JPS5811591A - Preparation of high calorie gas from coal gas as raw material - Google Patents

Abstract

PURPOSE:To obtain a natural gas substitute having high calorie, by desulfurizing or deoxidizing a blend of coal gas, naphtha, and LPG, followed by making it into methane in the presence of steam at a specific high temperature. CONSTITUTION:A blend of coal gas and naphtha and/or LPG is subjected to pretreatment such as desulfurization, deoxidation, etc., and made into methane in the presence of steam as gasifying agent and a cooling medium in an amount to make S/C=0.5-2.0 at 300-550 deg.C, to give the desired gas. The blend consists of preferably 1mol coal gas and 0.01-0.1mol naphtha and/or LPG.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing high calorific value alternative natural gas (hereinafter referred to as 5ING) using coal gas (hereinafter referred to as COG) as a raw material.

In recent years, liquefied natural gas (hereinafter referred to as LNG) has occupied a large share in city gas raw materials.
) is rapidly increasing, and the so-called natural gas conversion is likely to be further promoted in the future. and ζ
LNG requires large-scale facilities that are operated under certain suitable conditions for its amperage, storage, vaporization, etc., so it depends on the season.
It may not always be possible to respond appropriately to changes caused by economic fluctuations, etc. Furthermore, excessive dependence on LNG is thought to cause some problems in terms of stable supply of raw materials. Therefore, by absorbing demand fluctuations and diversifying raw materials, 9LNG will become the main source of electricity! ! There is an urgent need to develop a new production method for 8NG that does not depend on LN (1) to maximize the benefits of converting natural gas as a raw material.

As a method for producing gas with a high calorific value from 00G, several methods are considered to be possible, such as the following. For example, COG is first passed through an adsorbent such as Molecule 2-Sheep under pressure to separate it into hydrocarbon gas with small molecules adsorbed by the adsorbent and low molecular hydrogen gas which is not adsorbed, and then the hydrocarbon gas is passed under reduced pressure. One possible method is to desorb the gas from the adsorbent to produce a gas with a high calorific value. In this case, if a plurality of adsorption devices are provided, it is possible to continuously obtain a high calorific value gas by alternately performing adsorption and desorption. However, in this method, the mechanism of the adsorbent is 0.
Since it is inhibited by impurities in 00, it is necessary to remove tar, penzol, tar, etc. to the extent that it can be said to be an obstructive amount of gold, and large-scale *S equipment is required. Furthermore.

In the high-angle method, hydrogen in COO is 411 compared to carbon, so the calorific value of the generated gas is much lower than the desired value. be.

In view of the above, as a result of extensive research, the inventor has discovered that CO
Adding naphtha and/or LPG as a carbon source to O and subjecting JL Kusaka Metals to normal pre-treatments such as desulfurization and deoxidation, and then subjecting them to methanation treatment in the presence of steam as a gasification agent and coolant. K, I hope you can solve the above problem.
114 new ways to stop &#NG with various advantages as mentioned above#
Kjll completed the present invention by discovering that:
Ri'e. That is, the present invention involves adding soot and/or LPG as a carbon source to a coal-gas mixture and desulfurizing the mixture.
After pretreatment with oxygen, etc., this was heated to 810-0. G4
30G-! in the presence of steam as a gasifying agent and coolant in an amount of ! This invention relates to a method for producing a high calorific value gas using coal gas as a raw material, which is characterized in that it is methanated at 50°C.

The raw material for the method of the present invention is C00K napna and/or LPG.
Although the addition ratio of soot and/or LPO to COGK, which is a mixture of COG9 and COGK, is particularly limited, if combustion compatibility with city gas (13M), which is a direct supply of natural gas, is considered, COG1 Naphtha and/or LPG per mole
oO is preferably about O,01-0,1 mo.
, 1, carbonic acid may also be required due to the increase in CO8. In the present invention, the above mixture is first subjected to pretreatment such as deoxidation and desulfurization according to a conventional method. Examples of the deoxidizing reaction catalyst include Ni-Mo, Co-Mo, and N1B catalysts, which also function as desulfurization catalysts. When these catalysts are used, deoxygenation and organophilic sulfurization of the % mixture is accomplished by hydrogenation with hydrogen in the C0G. These deoxidation and desulfurization treatments may be carried out according to conventional methods, for example, the temperature at the outlet of the reactor is O.
Approximately 5Gk#/cdG, reactor outlet temperature 36-43G
It is best to do it under 43G conditions.

Then, the mixture is sent to adsorption desulfurization 11, and the normal Zn0
At 0ζζ when adsorption desulfurization by K is performed, the oxygen concentration in the mixture is substantially zero, and the total sulfur concentration is approximately 1 pPJI Jji. Since all of the desulfurization reaction lines mentioned above are exothermic reactions, if necessary, heat is recovered from the mixture using a waste heat generator or the like. It will be done.

The methanation step is carried out in the presence of a catalyst such as a platinum group metal catalyst or a Ni catalyst, so that 8/C (the number of oxygen atoms in water vapor per carbon atom in the hydrocarbon) is 0.6 to 2. This is carried out in a state where water vapor is added to the mixture in an amount of about 0. In the methanation step, the reactor inlet temperature is preferably about 260 to 300''C, the reactor internal pressure is about 6 to 10 to 9/cilG, and the reactor outlet temperature is preferably about 300N560C. Although it varies depending on the calorific value q of the finished product gas, the mixing ratio of LPG, the methanation reaction conditions, etc., COO
The initial calorific value of 5000 to 5300 km/Nff1'' is approximately 7000 to 85001 o1/Nll'.

This produced gas can be used for a while, but if necessary, it can be heated by adding more KLPG to 8
0 that can be used as NG In the method of the present invention, the pitch is determined according to the conventional method.

It is essential to add COJCLPG without ammonia, cyanide, naphthalene, penzole, etc., and to subject the resulting mixture to deoxygenation, desulfurization and methanation steps. In this way, (1) coo and LPG are uniformly mixed during the deoxidation and desulfurization treatment, so the methanation reaction progresses favorably and a gas with excellent combustibility is obtained. (1) L
Since the sulfur contained in PG can be desulfurized at the same time, the life of the methanation reaction catalyst is extended. ii9
The addition of LPG produces remarkable effects such as being able to effectively suppress temperature fluctuations during deoxidation and desulfurization treatments. In fact, first, COG alone was deoxidized and desulfurized, then LPG was added to it, and the M mixture was subjected to a methanation reaction. However, the sulfur content derived from LPG poisoned the catalyst, resulting in methane as a whole. In addition to the above-mentioned effects, the method of the present invention is also effective in expanding the use of COG, whose usage amount has been relatively reduced due to the introduction of LNG. Although COG is extremely useful, COG is generated in large quantities as a by-product during the production of coke, which has various uses, and the decline in demand for COG has been a problem.According to the present invention, during this period, COG
The issue was resolved by converting OG to 8NG).

Example! 0OG100ONIr/h with the composition shown in the C#It table below
If below! jig 1111 shows the fm configuration (D LPG
16 oky/h and use it as raw material O Table 1 H, 66, Ovoig II N, a, o' QQ 6.0 #C0,2,0' OHa N13 '' C, ~ 0.8.5' Q, O, i! #Organic sulfur compound sgpp table 1st exposure table C, Hll, Q vol 4s 1-04H,. 210# n-C4M1. Oxygen and desulfurization reaction alKj 1 ring, reactor inlet temperature approx. 60℃ 1
The treatment is carried out under conditions of reactor internal pressure cuff/-G1 reactor outlet temperature of about 400°C. The mixture is then sent to an adsorption desulfurization reactor filled with a ZnO-based catalyst for treatment. Thus, the oxygen content in the mixture is essentially 1 zero, and the total sulfur content is tppm.
0 Then, the above purified mixture of nine raw materials is fed to a methanation reactor filled with a platinum group metal catalyst, and 810=Q, $
The methanation reaction is carried out in the presence of water vapor. The inlet temperature of the methanation reactor is approximately 260℃, and the outlet temperature is approximately 35℃.
The pressure inside the reactor at 0° C. is approximately 6 Yu/ca G.

8 m of gas obtained by methanation reaction! ONm”/
The fiber formation and calorific value of h are as shown in the following ms table. Armpit gas can also be used as fuel, but underarm gas IN 56cLPG0.
Mixing # with 33 k・yop fever mttoo・Io
L/N is 0 (or more) that yields 8NG with a specific gravity of 0.711.

Claims (1)

[Claims] ■ After performing pretreatment such as desulfurization and deoxidation on a mixture of coal gas ~ S★ with naphtha and/or LPG added as a carbon source, 1. 810-0.6 to 2.0 in the presence of steam as a gasifying agent and coolant.
A method for producing a high calorific value gas using coal gas as a raw material, which is characterized by being methanized at 5IN)°C.