JPS5891002A - Gasifying method of heavy oil by fluid catalytic partial oxidation - Google Patents

Abstract

PURPOSE:To permit partial oxidation of heavy oil fractions at a lower temp., a less rate of oxygen consumption and a higher rate of gasification in a titled gasifying method by specifying the compsn. of catalysts. CONSTITUTION:Heavy oil fractions are brought into fluidized contact with gasifying agents at 800-1,000 deg.C and 1.0-10:1 total O atoms of the gasifying agents: the C atoms of the heavy oil fractions in the presence of fluidized bed catalysts contg. CaO deposited on alumina carriers and iron oxide as an assistant. Here, if the gasifying temp. for partial oxidation is below the lower limit, main reaction consists of a thermal decomposition and therefore essential components of tar and carbon are contained much and unsaturation components such as ethylene are increased in the formed gas. In excess of the upper limit, a secondary decomposition of the products is induced, by which carbon is formed and the consumption of O is increased. If the O atom/C atom ratio is below the lower limit, carbon deposits on the surfaces of the catalysts, the catalytic activity is decreased sharply, and unsaturated components are increased in the formed gas. In excess of the upper limit, the partial oxidation progresses so much that CO2 increases in the formed gas and a loss of energy is caused on account of an increase in the amt. of unreacted excess steam.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for catalytically partially oxidizing liquid hydrocarbons, particularly heavy oils such as atmospheric distillation residues and vacuum distillation residues, by contacting them with a fluid catalyst. Is it syngas J? It is useful for the production of city gas, production of hydrogen for coal liquefaction, hydrogenation of petroleum reagents, etc., and as a raw material for C-/chemistry.

Existing industrial heavy oil gasification operations are carried out at temperatures above 7000° C. using basic catalysts, and partial oxidation without catalysts has also been used for this gasification operation to a limited extent.

In this non-catalytic method, a coking reaction occurs in the partial oxidation reactor, and the raw material gas is converted to carbon, resulting in a lower gasification rate.In addition, the structure and structure of the equipment was designed with special consideration given to the treatment of by-product carbon. This requires the installation of a carbon collector and quenching bath6 for removing carbon, and the addition of a pellet system for carbon reuse, or the extraction of carbon and recycling by mixing it with raw oil. Since this is a non-contact method, a gasification temperature of 7,300° C. or higher is required.

Further, in the catalytic partial oxidation method in this field, as mentioned above, catalysts made of basic substances, such as calcium oxide, magnesia, dolomite, etc., have been used. However, this type of catalyst has low activity at low temperatures, so
A gasification temperature of .degree. C. or higher is required, and therefore, measures must be taken to prevent problems such as fire resistance and spalling resistance of the equipment, as well as disintegration and wear due to combination with the heavy oil.

The objectives of the present invention are (1) high gasification rate (gasification with virtually no by-products such as carbon and tar), (2) simple equipment W, operation and accounting, and (3) clean and high quality gas. The object of the present invention is to provide a method for the catalytic partial oxidation of liquid hydrocarbons, especially heavy oils, such as ordinary L[distillation residues and vacuum distillation residues], which enables the production of (4T) and the use of lower gasification temperatures.

Another object of the present invention is to produce hydrogen for hydrogenation in coal liquefaction, petroleum refining, etc. for synthesis gas production, city gas production, etc.
) manufacturing, C/chemical raw materials, etc. are all provided.

The purpose of this is to convert hydrocarbons, especially heavy oil, into an alumina phase.
[Calcium oxide, auxiliary agent, and gasifying agent at a flow rate of 7.0 to /θ: / in the presence of a fluidized bed catalyst containing all iron at 17°C to 100°C; Purple atom: j
This can be achieved by a method for partially oxidizing hydrocarbons, especially heavy oil, by fluidizing and gasifying hydrocarbons, especially heavy oil, by bringing them into fluid contact at an atomic ratio of N hydrogen carbon atoms (O atoms/C atomic ratio).

The hydrocarbons used in the process of the invention can in particular be depleted oils such as atmospheric distillation residues or vacuum distillation residues.

Heavy oil with a carbon atom/hydrogen atom ratio of about 2 IM- can be cheaply converted into gas.

1ij/IZ medium alumina is t+ for this type of catalyst!
Aluminas of the type commonly used are preferred, especially alpha-aluminas. Calcium oxide is different from alumina.
It is preferable to use iron oxide as an auxiliary agent in an amount of 7 to 10% based on Cao.

The catalyst is α-aluminum by calcining r-alumina at 7200℃ for 2 hours.
It was prepared by a wet method using alumina. That is, alumina was loaded with 111 using calcium and iron nitrates, and the nitrate radicals were removed by heating, and the mixture was calcined at 7,200° C., sized, and used in the reaction.

Oxidation gasification for 40 minutes at gθ0℃~/θ00℃ a,
A degree is used, but if it is less than goo'c, the main reaction is thermal decomposition, so a lot of tar and carbon are produced, and the composition of the gas produced is also unsaturated components such as ethylene and propylene (
These components are unsuitable for the purpose of the present invention). Moreover, when the temperature exceeds 100θ°C, secondary decomposition of the product is completely induced and carbon is generated. Moreover, raising the temperature more than necessary increases the consumption of oxygen, which not only deteriorates the composition of the produced gas but is also economically unfavorable.

Gasifying agents dissolved in water vapor and oxygen or air are used. Oxygen or air supplies the oxygen necessary for the reaction, prevents the catalyst activity from decreasing, and supplements the reaction heat.

The ratio of the gasifying agent to the hydrocarbon is the oxygen atom in the gasifying agent (
Atomic ratio of carbon atoms in hydrocarbons: oxygen in water vapor (ten pure oxygen or oxygen in air or oxygen in mixtures thereof)
0/C) is limited to /~10:/. If 0/C is less than 7, carbon will precipitate on the surface of the catalyst, rapidly reducing the catalyst activity and making it difficult to use it for a single period. In addition, if the composition of the generated gas is rich in unsaturated components and the C ratio exceeds 10, H1t1t will progress too much and CO2 gas will increase in the generated gas (when air is used, N2 will also increase). ), resulting in deterioration of the quality, or an increase in unreacted surplus water vapor, resulting in energy loss.

According to the method of the present invention, hydrocarbons, especially heavy oils, can be partially oxidized, thereby producing N2 and 00, which can be used for synthesis gas production, city gas production, C/chemistry, coal liquefaction and oil It can be used to provide hydrogen needed in refining and other processes.

The present invention will be explained in more detail below with reference to Examples.

A predetermined amount of steam is added to the raw material heavy oil (O//n=f, ko) and preheated in the usual manner, and nitrogen or oxygen is separately supplied to the gasification furnace for gasification. Inside the furnace, a dense flow layer is formed by the above-mentioned catalyst, and gasification by catalytic partial oxidation is performed at gooC to 100θC, preferably 900C.

The following reaction occurs in the gasifier: OnHm+(n+−) 02j”neo□+2H20gOnHm+nH,04nOO+(j+n)H
20nHm +00, 4 pieces nOO+-1H2 (30+
H, O'; 1002+H2 Here, oxygen supplies the oxygen necessary for partial oxidation, prevents a decrease in catalyst activity, and supplements the entire reaction heat.

OaO, which is the main component of catalytic activity, is A420. Reacts with 0aAf203.11g 0aO-A4,05. ,
? OaO-Af, 03°JOaO-5AJ20. It is thought that the balance of these components influences the activity. In addition, Fe2O, at least in part, is in the form of Fe2O4, and the presence of these iron oxides is effective in the partial oxidation method, and the above is synthesized to produce a complex effect. , I don't think that the catalytic function will be fully established.

Figure 1 shows the atmospheric distillation residual oil at a partial oxidation temperature (gasification temperature) of 900°C using an alumina-0aO-Fe catalyst (30% Oao to alumina, 5% iron oxide to OaO),
/. Water vapor with atomic ratios −/, 2:/ (curve B) and/. Atomic ratio /, Coni / of (water vapor., 9 moles / C atoms 10 oxygen 0
．． 3 atoms/C atoms) (curve 0) shows the change in gasification rate over time when t- is used.

Under the conditions of curve A, the gasification rate ij is as high as 97%, but since a large proportion of water vapor is required, there is a drawback that the total amount of energy is too large. In curve B, a decrease in activity is observed from around 7 hours after the start of the reaction, but the oxygen atoms in the gasifying agent ft/
, - its original oxygen curve C).

In Figure 2, atmospheric distillation residual oil is used as the hydrocarbon (heavy oil), an alumina-0aO-Fe catalyst with the same composition as in Figure 7 is used, the 10 atomic ratio is fixed at /1.2, and the amount of air is (In some cases, pure oxygen is used, so the nitrogen in the air is removed and the comparison is made in a state close to pure oxygen.) By varying the water vapor:oxygen ratio, the product gas H, 00, 002 and the composition (%) of OH4. ! Oxygen atoms in each air/CU! The calorific value (kilocal/NMJ) of the partial oxidation product gas obtained by the atomic ratio of the particles is also shown (track mD). From Figure 1, increasing the amount of oxygen fed into the air will yield a high-quality gas, while reducing the amount of oxygen fed into the air will yield a gas with a considerable amount of heat generation i:Th for fuel gas such as city gas. I know that it will happen.

For example, in the case of 0 atoms (air oxygen) 10 atoms 0.3 (total 0 atoms (water vapor 10 oxygen) 10 atoms - /, ko), the calorific value exceeds 2jθθ kg/NMB, and city gas It can be seen that it is advantageous for energy applications such as, and its gasification rate is 95 degrees.

Compared to the heavy oil gasification technology industrialized by the prior art, the method of the present invention has (1) a lower gasification temperature (the present invention ranges from 0°C to 1000°C, preferably 900°C, prior art/3
θθ℃~/600°C), (,2) low oxygen consumption (0.3 mol oxygen/C atom in the method of the present invention, 10.J atoms in the prior art) and gas It has the advantage of a high conversion rate (fi of as high as 9Q% can be obtained with the method of the present invention, compared to 0-43% with the prior art), and has great significance in the heavy oil partial oxidation gasification industry. be.

[Brief explanation of drawings]

FIG. 1 is a diagram showing the change over time in the gasification rate according to the method of the present invention, and FIG. 1 is a diagram showing the oxygen atomic ratio in the introduced air, the product gas composition, and the calorific value. Patent applicant: Japan Steel Works Co., Ltd. ``Teru Soga Michi'' 1)

Claims (1)

[Claims] In gasifying heavy oil by partially oxidizing it with a gasification agent through a fluid contact operation, a catalyst containing an alumina carrier, calcium oxide, and iron oxide as an auxiliary agent is used, and goo'c~ A method characterized in that partial oxidation is carried out at a temperature of 100° C. under conditions in which the atomic ratio of carbon atoms of all oxygen atoms in the gasifying agent to carbon atoms of the dual quality oil is /~10:/.