JP2003049172A - Desulfurization of liquid hydrocarbon fuel - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a desulfurization process that can effectively desulfurize a trace amount of sulfur compounds included in liquid fuel, for example, lamp oil under the standard pressure and temperature for a long period of time, to reduce sulfur components to <=1 ppm, preferably <=0.1 ppm. and to provide a desulfurizer to be used before the steam reformer in the fuel cell system using a liquid fuel, for example, lamp oil. SOLUTION: An adsorbent including either activated carbon or NaY type zeolite is subjected to thermal dehydration treatment at 100-500 deg.C and the product is used as the desulfurizer. At least one additive selected from Cu, K, Zn, sodium metasilicate is supported on activated carbon or NaY type zeolite is used as the desulfurizer. The liquid fuel is brought into contact with the desulfurizer under the standard temperature and pressure at LHSV is 0.1-10/hour.

Description

DETAILED DESCRIPTION OF THE INVENTION [0001] TECHNICAL FIELD The present invention relates to a liquid fuel such as kerosene.
Desulfurization method to remove sulfur compounds contained in trace amounts, details
In other words, hydrogen used mainly as fuel for fuel cells
Raw material for producing hydrogen-rich gas such as fuel gas
And a method for desulfurizing a liquid fuel. [0002] 2. Description of the Related Art At present, hydrogen sources for fuel cells in Japan
Only natural gas is practically used as
The technology for using kerosene as a hydrogen source has not been established. light
Liquid hydrocarbon fuels, such as oil, use energy as a source of hydrogen.
Extremely high energy density, portable, storable, household
Suitable as fuel for stationary fuel cell systems. Toko
However, kerosene still contains a considerable amount of sulfur (3
0-100ppm), a large amount of sulfur is fuel cell system
Causes steam reforming to not proceed smoothly
Unsuitable for producing hydrogen for fuel cells
Therefore, a desulfurization operation is required. In the oil industry
Conventional desulfurization technology in high temperature high temperature using hydrodesulfurization catalyst
Pressure reaction, but based on (di) benzothiophene
Chemically stable aromatic alkyl derivatives such as skeleton
If the body contains sulfur, reduce it
In some cases, it is difficult to achieve a sufficient desulfurization effect.
There was a disadvantage that it could not be done. Normal hydrodehydration
Sulfur technology also requires a number of fairly high-level technologies
However, these technologies operate at a high pressure of 10 kg / cm2 or more.
Households, small businesses (hospitals, buildings, etc.)
Do not pay economically to install
There must be a license holder. Therefore, small
Build a fuel cell system that can be installed in large-scale business establishments
To develop a new catalyst capable of desulfurization under low pressure
Need to be [0003] Conventionally, in the petroleum industry, medium and light oils
Fuel cells using liquid fuels such as sulfuric acid and kerosene
In sulfuric acid, sulfur compounds in fuel are hydrocracked to form hydrogen sulfide.
After that, the method of desulfurization with zinc oxide is used
I have. As an example, JP-A-6-91173 discloses Y
Ni-Mo supported in addition to Ni ion exchange of zeolite
Catalyst is used for the steam reformer in the fuel cell system.
Effective for hydrocracking desulfurization for use in the first stage
Is disclosed. However, this technology is not suitable for the desulfurization process.
Supply of hydrogen or hydrogen-rich gas discharged from electrodes
The need for recycling complicates the desulfurization equipment. Change
At a reaction temperature of 400 to 450 for the hydrogenolysis reaction.
Operating at a high pressure of about 2-6 kg / cm2
Energy loss and equipment and operating costs
Is also expensive. Operation and maintenance of home fuel cell systems
Defense is also difficult. Further, Japanese Patent Application Laid-Open No. 3-261002 discloses
Replaces deep desulfurization of medium and light oil with Ni or NiO with ZnO
Contact with hydrogen in the presence of a supported catalyst to
Sulfur compounds converted to hydrogen sulfide by hydrogenolysis
Then, a method of removing the catalyst by adsorption to a catalyst is disclosed.
Also in this case, supply of hydrogen to the desulfurization process or discharge from the electrode
It is necessary to recycle the released hydrogen-rich gas
The desulfurization equipment becomes complicated, and the hydrogenolysis reaction and sulfuration
The reaction temperature of the hydrogen adsorption reaction is 200 to 400 ° C.
High energy loss is high. [0005] In particular, used in hospitals and offices for consumer use
In a distributed fuel cell with an output of 500 kW or less,
The place of installation of the body is in the basement of the building, near the building, etc.
Fuel gas production facilities must be as small as possible
It can be used at room temperature and is compact
There is a need for a desulfurization method that can be used. [0006] JP-A-11-140462 discloses that
An oxidizing agent is added to the liquid containing the organic sulfur compound, and the catalyst is added.
Oxidation using an organic compound
Oxidize to a side compound and / or a sulfone compound, and then
Absorbs the generated sulfoxide and sulfone compounds.
A desulfurization method that separates and removes by means such as deposition and filtration is disclosed.
Have been. This method is warmer than the catalytic hydrogenation reduction method.
Although desulfurization can be performed efficiently under mild conditions,
Peroxide, organic hypochlorite compound and organic hypobromite
An oxidizing agent such as a compound is converted to an acid of a sulfur atom in an organic sulfur compound.
It is necessary to add more than the stoichiometric amount necessary for
Separation operation of generated sulfonic acid and sulfone
It is difficult to do in small facilities. [0007] Japanese Patent Application Laid-Open No. 11-169601 discloses a
-Treated and stabilized nickel-based adsorbent
Efficient adsorption and removal of thiophene-based sulfur compounds
A method is disclosed. However, this method has a temperature of 17
0-220 ° C, pressure 0.8MPa
You. [0008] SUMMARY OF THE INVENTION The present invention relates to a liquid hydrocarbon
Sulfur compounds in trace amounts in raw fuel can be removed at room temperature.
Provision of a desulfurization method that can be used with compact equipment
It is a subject. For applications, use kerosene
Used before the steam reformer in the fuel cell system
After the desulfurization unit or the hydrodesulfurization tower for medium and light oil
Can also be used as a desulfurization means for residual trace sulfur in stages
It is. [0009] SUMMARY OF THE INVENTION The above objects of the present invention and
The purpose is to include either activated carbon or NaY-type zeolite.
Heat-dehydrated adsorbent at 100-500 ° C,
Or a small amount selected from Cu, K, Zn sodium metasilicate
At least one additive to activated carbon or NaY type zeolite
Thiophene, benzothiophene
Hardly decomposable trace sulfur compounds such as diene and dibenzothiophene
A liquid hydrocarbon fuel containing a temperature of 0 ° C. to 80 ° C. and pressure
Is 1kg / cm^Two, Liquid flow rate is LHSV 0.1-10
h^-1Characterized by contacting with a desulfurizing agent under the following conditions:
Achieved by the desulfurization method of liquid hydrocarbon fuel. The liquid containing an organic sulfur compound in the present invention is
Although not particularly limited, in particular, hydrodesulfurization reaction
The later, and the organic sulfuration contained therein
Compounds are generally considered the most difficult to remove
Thiophenes such as benzothiophene and dibenzothiophene
And the residual amount of sulfur is from several thousand ppm to several ppm or less.
Naphtha, gasoline, kerosene, light oil, heavy oil,
Falten, oil sand oil, coal liquefied oil, coal-based heavy
It is preferably oil or the like. [0011] BEST MODE FOR CARRYING OUT THE INVENTION
Commercially available activated carbon can be used.
And FAC-10 manufactured by Tadashi Pharmaceutical Co., Ltd. Used in the present invention
Y-type zeolite used in desulfurizing agents
For example, Y-type Zeola manufactured by Mizusawa Chemical Co., Ltd.
And the like. Next, activated carbon or Y-type zeolite
1 selected from the group consisting of Cu, K, Zn sodium metasilicate
Carrying one or more kinds of additives for use in the present invention
To obtain a desulfurizing agent. The method of loading is commonly used in the industry.
An impregnation method or an ion exchange method can be used. Carry amount
Is preferably in the range of 0.1% by weight to 10% by weight. The adsorbent is heated in air at a temperature of 100 to 50.
Heat treatment at 0 ° C for 0.5 hours or more
A desulfurizing agent from which water is removed is obtained. By using a desulfurizing agent as described above,
The removal of sulfur compounds by adsorption proceeds quickly even at room temperature. Ma
Also, if the temperature is high, the equilibrium of adsorption is advantageous for desorption,
In the present invention, adsorption is performed at room temperature of 50 ° C. or less, particularly at room temperature of 40 ° C.
Preferably. LHSV is 0.1h^-1Adsorb if lower
Low efficiency, LHSV is 10h ^-1If higher
Insufficient contact between the sulfuric acid and the sulfur compound makes it impractical.
No. As an example of the sulfur compound in the present invention,
Ofen, benzothiophene, dibenzothiophenes,
Thiols such as t-butyl mercaptan or dimethyl
Thioethers such as sulfide, carbonyl sulfide (CO
S) and the like. [0017] The following examples are provided to further illustrate the present invention.
Although shown, the invention is not so limited. Embodiment 1 Pre-treat 100ml eggplant type flask
After adding 0.1 g of various adsorbents, 40 wt.
ppm dibenzothiophene, 1800 ppm 1-me
20 ml of n-heptane containing tilnaphthalene
And stir at room temperature to increase the residual thiophene concentration at high speed.
Analyzed by liquid chromatography. Using activated carbon
The thiophene adsorption and removal rate can be
Saturation was reached at 99%. Embodiment 2 400mm in a cylindrical desulfurizer of 6mm in diameter and 100mm in length
0.42 ml of powdery desulfurizing agent heat-treated in air at ℃ for 30 minutes
(Filling density 0.5 g / l). In this desulfurizer,
400 ppm (8.53 mmol / l) of 4,6-dimethyl dibe
Nzothiophene, equimolar (8.53 mmol / l) 1-methyl
Flowing and contacting n-heptane containing naphthalene,
High-performance liquid chromatography of the liquid composition at the outlet of the adsorption layer
Was analyzed by Fig. 1 when activated carbon 1 is used as desulfurizing agent
FIG. 6 hours after distribution starts, 1-MN first
After that, the 1-MN concentration greatly exceeded the raw material concentration.
On the other hand, for 4,6-DMDBT,
The sulfur content in the spilled oil is less than 50 ppb until 17 hours
The eyes had a sulfur content in the spilled oil exceeding 1.0 ppm. 16:00
The adsorbing capacity of the desulfurizing agent up to about 18 wt% -S / g-
It was an adhesive. Similar tests were conducted with various desulfurizing agents, and sulfur
When the point when the concentration reaches 1 ppm is taken as the breakthrough point,
4,6-dimethyldibenzothiophene (4,6-DMDB
Table 1 shows the adsorption amount of T) and 1-methylnaphthalene (1-MN).
Was. [Table 1]Embodiment 3 The same test as in Example 2 was carried out using activated carbon 1 and a sulfur content of 40%.
ppm 4,6-dimethyldibenzothiophene (0.85 mmol / l),
100-fold molar concentration (85.3 mmol / l) of 1-methylnaphthalene
The n-heptane contained was contacted by flowing. 4,6-DMDBT
The concentration should be as low as about 50 ppb until the breakthrough time (about 22 hours).
Kept. Up to 22 hours desulfurizing agent adsorption capacity is 2.5W
t% -S / g-adsorbent. Embodiment 4 The same test as in Example 2 was carried out using activated carbon 1 with sulfur content of 4%.
0 ppm of 4,6-dimethyldibenzothiophene (0.85 mmol /
l), molar concentration 1000 times (853mmol / l) 1-methylnaphthalene
Was contacted by flowing n-heptane containing 4,6-DM
DBT concentration is as low as about 100 ppb until breakthrough time (about 4 hours).
Kept the bell. 0.5W desulfurizing agent adsorption capacity up to 4 hours
t% -S / g-adsorbent. Embodiment 5 The same test as in Example 2 was carried out using activated carbon 1 with flowing yellow content of 4%.
0 ppm of 4,6-dimethyldibenzothiophene (0.85 mmol /
l), molar concentration 1000 times (853mmol / l) 1-methylnaphthalene
Was contacted by flowing n-dodecane containing 4,6-DM
DBT concentration is as low as about 100ppb until breakthrough time (about 1 hour)
I kept the level. The adsorbing capacity of the desulfurizing agent is 0.
It was 13 wt% -S / g-adsorbent. [0023] The desulfurization method of the present invention can be used at normal temperature and normal pressure.
Desulfurization treatment provides an energy-saving process
Wear. The desulfurization method of the present invention uses an organic
Only passing sulfur compound-containing liquid under mild conditions
Therefore, household fuel cell systems using liquid fuel such as kerosene
It can be used as a desulfurization process in a system. Ma
Also, as a post-process for hydrodesulfurization tower in the petroleum industry
No need to add any special changes to the process
The value is extremely large. The desulfurization method of the present invention uses the prior art hydrogenation
Since the principle is different from that of decomposition, no hydrogen supply is required. Obedience
Therefore, when producing fuel gas for fuel cells, hydrogen-containing gas
During the fuel gas production process or at the fuel cell electrode exhaust port
Piping, gas compressor, heat exchange
Eliminates the need for ancillary equipment such as vessels
It becomes compact.

[Brief description of the drawings] FIG. 1 is a characteristic diagram when activated carbon 1 is used as a desulfurizing agent. [Explanation of symbols]

Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat II (reference) C10G 25/00 C10G 25/00 29/04 29/04 29/06 29/06 C10L 1/00 C10L 1/00 H01M 8 / 06 H01M 8/06 G (72) Inventor Yoshie Kitayama 8050 Igarashi Ninomachi, Niigata City, Niigata Prefecture Inside (72) Inventor Go Hatamachi 8050 Igarashi Ninomachi, Niigata City, Niigata Prefecture F50 term in Niigata University 4D017 AA04 BA04 CA01 CA03 CA06 DA03 EA01 EB02 4G040 EA03 EA06 EB01 4G066 AA05B AA05C AA13D AA15D AA18D AA30D AA61B AA61C BA22 CA25 DA09 FA21 FA34 4H013 AA03 5H027 AA02 BA01 BA16

Claims (1)

Claims 1. An adsorbent containing either activated carbon or NaY-type zeolite that has been heated and dehydrated at 100 to 500 ° C.
Alternatively, at least one additive selected from Cu, K, Zn sodium metasilicate is supported on activated carbon or NaY-type zeolite as a desulfurizing agent, and at room temperature, normal pressure, LHSV 0.
A desulfurization method in which a liquid fuel is brought into contact under the conditions of ¹ to 10 h ^-1 .