JPS60106885A - Thermal reforming of heavy oil - Google Patents

Abstract

PURPOSE:To improve the yield of a light oil component, by separating thermal reforming reaction products into gas, light oil and heavy residual oil, subjecting at least part of the residual oil to a gravity precipitation treatment and adding the resulting heave dissolved matter to raw heavy oil for reuse. CONSTITUTION:Raw heavy oil fed through a line 1 and carbonaceous solid particles fed through a line 3 are introduced into a thermal reforming apparatus 7. Gas in the resulting thermal reforming reaction products is recovered in a gas- liquid separator 13 and light oil is recovered in a vacuum distillation column 17. At least part of the resulting heavy residual oil together with a solvent fed through a line 23 is fed to a gravity precipitation treatment device 27 to recover a liquid contg. neither heavy metals nor solid (the solid residual is fed to a distillation column 41 and the solvent is recovered from a line 43). Said liquid is fed to a distillation column 33, the solvent is recovered and the havy dissolved matter is recycled through a line 29 to add it to the raw heavy oil.

Description

[Detailed description of the invention] The present invention relates to a method for thermally reforming heavy oil.

In recent years, trends in the demand for petroleum products have been such that the consumption of so-called intermediate products, kerosene, light oil, and heavy oil, has been increasing. On the other hand, since Sennin crude oil tends to become heavier and heavier, eliminating the supply-demand gap between oil types has become a major issue. For this reason, research is being conducted on producing light oil by reforming heavy oil.

For example, there is a method of heating and holding the raw material oil under normal pressure or increased pressure for a certain period of time to thermally cleave the carbon chains of the raw material oil to make it lighter. However, in this thermal decomposition method, as the weighting reaction progresses as well as the weighting reaction, coke is generated in the reactor (hereinafter referred to as coking), making it impossible to continue operating the reactor for a long period of time. There is a problem. Various attempts have been made to prevent this coking phenomenon, one of which is a so-called co-production method in which gasoline fraction and coke are co-produced by alternately operating both tanks in two seed reactors. There is a dilate coker method. This method not only has a low light oil yield and a high olefin content, but also
It is also known to obtain a small amount of oil and pitch by controlling product variations caused by batch operations and heat loss during coke cutting, but in this case, a large amount of pitch is produced. However, there are disadvantages such as a large olefin content in the produced oil, a large heavy oil content, complicated operation as it requires batch operation, and high equipment cost.

In order to eliminate the drawbacks of each of the above methods, carbonaceous solid particles are added to heavy oil, and the mixture is continuously thermally reformed by pressurizing and heating, and the reaction product is distilled under reduced pressure. Methods for recovering oil are also publicly known (Special Publications Act, 1973).
(See Japanese Patent Publication No. 2-85681, Japanese Patent Publication No. 54-16961, etc.). However, since these methods are originally intended to produce pitch and coke from heavy oil, the yield of pitch and coke depends on the condition of the heavy oil as a raw material, but the yield of pitch and coke depends on the weight of the raw material. 30% of quality oil ff1til
The oil yield is relatively low, although on the order of ~50%. That is, in these methods, the oil content is
Separation and recovery is performed by vacuum distillation, but there is a limit to the distillation temperature due to the need to prevent deterioration of the treated liquid due to thermal decomposition, polycondensation, etc.
The upper limit is 50-540°C. Therefore, the boiling point is about 460
Components at temperatures above 540°C are taken out as a distillation residue together with the solid content, and are therefore not effectively utilized.

A method is also known in which the above-mentioned thermal reforming reaction product is treated with a centrifuge, a filter, a hydrocyclone, etc. to mechanically remove solid components and the like. However, with these methods, it is difficult to selectively separate and remove heavy metal components (V, Ni, etc.), solid components, ultra-heavy components, etc. Components, especially heavy metal components, are the cause of catalyst poisoning in subsequent heavy oil reforming and refining processing steps. Another disadvantage is that a part of the light oil, which is a useful component, is lost along with the residual liquid, resulting in a decrease in the yield of useful components in the entire process. Another drawback is that mechanical separation methods such as centrifugation are not suitable for industrial-scale large-scale processing.

The present inventor added carbonaceous solid particles to heavy oil, pressurized and
As a result of extensive research to further enhance the usefulness of reaction products obtained by heating, we have discovered that heavy residual oil (hereinafter referred to as heavy residual oil) is produced by recovering gas and light oil from thermal reforming reaction products. When gravity sedimentation treatment is performed by adding a specific solvent to (called), heavy metal components, solid components, and ultra-heavy components are selectively separated and removed. It has been found that among the above components, light oils can also be easily recovered, so that the oil yield can be elegantly improved. Furthermore, the oil recovered by the gravity sedimentation treatment is substantially free of heavy metals and solids, and the calm of the Conradson carbon residue (hereinafter referred to as CCR) is the CCRffi of the raw material heavy oil for the thermal reforming treatment. When the recovered liquid was mixed with raw material heavy oil and subjected to thermal reforming again, it was found that the overall yield of light oil was significantly improved.

That is, the present invention provides a step (II
) step of separating the thermal reforming reaction product into gas, @quality oil and heavy residual oil; (1) adding a solvent to at least a portion of the heavy residual oil and performing gravity sedimentation treatment to remove heavy metals; and (IV) a step of recycling at least a portion of the recovered oil to the step (1) and adding it to the heavy oil. This invention relates to a method for thermally reforming heavy oil.

The present invention will be described in detail below with reference to the flowcharts shown in the drawings.

In Figure 1, the heavy oil from line (1) is mixed with carbonaceous solid particles from the pipe (3) and transferred to the line (5).
is continuously supplied to the thermal reformer (7), and subjected to a thermal reforming reaction under pressure and heat. Examples of the heavy oil include pressure distillation residue, vacuum distillation residue (asphalt), natural asphalt, and bitumen.

Examples of the carbonaceous solid particles include coal powder, coke powder, graphite powder, carbonized resin powder, activated carbon, and carbon black. The particle size of the carbonaceous solid particles is 1 to 1 part for the latter 1 to 1 part.
It is about 0 parts by weight, and more preferably about 1 to 8 parts by weight of the latter to 100 parts by weight of the former. Thermal reformer (7)
The pressurization and heating conditions in the chamber are usually about 850 to 600°C, pressure of 5 Kjl/cm2·G or more, and opening time of about 1 minute to 80 hours. If the temperature is less than 350°C, the thermal reforming reaction will not proceed sufficiently, whereas if it exceeds 600°C, the amount of gas and coke produced will increase and the yield of light oil will only decrease. However, continuous operation becomes difficult due to an increase in the viscosity of the slurry of the treated material due to an increase in the amount of coke produced. The reaction time is determined based on the relationship with the reaction temperature, but if it is less than 1 minute, the thermal reforming of the raw material heavy oil will not proceed sufficiently, while if it exceeds 80 hours, gas and coke will be generated. This is not preferable because the generated power increases by 5. The pressure shall be the level necessary for the heavy oil chamber to exist in a liquid state at a predetermined temperature. ) is sent to the gas-liquid separator (11), where it is separated into gas and light oil from line (I3) and liquid components from line (15). It contains NH3 and H2S.

The liquid component further passes through line (15) to vacuum distillation equipment fJ.
I (17), where it is separated into light oil from line (I9) and heavy residual oil from line (21). The temperature inside the vacuum distillation apparatus Q71 is set at 450-540°C in terms of normal pressure in order to prevent deterioration of the liquid component due to thermal decomposition, polycondensation, etc.
It is preferable that the upper limit is about ℃. The heavy residual oil obtained here consists of oil, resin, asphaltenes, solids, etc. Asphaltene is a polymeric component that has a higher content of heteroatoms such as N and S and heavy metals than oil and resin. Further, the solid content is formed by coalescence of membranes produced by polycondensation of raw material heavy oil components with carbonaceous solid particles.

At least a part of the heavy residual oil with a normal pressure equivalent temperature of 450 to 540°C or higher from line (2I) is added with a solvent from line (4), and then passed through line (24) during gravity sedimentation treatment (a (2).
7). As the solvent, from the viewpoint of ease of handling, paraffin compounds and monocyclic naphthene compounds that are liquid at room temperature and have a critical temperature of 850° C. or lower are preferred. Table 1 shows the main solvents used in the present invention.

These solvents may be used alone or as a mixture of two or more.

The temperature during the gravity sedimentation treatment in Table 1 is 100°C or higher in order to reduce the viscosity and specific gravity of the liquid to be treated (a mixture of heavy residual oil and solvent) and to perform solid-liquid separation efficiently. 3 to prevent coking reactions caused by thermal decomposition and polycondensation of the treatment liquid.
The temperature shall be 50℃ or less. The pressure should be greater than or equal to the critical pressure of the solvent in order to stably maintain the solvent in a homogeneous phase.

The amount of solvent added to the heavy residual oil is usually about 2 to 12 parts by weight per 1 weight of the former. If the amount of solvent added is small, the viscosity of the liquid to be treated will not be sufficiently reduced and the ability to dissolve heavy residual oil will not be fully demonstrated.On the other hand, if the amount of solvent added is too large, the equipment cost will increase. do. In the gravity sedimentation treatment unit t27), almost all of the solids in the heavy residual oil and the heavier components of asphaltenes coalesce and aggregate without being dissolved in the solvent, increasing the solid particle size. As is well known, in gravity sedimentation, the sedimentation speed of particles is proportional to the square of the particle diameter, so according to the present invention, a liquid material substantially free of solids and ultra-heavy components is used as a supernatant liquid. It will be collected. It was also found that heavy metals such as V and Ni were selectively contained in the solid content and super heavy components, and that the recovered liquid material did not substantially contain any heavy metals.

The recovered liquid material thus obtained has properties equivalent to or superior to the raw material heavy oil in terms of CCR content, etc., so all or part of it is passed through line 9) to line +11.
The oil is circulated through the air and subjected to thermal reforming together with the raw material heavy oil. When the entire amount of recovered liquid material is circulated and mixed with the raw material heavy oil, the oil content acquisition rate increases by 20% or more based on the raw material heavy oil compared to the case where no circulation is performed at all.

The recovered liquid obtained from the gravity sedimentation treatment equipment is transferred to the line (
After supplying the solvent from 31) to the distillation apparatus and recovering the solvent from line C451, all or part of it can be circulated and mixed with raw material heavy oil via line ρ9), and the remainder can be recovered as a product. .

The residue containing solids and heavy metals settled in the gravity sedimentation treatment device (27) passes through line 139) to the distillation device (41).
) and is separated into the solvent from line (4→) and the solid residue from line (4υ).

The solvent recovered from line 1 and line 4 is circulated to line (c) and reused.

In addition, in the present invention, it is not necessary to send the heavy residual oil obtained by the vacuum distillation device θ'7) to the gravity sedimentation device and supply it to η, and a part of the heavy residual oil obtained by the vacuum distillation device θ'7) is not required to be supplied to η, for example, through a line branching from the line (21). 147) and may be taken out of the system and used as is.

Reference example 1 Arabian heavy asphalt (CCR=22.8% by weight) 100! Add 5.8 parts by weight of keystone charcoal powder (residual carbon 88.2% by weight) of 74 μm or less to the ffi part and charge it into an autoclave with a stirrer having a content of ff1ll.
20Ky/. It was maintained under conditions of m2·G and 410°C for 5 hours. At this time, 10 parts by weight of gas was generated.

The reaction product remaining in the autoclave was removed under real pressure (5 m
mH, abs) until the distillation temperature reached 250° C. to obtain 40 parts by weight of light oil. The contents of each component in the heavy residual oil were as shown in Table 2.

Table 2 V B86ppm Ni 1141) I) In CCR 51% by weight Asphaltene 22 parts by weight Next, 6 parts by weight of a mixed solvent with a critical temperature of 200 to 850°C shown in Table 1 was added to 1 part by weight of the above heavy residual oil. was added to an autoclave with an internal volume of 3.51 mm and equipped with a stirrer, and the temperature was set to 2.
10°C, pressure 40 to 9/. After extraction with m2·G, the mixture was allowed to stand for 15 minutes and the supernatant liquid was collected. Next, the solvent was removed by distilling the clear liquid, and 32.5 parts by weight of a liquid material substantially free of heavy metals and solids was recovered. The properties of the liquid are shown in Table 3.

Table 8 y 14Prl) m Hls ppm CCR10 heavy equipment asphaltene 4 nails amount % Example 1 32.5 weight of recovered liquid obtained in Reference Example 1 and Arabian heavy asphalt (similar to that used in Reference Example 1) 67.
Thermal reforming treatment and distillation were carried out in the same manner as in Reference Example 1, except that a mixture consisting of 5 polymeric parts was used as the raw material.

The amount of gas generated was 9.2 parts by weight, and the amount of light oil produced was 40 parts by weight.
Parts by weight.

When the obtained heavy residual oil was subjected to gravity sedimentation treatment and distillation in the same manner as in Reference Example 1, 82.9 parts by weight of a liquid material substantially free of heavy metals and solids was recovered. The properties of the recovered liquid material are shown in Table 4.

Table 4 V 16 ppnl Ni '9 ppm CCR1B weight % Asphaltene 6 types % Judging from the production amounts of gas, light oil and recovered liquid in Reference Example 1 and Example 1, Arabian Heavy Asphalt and Reference Example 1 It can be said that the reactivity of the recovered liquid material is almost the same.

In addition, in Reference Example 1, the oil content acquisition rate is 40/100=
While it was 0.40, in Example 1, the oil content acquisition rate was 40/(100-82,5)=0.59. That is, compared to Reference Example 1 in which only heavy oil is thermally reformed, in Example 1 in which the recovered liquid material is circulated, the amount of oil obtained is increased by about 50%.

[Brief explanation of drawings]

FIG. 1 is a flowchart showing an example of an embodiment of the present invention. (7) is a thermal reforming device for a mixture of heavy oil and carbonaceous solid particles, (11) is a gas-liquid separation device, (17) is a vacuum distillation device, (
) is the solvent addition line, η is the gravity sedimentation treatment device, 4 is the recovered liquid circulation line, 1 is the distillation device, (10 is the distillation device. (and above)

Claims (1)

[Claims] ■ (1) A process of thermally reforming heavy oil by adding carbonaceous solid particles to the mixture and pressurizing and heating it; (11) converting the thermal reforming reaction product into gas, light oil (+n) a step of adding a solvent to at least a portion of the heavy residual oil and performing a gravity sedimentation treatment to recover an oil that is substantially free of heavy metals and solids; , and 4Vl. A method for thermally reforming heavy oil, comprising a step of circulating at least a part of the recovered oil component to the middle step and adding it to the heavy oil.