JPS582162B2 - Datu Asphalt Yuno Seihou - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention is capable of extracting components containing asphaltenes and heavy metals from asphaltic heavy petroleum oil without using a countercurrent extraction column used in conventional solvent deasphalting methods. It relates to a method of removal, and more specifically, it involves mixing and stirring one or more C3 to C5 paraffinic hydrocarbons with asphaltic heavy petroleum oil using a line-type stirring device, and then centrifuging at 1000 G or more. The present invention relates to a method for producing de-asphalted oil, which is characterized in that asphaltene and heavy metal-containing components in a solid state at room temperature are separated from oil by applying force.

As a solvent refining method for petroleum residue oil, the deasphalting method using propane is well known, and there is also a method of removing heavy metal-containing components and asphaltic substances from petroleum residue oil using C4 or higher paraffinic solvents. Are known.

However, these methods generally separate both components in the liquid phase, and the micelles of asphaltic and heavy metal-containing components are grown by heating under pressure, etc., and are separated after they grow to a large size. Therefore, the process involved two stages of growth and separation, and had the disadvantage that the amount of oil passed and the processing speed were low despite the large size of the equipment.

Furthermore, in these methods, the amount of solvent used (solvent ratio) relative to the amount of oil passed is large, and it has also been required to reduce the solvent ratio.

As an improvement on these known solvent deasphalting methods, a method has been proposed in which asphalt and heavy metal-containing components are separated from oil using a hydrocyclone using a C5 to C7 hydrocarbon as a solvent (Japanese Patent Publication No. 42-153).
86), also in this method, 1
Since the asphalt requires stirring for ~10 minutes, the solvent ratio is as high as 3 to 6, and the asphalt is recovered in a suspended state as a mixture with a large amount of solvent, it is necessary to provide a separate means for recovering the solvent (Tokuko Showa). 43-30430).

The development of a cheap and economical method for removing bituminous and heavy metal-containing components from petroleum residue oils has led to the spread of crude oil for pollution prevention, direct desulfurization of residual oils, increasing demand for high-quality fuel oil, shale oil, etc. development of untapped oil resources,
This has become an important issue as it is put into practical use.

The present invention solves the above problems and makes it possible to obtain high quality deasphalted oil easily and inexpensively.

Petroleum-based heavy oils to be treated in the method of the present invention include atmospheric distillation residues of crude oil, vacuum distillation residues, heavy crude oils, shale oils, sand oils, cracked oils, and the like.

The solvent used is a C3-C5 paraffinic hydrocarbon, specifically propane, butane, pentane or a mixture thereof.

Butane or pentane may be a single substance such as n-butane or n-pentane, or may be a mixture of these isomers.

The most suitable solvents for carrying out the process of the invention are butanes, pentanes, mixtures of butanes and pentanes, or mixtures of butanes and propane.

The presence of some other components (such as small amounts of unsaturated hydrocarbons) as impurities in the solvent does not pose any problem.

-The ratio of the solvent used to the oil to be treated (solvent ratio) is not constant but varies within the range of 1/1 to 8/1 depending on the heavy oil to be treated, the properties of the target product, and the type of solvent selected. However, it is generally within the range of 1/1 to 6/1, and by appropriately selecting the solvent, preferable results can be obtained with a solvent ratio as low as 1.5/1 to 3/1.

Processing temperatures can vary from room temperature to 100°C, generally ranging from 30 to 75°C, with preferred results at 40°C.
Obtained at a processing temperature of ~60°C.

Unlike conventional methods, the method of the present invention does not require measuring the growth of micelles, and the purpose is to separate asphaltic and heavy metal-containing components from oil in a solid phase, so it is unnecessary to measure the growth of micelles. Temperature raising treatment is not preferred.

The processing pressure may be any pressure that can maintain the system as a phase liquid, and generally it can be operated at a pressure of 10 kg/cm2g or less.

When carrying out the method of the present invention, it is necessary that the oil to be treated and the solvent are thoroughly mixed.

This mixing is not sufficient merely to bring the oil to be treated into contact with the solvent, but is to ensure that the asphalt-based substances and heavy metal-containing components are stripped out by stirring to facilitate subsequent separation.

Mixing and stirring of the oil to be treated and the solvent can be achieved by any means that can provide good mixing and stirring effects, but as described later, when implementing this method, no residence time is required, so a line-type stirring device is used. is appropriate.

Agitation by vigorous movement, for example in a pump or in an orifice mixer, gives good results.

One feature of the method of the present invention is that it does not utilize the growth or enlargement of micelles of asphalt-based materials or heavy metal-containing components, but simply leaves them in a naked state and forcibly separates them, which is indispensable in conventional methods. Since the aging period, which was a requirement, is not required, the device can be significantly downsized.

The contact time is generally 10 seconds or less, and usually about 1 to 5 seconds is sufficient.

The oil to be treated that has been mixed with the solvent and stirred is then subjected to a forced separation operation by the action of strong centrifugal force.

The centrifugal force to be applied is 1000G (G is acceleration of gravity) or more, and is generally in the range of 1500 to 4500G.

A sufficient separation effect cannot be obtained with a centrifugal force of 1000 G or less.

According to the method of the present invention, for example, using the atmospheric distillation residue of crude oil as a raw material, the yield is about 95% by volume, the C7 asphaltene (heptane extraction residue) content is 0.1% by weight or less, and the heavy metal content is also low. High-quality deasphalted oil, which is about 1/2 to 1/3 of the raw material oil, can be easily obtained using equipment that is small compared to the processing amount (considered essential in conventional solvent deasphalting methods). There is no need to use conventional equipment or countercurrent extraction columns, which are expensive to operate.

), and because the process is performed under relatively low temperature and low pressure conditions, the safety of the equipment is high.

The method of the present invention is particularly suitable as a preliminary treatment when crude oil residue from atmospheric distillation is directly used as a raw material for a desulfurization equipment.
It is also an excellent method for treating feedstock feedstock for crackers and for improving the quality of heavy oil, and depending on the selection of conditions, it can also be applied to the treatment of lubricating oil raw materials.

Examples will be shown below to further specifically explain the structure and effects of the present invention, but these are merely disclosed for the purpose of illustration and are not intended to limit the scope of the present invention.

The following examples were obtained using an apparatus as outlined in FIG.

In the figure, the oil to be treated (raw oil) is discharged from route 1 by pump 2 into route 3, and the solvent is discharged from route 4 to pump 5.
The oil is discharged into the path 6 and joins the oil to be treated in the path 3.

Path 7, pump 8, and path 9 are piping when a mixed solvent is used, and in the figure, path 9 is directly connected to path 3, but of course it may be connected to path 6, and the type of pump used is also free.

The oil to be treated and the solvent are combined in a path 3 and a mixing pump 10
and/or sufficiently mixed and stirred in the mixing and stirring area indicated by the orifice 11.

It is not necessary to operate both the pump 10 and the orifice 11, and usually only one of them is required.

The raw materials that have passed through the mixing and stirring zone immediately enter a centrifugal separator 12, where they are forcibly separated and deasphalted oil is recovered from a route 13, and asphaltic and heavy metal-containing components (hereinafter referred to as separation residue) are recovered from a route 14. Ru.

Example 1 Atmospheric distillation residue oil 1 of Kuwait crude oil heated to 60°C
00 parts and a solvent heated to 48°C (consisting of 85 parts of butane and 15 parts of pentane, the composition of butane is n-C4 70%
, i-C430%, pentane composition is n-C580%,
300 parts of i-C5 (20%) were respectively fed and combined using pumps, passed through a mixing pump 10 and an orifice 11 for complete contact mixing, and immediately fed to a centrifuge 12.

The supply temperature to the centrifuge was 52°C, and the operating conditions of the centrifuge were as follows.

Effective diameter of centrifuge: 152 mm Internal volume: 3 liters Feed material: 7,000 liters/hour Centrifuge rotation speed: 6,000 rpm Centrifugal force: Approximately 3,050 G Ring dam height: 8 mm Internal pressure (inert gas pressurization): 8 kg/cm2 Asphalt-free oil obtained by the above operation Table 1 shows the yield and properties of the desolvated products of the separation residues and the separation residues, together with the properties of the raw materials.

Considering that the detection limit for C7 asphaltene is 0.05 wt%, the deasphalted oil obtained in this example can be said to contain almost no asphaltene, and the content of heavy metals compared to the raw material is also lower than that of the deasphalted oil. So 1/
It is recognized that the amount has decreased by 2 to 1/3.

Example 2 The following experiment was conducted using the same raw material oil and the same centrifuge operating conditions as in Example 1.

To 100 parts of raw oil heated to 62°C, 300 parts of a mixed solvent of 50 parts each of butane/pentane heated to 52°C (compositions of butane and pentane are the same as shown in Example 1) were supplied using a pump. After mixing and stirring using orifice 11, the mixture was immediately processed using a centrifuge.

The centrifuge inlet temperature was 54°C. The properties of the de-asphalted oil were as follows.

C7 asphaltene (wt%) 0.08 residual carbon
CCR (wt%) 7.1 Vanadium (
ppm) 25 Nickel (ppm) 10 Example 3 Using the same raw material oil and centrifuge as used in Example 1, butane was used as a solvent, and by pump mixing at a solvent ratio of 2.5/1 (solvent/raw material). The raw materials and solvent were mixed and immediately supplied to a centrifuge.

The centrifuge inlet temperature was 45°C, and the operating conditions of the centrifuge were as follows.

Centrifuge rotation speed: 5000 rpm Centrifugal force: Approximately 2150 G Ring dam height: 12 mm System pressure: 8 kg/cm2-g Table 2 compares the yield and properties of the obtained deasphalted oil with the properties of the raw material.
Shown below.

Example 4 The following experiment was conducted using the same raw material oil as used in Example 1 and using the same centrifuge operating conditions as in Example 1.

330 parts of pentane heated to 70° C. were fed to 100 parts of the above raw material oil heated to 80° C. by each charge pump, and after mixing with the pumps, the mixture was immediately fed to a centrifuge.

The obtained results are shown in Table 3 together with the properties of the raw material oil.

Example 5 The following experiment was conducted using the same centrifuge operating conditions and raw material oil as in Example 1.

Pentane (n-C5 82%, i-C5 18%) heated to 70°C for 100 parts of residual oil heated to 80°C 5
60 parts were supplied by a charge pump, combined, thoroughly mixed with an orifice, and immediately supplied to a centrifuge.

The centrifuge inlet temperature was 70°C.

The properties of the obtained deasphalted oil and separation residue are shown in Table 4 together with the properties of the raw materials.

[Brief explanation of the drawing]

FIG. 1 is a system diagram showing an example of an apparatus for carrying out the method of the present invention.

Claims (1)

[Claims] 1. Mixing and stirring one or more C3 to C5 paraffinic hydrocarbons with asphaltic-containing petroleum heavy oil using a line-type stirring device, and then applying a centrifugal force of 1000 G or more to asphalt-containing and heavy metal-containing heavy oil. A method for producing de-asphalted oil, which is characterized by forcibly separating components from oil.