons is added. A lower hydrocarbon and aromatic hydrocarbon removing device (for example, a pre-reforming device) that performs pre-reforming to remove residual lower hydrocarbon and aromatic hydrocarbon. A) 17, the purified gas (except after the desulfurization: sulfur compounds) 15 reformed to the reformer 19 for generating CO _2, CO and hydrogen, methanol 26 using the reformed gas (syngas) 18 And a methanol synthesizer 27 for synthesis.

  The lower hydrocarbon removal apparatus 12 which is a raw material gas advanced purification apparatus which highly removes lower hydrocarbons remaining in the raw material gas 11 of the present invention, and the lower hydrocarbons and aromatics which remove residual lower hydrocarbons and aromatic hydrocarbons. Since the hydrocarbon removing device 17 is used, lower hydrocarbons and aromatic hydrocarbons remaining in the raw material gas 11 are removed. As a result, coking in the desulfurization device 14 and the piping equipment is prevented, and the reforming device 19 is used. The catalyst is no longer degraded. As a result, the system life of the methanol synthesis system can be secured for 3000 hours or more.

  In this embodiment, the highly purified gas is applied to the production of methanol. However, the present invention is not limited to this, and other than the production of methanol, for example, as appropriate in C1 chemistry such as DME (dimethyl ether) and gasoline. Can be used.

  As described above, according to the present invention, high-level removal of lower hydrocarbons and aromatic hydrocarbons remaining in the raw material gas prevents coking in the desulfurization apparatus and piping equipment and improves the gas. It is possible to prevent the reforming catalyst to be poisoned from being poisoned and to improve the system life.

It is a conceptual diagram which shows the synthesis gas manufacturing system which concerns on 1st Embodiment. It is a conceptual diagram which shows the other synthesis gas manufacturing system which concerns on 1st Embodiment. It is a conceptual diagram which shows the other synthesis gas manufacturing system which concerns on 1st Embodiment. It is a conceptual diagram which shows the synthesis gas manufacturing system which concerns on 2nd Embodiment. It is a conceptual diagram which shows the other synthesis gas manufacturing system which concerns on 2nd Embodiment. It is a conceptual diagram which shows the other synthesis gas manufacturing system which concerns on 2nd Embodiment. It is a conceptual diagram which shows the synthesis gas manufacturing system which concerns on 3rd Embodiment. It is the schematic of the layout at the time of starting of the 1st gas supply pipe | tube which concerns on 4th Embodiment. It is the schematic of the layout at the time of the normal time of the 1st gas supply pipe | tube which concerns on 4th Embodiment. It is the schematic of the layout at the time of starting of the 2nd gas supply pipe | tube which concerns on 4th Embodiment. It is the schematic of the layout at the time of the normal time of the 2nd gas supply pipe | tube which concerns on 4th Embodiment. Fifth Embodiment FIG. 5 is a schematic view of a methanol synthesis system using a mcoke oven gas according to the present invention. FIG. 4 is a relationship diagram between the methane concentration at the outlet of the reformer and the time depending on the presence or absence of a pre-reforming catalyst.

Explanation of symbols

DESCRIPTION OF SYMBOLS 10 Syngas production system 11 Raw material gas 12A Lower hydrocarbon removal apparatus 12B Lower hydrocarbon absorption and removal apparatus 12C Hydrogen addition apparatus 13 Highly refined gas (excluding lower hydrocarbon)
14 Desulfurization equipment 15 Refined gas (excluding sulfur compounds)
16 Steam 17 Lower hydrocarbon and aromatic hydrocarbon removal equipment 18 Reformed gas (syngas)
19 reformer

Claims (22)

A purification step for removing impurities in the raw material gas containing hydrocarbon as a main component;
A lower hydrocarbon removing step for removing low-concentration lower hydrocarbons remaining in the raw material gas; a desulfurizing step for desulfurizing a sulfur compound in the raw material gas;
A lower hydrocarbon and aromatic hydrocarbon removing step for removing residual lower hydrocarbon and aromatic hydrocarbon;
And a reforming step for generating CO ₂ , CO, and hydrogen. In claim 1,
The removal of the lower hydrocarbon is performed by any one or a combination of hydrogenation / cracking catalyst removal, absorption removal, adsorption removal, or condensation removal,
Synthesis gas characterized in that the removal of the lower hydrocarbon and aromatic hydrocarbon is performed by any one or a combination of hydrogenation / cracking catalyst removal, absorption removal, adsorption removal, condensation removal, and pre-reforming removal. Production method. In claim 1 or 2,
A synthesis gas production method comprising a hydrogenation step of adding hydrogen to a raw material gas to make a hydrogen concentration 60% or more. A purification step for removing impurities in the raw material gas containing hydrocarbon as a main component;
A desulfurization step of desulfurizing a sulfur compound in the raw material gas;
Either before or after the desulfurization step, a lower hydrocarbon and aromatic hydrocarbon removal step of absorbing and removing residual low-concentration lower hydrocarbon and aromatic hydrocarbon;
And a reforming step for generating CO ₂ , CO, and hydrogen. A purification step for removing impurities in the raw material gas containing hydrocarbon as a main component;
A hydrogen addition step of adding hydrogen to the source gas to make the hydrogen concentration 60% or more;
A desulfurization step of desulfurizing a sulfur compound in the raw material gas;
Either before or after the desulfurization step, a lower hydrocarbon and aromatic hydrocarbon removal step of removing residual low-concentration lower hydrocarbon and aromatic hydrocarbon;
And a reforming step for generating CO ₂ , CO, and hydrogen. In claim 4 or 5,
Synthesis gas production characterized in that the removal of lower hydrocarbons and aromatic hydrocarbons is performed by any one or a combination of hydrogenation / cracking catalyst removal, absorption removal, adsorption removal, condensation removal or pre-reforming removal Method. In any one of Claims 1 thru | or 6,
A method for producing synthesis gas, characterized in that the concentration of residual lower hydrocarbon is 1.5 vol% or less and the concentration of aromatic hydrocarbon is 300 ppm or less. In any one of Claims 1 thru | or 7,
A synthesis gas production method, wherein a hydrogen concentration in the raw material gas is 30% or more. In any one of Claims 1 to 8,
The raw material gas containing the hydrocarbon is any one of a coke oven gas, a coal gasification gas, a blast furnace gas, a converter gas, a petroleum coke gasification gas, a biomass origin gas, or a combination thereof. Syngas production method. In any one of Claims 1 thru | or 9,
A synthesis gas production method characterized in that the concentration of residual lower hydrocarbon is 0.5 vol% or less and the concentration of aromatic hydrocarbon is 100 ppm or less. A purification step for removing impurities in the raw material gas containing hydrocarbon as a main component;
A hydrogen addition step of adding hydrogen to the source gas to make the hydrogen concentration 70% or more;
A desulfurization step of desulfurizing a sulfur compound in the raw material gas;
Either before or after the desulfurization step, a lower hydrocarbon and aromatic hydrocarbon removal step of removing residual low-concentration lower hydrocarbon and aromatic hydrocarbon;
And a reforming step for generating CO ₂ , CO, and hydrogen. A purification device for removing impurities in the raw material gas containing hydrocarbon as a main component;
A lower hydrocarbon removing apparatus for removing low-concentration lower hydrocarbons remaining in the raw material gas;
A desulfurization apparatus for desulfurizing a sulfur compound in the raw material gas;
Either one of the lower hydrocarbon and aromatic hydrocarbon removing device for removing the remaining lower hydrocarbon and aromatic hydrocarbon;
A synthesis gas production system comprising a reformer that produces CO ₂ , CO, and hydrogen. In claim 12,
The removal of the lower hydrocarbon is performed by any one or a combination of hydrogenation / cracking catalyst removal, absorption removal, adsorption removal, or condensation removal,
Synthesis gas characterized in that the removal of the lower hydrocarbon and aromatic hydrocarbon is performed by any one or a combination of hydrogenation / cracking catalyst removal, absorption removal, adsorption removal, condensation removal, and pre-reforming removal. Manufacturing system. In claim 12 or 13,
A synthesis gas production system, wherein hydrogen is added to a raw material gas so that a hydrogen concentration is 60% or more. A purification device for removing impurities in the raw material gas containing hydrocarbon as a main component;
A desulfurization apparatus for desulfurizing a sulfur compound in the raw material gas;
A lower hydrocarbon and aromatic hydrocarbon removal device that is provided either before or after the desulfurization device and absorbs and removes residual low-concentration lower hydrocarbons and aromatic hydrocarbons;
A synthesis gas production system comprising a reformer that produces CO ₂ , CO, and hydrogen. A purification device for removing impurities in the raw material gas containing hydrocarbon as a main component;
A hydrogenation device for adding hydrogen to the source gas to make the hydrogen concentration 60% or more;
A desulfurization apparatus for desulfurizing a sulfur compound in the raw material gas;
A lower hydrocarbon and aromatic hydrocarbon removing device that is provided either before or after the desulfurization step and removes residual low-concentration lower hydrocarbon and aromatic hydrocarbon;
A synthesis gas production system comprising a reformer that produces CO ₂ , CO, and hydrogen. In claim 15 or 16,
A synthesis characterized in that the removal of lower hydrocarbons and aromatic hydrocarbons is carried out by one of hydrogenation / cracking catalyst removal, absorption removal, adsorption removal, condensation removal or pre-reforming removal, or a combination thereof. Gas production system. In any one of Claims 12 thru | or 17,
A synthesis gas production system characterized in that the concentration of residual lower hydrocarbon is 1.5 vol% or less and the concentration of aromatic hydrocarbon is 300 ppm or less. In any one of claims 12 to 18,
A synthesis gas production system, wherein a hydrogen concentration in the raw material gas is 30% or more. In any one of claims 12 to 19,
The raw material gas containing the hydrocarbon is any one of a coke oven gas, a coal gasification gas, a blast furnace gas, a converter gas, a petroleum coke gasification gas, a biomass origin gas, or a combination thereof. Syngas production system. In any one of claims 12 to 20,
A synthesis gas production system characterized in that the concentration of residual lower hydrocarbon is 0.5 vol% or less and the concentration of aromatic hydrocarbon is 100 ppm or less. A purification device for removing impurities in the raw material gas containing hydrocarbon as a main component;
A hydrogen adding device for adding hydrogen to the source gas to make the hydrogen concentration 70% or more;
A desulfurization apparatus for desulfurizing a sulfur compound in the raw material gas;
A lower hydrocarbon and aromatic hydrocarbon removing device that is provided either before or after the desulfurization step and removes residual low-concentration lower hydrocarbon and aromatic hydrocarbon;
A synthesis gas production system comprising a reformer that produces CO ₂ , CO, and hydrogen.

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