JPS62119294A - Hydrocarbon solvent extraction method and bis-breaking method - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION This invention relates to selective solvent extraction of hydrocarbon mixtures, and more particularly to the solvent extraction of lubricating oils using furfural. The present invention also relates to a process for treating residue stocks by visbreaking in the presence of certain highly aromatic hydrogen donors obtained from solvent extraction processes.

Solvent extraction is a well-known method for separating aromatics from a mixture of aromatics and non-aromatic hydrocarbons of the same boiling range.

Furfural has been found to be a solvent with excellent selectivity for the separation of relatively high boiling hydrocarbons, such as those useful in lubricating oil production and catalytic cracking feedstocks. Furfural extraction has also been found to be useful in the production of kerosene and low boiling gas oil products to produce raffinates with low aromatic content.

In a typical furfural extraction method, a liquid hydrocarbon mixture containing aromatic and non-aromatic hydrocarbons is brought into contact with liquid furfural in an extraction column to form a raffinate phase, which removes the main non-aromatic hydrocarbons. A raffinate phase containing a fraction is recovered from the top of the extraction column, containing most of the furfural containing the main fraction of aromatic hydrocarbons and remaining non-aromatic hydrocarbons and containing most of the dissolved hydrocarbons. The extracted phase is then recovered from the bottom of the extraction column.The two phases can then be separated into their components by distillation. U.S. Pat. No. 3,205,167 processes the extraction phase by cooling it, thereby converting the extraction phase into one phase consisting of a naphthenic oil known as pseudodraphinate and containing only a small amount of solvent and in oil. He proposes that the extract be separated into another phase called the extract proper, which contains larger amounts of aromatic and sulfurized components and a large amount of solvent. However, U.S. Patent No. 3,205,167
The specification does not specify a specific temperature range in which this cooling operation is performed, nor does it say anything about the composition and properties of the extract liquid proper.

The visbreaking process is a process in which vacuum gas oil is pyrolyzed or cracked under relatively mild conditions to obtain a product with a lower viscosity and pour point. 1% is a known petroleum refining operation whereby a fuel oil and a lubricant stock of l... This reduces the amount of mixed oil, which is both expensive and expensive.

Visbreaking feedstocks typically consist of two or more refined streams derived from sources such as atmospheric distillation residues, vacuum distillation residues, furfural extracts, propane deasphalted tar, or catalytic cracking unit residues. Consists of a mixture. Most of the above-mentioned feedstock components, other than heavy aromatic oils, behave individually in the visbreaking operation. As a result, the severity of operations on mixed charges is significantly limited by the least desirable component (i also the component that is prone to coke formation). In a typical visbreaking method, crude oil charge material or residual oil charge material is passed through a heater and heated at 425 to 525 degrees at a pressure of 450 to 7000 kPa.
Heat to temperature C. Light gas oil can be recycled to reduce the temperature of the effluent stream. The cracked products from the reaction are flash distilled, the vapor overhead stream is distilled into light fraction overhead products such as gasoline and light gas oil residues, and the 7α residue is vacuum purified into heavy gas oil fractions and residual tar. stay An example of the visbreaking method mentioned above is
・The Oil Ends Journal
nd Gas Journal 57:46 (1959
Be
Thermal visbreaking of
Heavy Residence Youth (Ther+nal Visbr
eakingof l1eavyRe5idues)
;Hydro-bon processingll droc
arbon Processin (January 1979) pp. 131-136 [Visbreaking;
eaking;＾Flexible Process)
”; and U.S. Pat. No. 4,233,138.

European Patent Application No. 133.774 describes the treatment of heavy petroleum residues with H(A) containing at least 20% of the total hydrogen content.
r) hydrogen (a proton that is directly bonded to an aromatic ring and constitutes a moderate amount of aromaticity of the substance) and H(α) hydrogen (a proton that is bonded to a non-aromatic carbon atom itself that is directly bonded to an aromatic ring; 427 in the presence of 0.1 to 50% by weight based on the residual oil.
of heavy petroleum residues, comprising exposing them to heating for a period corresponding to an equivalent reaction time of 250 to 1500 ERT seconds at a temperature of Describes the visbreaking method. The hydroaromatic component used in this process is a thermally stable polycyclic aromatic/hydroaromatic distillate hydrogen donor, preferably obtained from one or more petroleum refining operations. It is a hydrogen donor substance. This hydrogen-donating solvent usually has a nominal average boiling point of 200-500°C and 0.85°C.
Examples of suitable hydrogen donor materials with nominal densities of ~1,1 g/cc are highly aromatic raw petroleum refinery streams such as fluid catalytic cracker main distillation column bottoms and fluid catalytic cracker light cycle oils. and thermophore catalytic rubking device syntower residues are very suitable, all of which include, for example, naphthalene, dimethylnaphthalene, anthracene, phenanthrene, fluorene, chrysene, pyrene, veraline, diphenyl, benzothiophene, tetralin and didronaphthalene. Contains a significant proportion of polycyclic aromatic hydrocarbon components such as. The heat-resistant petroleum materials described above are resistant to conversion to lighter (lower molecular weight) products by conventional non-hydrogenation operations.

Typically, the above-mentioned petroleum refinery residues and recycle fractions are hydrocarbonaceous mixtures with an average carbon/hydrogen ratio of 1/2 or higher and an average boiling point of 230° C. or higher.

In the solvent extraction method of the present invention, (a) a liquid hydrocarbon charge containing aromatic components and non-aromatic components is brought into contact with an extraction solvent under heating to remove non-aromatics from the charge; a raffinate phase containing a major fraction of components and a minor fraction of extraction solvent and a major fraction of aromatic hydrocarbon components of the charge and a minor fraction of non-aromatogenic hydrocarbon components and a major fraction of extraction solvent; (b) cooling the extraction phase; and (C) decanting the cooled extraction phase to obtain pseudoraphinate containing most of the non-aromatic components of the extraction phase and the aroma of the extraction phase. Tribe ¥! According to the rule 4, the extraction medium is separated into a pseudo extract containing at least 20% of the total hydrogen. The object of the present invention is to provide a solvent extraction method characterized in that it has a hydro-aromatic content of H(α) hydrogen.

The pseudoextract obtained from the operation described herein as a double decantation operation is for use in methods using hydrogen donors, such as the visbreaking method described in European Patent Application No. 133,774. Ideal for Pseudoraffinate is advantageously used as a charge in other conventional catalytic cracking operations, the operating parameters of which are well known in the art. The pseudodraphinate can also be recycled to the first extraction step of the process of the invention to further produce lubricating oil stock.

First, referring to FIG. 1, a liquid hydrocarbon charge containing aromatic hydrocarbon components and non-aromatic hydrocarbon components, such as Arab Medium crude oil, is prepared using a suitable extraction solvent (in this case, a suitable solvent). (furfural) is introduced into the extraction column. The amount of extraction solvent can vary widely and is often between 100 and 30% of the feedstock.
It is within the range of 0% by volume. The extraction method of the present invention is intended to use conventional solvent extraction equipment operated under conventional conditions. For example, in a typical lube oil system, the extraction column is The raffinate phase is operated at The extraction column is operated at a temperature of 65 to 150 °C, preferably 80 to 120 °C, and the temperature at the top of the extraction column is 10 to 35
℃, preferably 15-30℃ higher.

The above-mentioned temperature distribution is optimal for carrying out the extraction harvest of the present invention. Under these conditions, the extraction phase usually contains a relatively small amount of non-aromatic components, e.g. 10-25% by weight of the initial charge.
Contains non-aromatic components.

By lowering the bottom temperature of the extraction operation, more of these non-aromatic components can be transferred to the raffinate phase, but this can only be achieved if the quality of the lubricating oil stock is reduced. Of course, if the quality of the lubricating oil stock is not a mandatory issue, the extraction column can be operated with different temperature profiles.

After collecting the extraction phase from the bottom of the furfural extractor,
The extraction phase is sent to a heat exchanger where it is cooled and separated into pseudodraphinate, which contains most of the non-aromatic components of the extraction phase, and pseudoextract, which contains most of the aromatic components. The greater the degree of cooling that is performed, the more aromatics can be transferred to the pseudo extract.

At a minimum, the cooling mentioned above should be sufficient to obtain a pseudo-extract with a hydroaromatic content of H(α) hydrogen of at least 20%, preferably up to 50%, based on the total hydrogen content. Cooling of the extraction phase to a temperature of 30-70°C, preferably 38-50°C is usually sufficient to obtain a pseudo extract as described above. The cooled two-phase stream is then separated in a decanter to obtain a pseudo-extract from which the furfural (or other solvent, as appropriate) is then removed, e.g. by distillation, to provide the hydrogen donor. It can be easily used as

The pseudodraphinate obtained from the double decantation process, enriched in non-aromatic hydrocarbon content, can be advantageously used as co-charge in catalytic cracking operations such as the I" CC operation or the '[' CC operation. Alternatively, the pseudodraphinate can be recycled to the first extractor to produce more lubricating oil.

The use of pseudoextracts as hydrogen donors in visbreaking is conveniently carried out in an apparatus of the type shown schematically in FIG. The hydrocarbon oil charge feedstock is sent through a conduit (22) to a visbreaking device (visbreaking heating device) (25). The charged raw material is passed through the conduit (50
) 0.1 to 50% by weight, preferably 0.1 to 20% by weight hydrogen donor/residual oil weight based on the charged raw materials. 0.001/1 to 0.2/1). In the visbreaking device (25), mild thermal decomposition of the residual oil occurs under visbreaking conditions, producing a visbreaking device effluent stream that travels by conduit (28).

Visbreaking operating conditions can be varied based on the nature of the heavy oil material, hydrogen donor pseudoextract, and other factors.9 Typically, the operation is between 350 and 485°C, preferably between 425 and 455°C. temperature in the range of 1 to 60 minutes,
Preferably it is carried out with a residence time in the range 7 to 20 minutes. E
The term "equivalent reaction time", also written as RT, is 427°C.
The severity of the visbreaking operation is expressed as the residence time in seconds in a reactor operated at Very generally, the reaction rate doubles for every 12-13°C increase in temperature. That is, a residence time of 50 seconds at 427°C is 50
ERT, and increasing the temperature to 456°C results in a 5 times harsher operation, or 300 ERT. Expressed as IERT, the output value is 76 ('p. It is operated with an equivalent reaction time of .

The pressure used in visbreaking equipment is usually sufficient to maintain most of the material in the reactor coil and/or soaker drum in the liquid phase. Although pressure is not usually considered as a limiting variable, the pressure used in visbreaking equipment is Efforts should be made to maintain a pressure high enough to maintain most of the material in the device in the liquid phase. Although some vapor formation in the visbreaking equipment is not harmful, some vapor formation is often unavoidable because some light fraction is produced during the visbreaking operation. Some visbreaking operations are performed at the visbreaking device coil outlet.
It is operated with ~40% vaporized material content. The lighter the solvent, the more vaporization will occur and the vapor will do less to improve cracking of the liquid phase material. Therefore, although operation in the liquid phase is preferred, large amounts of vaporization can also be tolerated. Pressures normally encountered in visbreaking equipment range from 170 to 10,480 kr'a, with the majority of equipment operating at pressures from 1,480 to 7,000 kPa. Such pressure is sufficient to maintain liquid phase conditions and obtain the desired degree of conversion.

The visbreaking unit effluent traveling by conduit (28) is cooled by mixing with the quench stream from conduit (31), and the visbreaking unit effluent is transferred via conduit (29) to the distillation column (30). The effluent is rectified and Cs-gases (C3
, C4 or below) and Cs-135°C naphtha sections are obtained. The 220-370°C gas oil section is removed as a residual oil stream passing through conduit (33), which section is connected to conduit (31).
The fuel oil can be recycled as a quenched stream through the fuel oil, recovered as heavy fuel oil (32), or mixed with cutter stock via conduit (33) to meet fuel oil product specifications.

The overhead section removed from the distillation column in conduit (34) provides a mixed liquid stream with a C6-off gas stream (38), primarily C8 or C1 and below, and C removed through conduit (40).
s to a chilled separator (36) operated under conditions effective for separation into 135°C naphtha sections. Due to the boiling range and quality of the hydrogen donor, it can remain in the resid fraction mentioned above and be used directly as a heavy fuel oil, thereby avoiding the need for separation. I can do it.

The use of pseudoextracts as hydrogen donors during visbreaking is not limited to the visbreaking apparatus/distillation column arrangement described above, from tubular reactors completely enclosed in heaters to soaking drum reactors. Any visbreaking equipment can be used ranging from soaking drum reactors in which most of the visbreaking reactions occur. Also, a combination of the two operations can be used, for example, the bulk of the visbreaking reaction can take place in the coil, and the remainder of the visbreaking reaction takes place in a soaking drum downstream of the coil. .

Similarly, distillation processes known in the industry treat the visbreaking device reactor effluent stream7. r police kh 1. Special (
di IFI 1 to 7- +HI In//'+Via)'l/-& ”///In operation, it is preferable to quench the visbreaking device outflow with a quenching stream as shown, but heat exchange Heat exchanger tubes, fin/fan coolers, or other conventional means for cooling the visbreaking effluent stream may also be used. However, in the arrangement described above, the heat exchanger tubes may accumulate coke. Due to the risks, the use of quenching streams is preferred.

The present invention will be further explained with reference to Examples (hereinafter simply referred to as "examples" unless otherwise specified).

The following examples illustrate the double decantation method of the present invention (Examples 1 to 3).
), illustrating the use of pseudoextracts as hydrogen donors in visbreaking (Example 4) and the use of pseudodraphinate in thermophoric catalytic cracking operations (Example 5).

The data set forth in Table 1 below describe the operating conditions of the furfural extraction column and decanter, and the properties of the pseudoraphinate and pseudoextract obtained.

Nail-1-1-person 11 (α), car day% 22 2
6 22 or more Tsuba-! Arab heavy residue oil base stock (580
vis-braking was carried out. The use of the Busoidra extract allowed the Visbroking apparatus to operate under more severe conditions, expressed as equivalent reaction time (ERT), as described above.

The operating conditions and visbreaking results are listed below.
00 Pseud Extract Example 1) --250 Visbrane Inlet Pressure, kl'a 4200
4200 outlet pressure, kPa 285
0-3200 2850-3200 Reactor temperature, °C 454 454 Residence time, seconds 130 150 Equivalent reaction time 700 8
00 bisbraing raw '〒mko
-Shame-Gasoline 3
12 331 119 distillate oil
176 +
IZ35:3 Cutter stock from outside 1428
914-514 (M required to meet heavy fuel oil specifications) These data indicate that more severe visbreaking equipment conditions are possible by adding pseudoextract as a hydrogen donor. , resulting in higher cullin and distillate yields and a significant reduction in the amount of cutter stock required to provide compliant heavy fuel oil (HFO).

0 reactor conditions and results for thermophore catalytic cracking of virgin gas oil (VGO) with and without the addition of pseudodraphinate of Example 2 are described below.

→-Mohoar Cooling Charge Speed VGOVGO C'Hi Pusozumi Tsufitotoshi 7 Ga or above? 7
Comb V G O26552655 Example 2 pseudotyfinate --397 gain (gΣ 1 mortar and catalyst circulation rate, ton/hour 870
870 catalyst/oil weight ratio 3.59
4.24LH3V 3.03
2.61 Reactor temperature, “C488496 Catalyst activity 47.5 4
7.5 Bell - Keiichi Gasoline 1436
1570 +134 distillate oil 48
0 540 4160 Heavy fuel oil
120 350 +230
The significant advantages obtained using the pseudodraphinate obtained according to the invention for 'T' CC operations will be evident from the above data; an increase in the operating severity is possible by using pseudodraphinate. As a result, production of gasoline, distillate oil, and heavy fuel oil increased.

[Brief explanation of drawings]

FIG. 1 is a schematic representation of the solvent extraction method of the present process carried out using a suitable solvent, namely furfural, and FIG. 2 is a visbrake using the pseudo extract obtained by the solvent extraction method as a hydrogen donor. A schematic diagram of the
In the figure: 22... Conduit, 25... Visbreaking device, 28... Conduit, 29... Conduit, 30... Distillation column, 31... Conduit, 32... Heavy fuel Oil, 33...
- Conduit, 34... Conduit, 38... Cs-exhaust gas flow,
40... conduit, 50... conduit.

Claims (1)

[Claims] 1. In the solvent extraction method, (a) a liquid hydrocarbon charging material containing aromatic components and non-aromatic components is brought into contact with an extraction solvent under heating to extract the charging material; a raffinate phase containing a major fraction of non-aromatic hydrocarbon components and a minor fraction of an extraction solvent and a major fraction of aromatic hydrocarbon components of the charge and a minor fraction of non-aromatic hydrocarbon components and an extraction solvent; (b) cooling the extract phase; and (c) decanting the cooled extract phase to obtain a pseudoraphinate containing most of the non-aromatic components of the extract phase. and a pseudo extract containing most of the aromatic components of the extraction phase and most of the extraction solvent, and the degree of cooling is such that the pseudo extract contains at least 20% of the total hydrogen hydroaromatics of H(α) hydrogen. A solvent extraction method characterized by a certain amount of content. 2. The solvent extraction method according to claim 1, wherein the solvent is furfural. 3. Performing the extraction step (a) in an extraction tower, 65 to 150
3. The solvent extraction method according to claim 1 or 2, wherein the solvent extraction method is operated at a temperature at the bottom of the extraction tower of 10°C and a temperature at the top of the extraction tower 10 to 35°C higher than the bottom temperature. 4. The solvent extraction method according to claim 3, wherein the extraction column is operated at a bottom temperature of 80 to 120°C and a top temperature of 15 to 30°C higher than the bottom temperature. 5. The solvent extraction method according to any one of claims 1 to 4, wherein the extraction phase is cooled to a temperature of 30 to 70°C in step (b). 6. The solvent extraction method according to claim 5, wherein the extraction phase is cooled to a temperature of 38 to 50°C in step (b). 7. Heavy petroleum residue at least 20% of the total hydrogen content
a hydroaromatic solvent having a H(α) hydrogen content of , wherein the hydroaromatic solvent is substantially free of extraction solvent. 0 based on the residual oil of the hydroaromatic solvent, which is a pseudo extract obtained by the method described in
．． 250 to 427 °C in the presence of 1 to 50% by weight
A process for visbreaking heavy petroleum residues comprising exposure to heating for a period corresponding to an equivalent reaction time of 1500 ERT seconds and recovering a fuel oil product having a viscosity lower than that of the feed residue. 8. Visbreaking at a temperature of 350-485℃, 1
8. The method of claim 7, wherein the method is carried out for ~60 minutes. 9. Visbreaking is 0.1-2 based on residual oil
9. A process according to claim 7 or 8, which is carried out in the presence of 0% by weight of a hydroaromatic solvent. 10. The method according to claim 9, wherein the amount of hydroaromatic solvent is 10 to 20% by weight.