JPS6146518B2 - - Google Patents

Description

[Detailed description of the invention]

Intermediate and high grade lubricants and asphalts have been developed over the years for many different applications. Whatever the intended use, lubricating oils or asphalts are stable, have high flash points,
They must maintain their properties over long periods of use. Separation of crude oil into base oils of various viscosities is commonly accomplished by vacuum distillation, followed by separate treatment of each fraction by solvent extraction and hydrorefining for specific applications. The equipment used to process the obtained crude oil will depend on the quality of the crude oil being processed and the desired product properties. These studies have become important as product quality has improved. In prior art equipment, large quantities of available crude oil were processed to produce the desired products. However, given the current scarcity of available crude oil, it is important to provide a method to reduce the amount of processed feedstock without reducing the amount of product produced. The present invention relates to such an improved method. This invention relates to a method for producing lubricating oil and asphalt. In a more particular aspect, the invention relates to an improved combination of processing steps for producing lubricating oil formulation base oils and asphalt formulation base oils. More particularly, this invention relates to improved vacuum distillation column operations for more selective separation of lubricating oil formulation and asphalt production fractions. In one particular aspect, the present invention provides a method for solvent extraction under conditions that specifically limit the volume of feed oil required to produce the desired lubricant formulation stock and asphalt formulation product. The number of seconds required for 60 ml of a lubricating oil fraction to pass through a capillary tube in a Saybolt Universal Viscometer at 38°C with a viscosity in the boiling range selected for easy hydrorefining (this defines the lubricating oil fraction). 100 is an idiomatic term used to
300 seconds, 300 seconds and 700 seconds neutral fraction recovery. Hereinafter, the fractions will be distinguished based on the measured values of this viscometer. In the combined operation of this invention, which includes vacuum distillation, furfural extraction, methyl ethyl ketone-aromatics extraction, and hydrorefining, the bottom pressure of the vacuum distillation column is maintained below 50 mm Hg, preferably at a bottom pressure of about 40 mm Hg or less. It has been found to be particularly advantageous to use a low-pressure drop vacuum distillation column operation, ie a low-pressure packed column operation, designed to operate under low pressure conditions. More specifically, in order to improve the quality of the asphalt production component, the vacuum distillation column of the present invention extracts an overflush fraction with a boiling point higher than the recovered 700 seconds neutral fraction [i.e., under the conditions in the vacuum distillation column]. The first distillate (5% distillate fraction) boils in a range with a boiling point of 535°C (995〓) or higher] is taken out from the bottom of the column, and this is collected together with a part of the residue at the bottom of the distillation column.
It is sent to the PDA (propane deasphalt) extraction zone. By implementing the processing concept of this invention, the capital investment of the combinatorial operation of this invention is reduced by as much as 10%. Utility consumption will be reduced by 30% and the amount of crude oil required will be reduced by 15%. Also, the lubricant quality of the product is improved and higher melting point paraffin waxes are obtained by the method of the invention. In the combined operation of this invention, the vacuum distillation column used to separate, for example, Middle East crude oil into the desired lubricant base oil, has a lower bottom pressure than conventionally used in normally packed columns. Maintain low pressure, pressure drop no more than about 15 mmHg. The vacuum distillation column used in this invention has a flash zone temperature of 366 to 390℃ (690℃).
~735〓) and 49~57℃ (120〓
The temperature at the top of the tower is maintained within the range of ~135〓). 100 for this inventive low pressure drop tower design
Other variable fractions such as the 300 sec and 700 sec neutral fractions, or two types of operations including the 250 sec neutral fraction or the 450 sec neutral fraction are identified in the table below. It becomes possible to collect it more selectively together with the flash fraction. The vacuum distillation column design of this invention is therefore a novel design. Low operating pressures with low pressure drops, preferably less than 15 mm Hg, are achieved by the use of preferably essentially packed columns containing very few, if any, distillation shelves. That is, conventional lubricating oil vacuum distillation columns use plate columns to separate fractions, and are typically operated at a total pressure of 60 to 100 mmHg. The pressure drop in a conventional vacuum plate distillation column is significantly greater than 15 mmHg, depending on the number of plates. On the other hand, in the method of the present invention, the vacuum distillation column is a packed column, so the operating pressure is 50 mmHg and 15
It operates with a pressure drop of less than mmHg, thereby allowing more effective separation of lubricating oil fractions with narrow boiling point ranges. Thus, the design and method of operation of the vacuum distillation column is unique in that it allows a more selective and narrow range of fractions to be recovered for processing into the desired pharmaceutical product by solvent extraction and hydrorefining. belongs to.

Table 1 The lubricating oil fractions of Table 1 recovered from the vacuum distillation column described herein are then subjected to further processing of furfural extraction and MEK extraction. Polycyclics are undesirable in lubricating oils because of their low viscosity index and poor stability. These polycyclic aromatics are removed by furfural extraction in the combined operation of this invention. The furfural extraction operation shown in the block diagram sequence consists of a suitable equipment or column arrangement for contacting the oil feed with a selective solvent and equipment for separating the solvent from the extract stream and the raffinate stream. This operation evaporates the solvent, and the amount of heat required for this purpose is usually large. Therefore, any savings achieved in this high cost process would greatly contribute to the efficiency of the operation. In the particular operation of this invention which processes fractions in the more selected boiling point ranges of the 100 s, 300 s and 700 s neutral fractions, significant savings in the conditions of the extraction operation are made only in the amount of material processed. However, it is possible to improve the amount of solvent (volume) and heat required. By treating the more selective and limited boiling range materials recovered as described above, excessive solvent treatment of the low-boiling fraction of a particular fraction and depletion of high-boiling subcomponents of the fraction can be avoided. Extensive solvent treatment can be avoided. These savings also contribute significantly to the savings of devices such as those described herein. More specifically, the 100 second neutral fraction furfural extraction uses 175% by volume of furfural based on the feed, and the furfural extraction column is
This can be achieved by operating at an effective temperature of approximately 90.6°C (195°) while maintaining a top/bottom temperature gradient of 104°C/82°C (220°/180°). The 300 second neutral fraction has an effective temperature of approximately 96°C (205〓) and a top temperature of approximately 110°C/87.8°C (230〓/190〓).
Bottom column temperature gradient 200% relative to feed
Furfural can be extracted with a volume of solvent. On the other hand, the 700 second neutral fraction is 225 volumes based on the feed with a top-to-bottom temperature gradient of about 129°C/113°C (265〓/235〓) at an effective temperature of about 121°C (250°C). Furfural can be extracted with % solvent. After removal of undesirable polycyclic aromatics, the relatively narrow boiling range lubricating oil fractions defined herein are then further subjected to solvent extraction and solvent dewaxing with a methyl ethyl ketone (MEK) solvent-aromatic solvent. The ketone solvent solidifies the wax into a transparent crystalline form. The aromatic component of the solvent increases the oil-dissolving ability of the solvent. In the MEK extraction operation, the wax-containing feed oil is mixed with a solvent and the resulting mixture is cooled to crystallize the wax. The cooled feed is continuously passed through to recover the wax cake. MEK dewaxing operations are carried out at temperatures several degrees below the pour point of the desired oil product in the temperature range 5°C to 20°C below. A liquid consisting of oil and solvent is thus recovered and separated to separate the dewaxed oil fraction from the solvent. In the combination processing of this invention, 50/
A 50 MEK/toluene solvent composition is commonly used to dewax the particular lubricating oil fraction. This is about
It can be varied by 25% by volume in either direction. Overtemperature for 100 seconds neutral fraction is approximately -28℃
(-20〓), the supertemperature for the 300 second neutral fraction is about -26°C (-15〓), and the supertemperature for the 700 second neutral fraction is -15°C (5〓). The amount of solvent used in the various steps of MEK solvent dewaxing varies for each fraction, but is kept at a minimum consistent with obtaining the desired results. The overflush fraction recovered from the bottom of the vacuum distillation column is combined with a portion of the vacuum distillation column residue and passed through a propane deasphalting step. In one particular example, an overflush fraction of about 4% by volume based on the crude feedstock is combined with a portion of the vacuum distillation column bottoms varying from about 10% to 60% by volume to create a PDA (propane deasphalter). equipment). The viscosity of the bright stock can be varied by varying the amount of residue passed through the PDA device. In a PDA device, the mixture defined above is treated with a propane solvent near the extreme temperature that dissolves the hydrocarbon phase but rejects the asphaltic material. In this inventive combination, this separation is facilitated by recovering the overflush fraction and combining it with the desired portion of the residue taken from the bottom of the vacuum distillation column. Elevating the temperature of propane in the range of conditions used in PDA operations, such as 38-65.6 °C (100〓-150〓) at the bottom and 65.6-82 °C (150〓-180〓) at the top, will cause its dissolution. Although the capacity is reduced, the selectivity is improved. On the other hand, increasing the propane to oil ratio further increases the sharpness of the separation. The operating pressure is sufficient to maintain the propane in the liquid phase. The heavy oil product of the PDA treatment is then subjected to furfural treatment and MEK treatment under conditions specifically selected to maintain substantially maximum yield of the oil product. FIG. 1 is a schematic arrangement diagram in a process diagram showing the combination processing method of the present invention in a block diagram. In the arrangement shown, the crude oil feedstock is introduced by conduit 2 into a vacuum distillation column 4 whose bottom pressure is maintained at about 40 mmHg. The pressure drop in vacuum distillation column 4 is approximately 15
It is mainly a packed tower adjusted to mmHg. This vacuum distillation column is adapted to produce the fractions described in Table 1 above, with a gas-oil fraction discharging from the top of the column via line 6 and a residue discharging from the bottom of the column via line 8. Operate under selected conditions. In one particular operation, the gas oil fraction is about 10% by volume of the feed and the remainder is about 11.5% by volume of the feed. The 100 second neutral fraction is removed via conduit 10. This is approximately 8.6% by volume of the feedstock. Any excess of this material over the desired throughput is transferred to conduit 12.
Excluded by. 300, which amounts to about 7.5% by volume of the feed material
A second neutral oil fraction is removed via conduit 14 and stream 16 for use in manufacturing intermediate grade products.
and is separated as stream 18 for use in producing high grade oil formulation products. Materials described in Table 1 as overflush boiling range materials and amounting to about 4.0% by volume of the feed are removed by conduit 26 from above the feed inlet at the bottom of the vacuum distillation column. A portion of the vacuum distillation column bottoms removed via conduit 8 is removed via conduit 28 and combined with overflush material in conduit 26 before passing via conduit 30 to PDA unit 32. The mixing and processing conditions of the overflush and residue in the PDA unit are such that an oil product comprising approximately 48.8% by volume of the feed to the PDA unit is obtained, and this oil product is removed via conduit 34. . The asphalt product of this process is removed via conduit 36. The heavy oil product in conduit 34 is then subjected to furfural extraction conditions to remove polycyclics, resulting in a product that is approximately 68% by volume of the oil stream fed thereto. The raffinate of the furfural extraction step is then passed via conduit 38 to a solvent dewaxing process carried out with a MEK-toluene mixture. In this process, process conditions are selected such that approximately 77% by volume of the feed is recovered as a dewaxed oily product. The resulting dewaxed oil product is then passed through a hydrorefining process via conduit 40;
Here, the dewaxed oil product is heated to 204-371℃ (400-700℃).
〓) (preferably 232 to 288 °C (450〓 to about 550〓)) and 14 to 42 Kg/ ^cm2 gauge pressure (200
~600 psig) with a hydrorefining catalyst. In one particular processing example, a 95 (viscosity index) heavy lubricating oil bright stock in conduit 40 is hydrorefined to a lighter colored product than 5 ASTM. This product is typically around 482°C (900°C
〓) Boil at above temperature and take out from conduit 42. The 700 second neutral oil fraction in conduits 22 and 24 is passed through a furfural extraction process for polycyclic removal. The extraction processing conditions are such that approximately 55% by volume of the oil feed in conduit 22 is recovered by conduit 44 and approximately 45% by volume of the oil feed in conduit 24 is recovered by conduit 46. The raffinate phase of the furfural extraction process recovered by conduits 44 and 46 is passed through the MEK solvent dewaxing process described herein. Conditions in the solvent dewaxing process are such that the oil product amounting to approximately 77% by volume of the feed in conduit 44 is transferred to conduit 48.
approximately 66% by volume of the feed in conduit 46
is selected such that it can be collected by conduit 50.
The oil product in conduit 48 made from 700 seconds neutral material is intermediate 97 dewaxed material. This material prepared for use as an intermediate formulation product may optionally be subjected to hydrorefining conditions. conduit 50
The recovered high-grade oil formulation product is subjected to hydrorefining temperature conditions and contact with a selected catalyst to improve the quality of this product to make it suitable for use as a high-grade formulation product. In this particular arrangement, 100 dewaxing materials are produced and conduit 52
is removed from the hydrorefining process. The 300 seconds neutral material recovered from the vacuum distillation is passed via conduits 16 and 18 to a furfural extraction step specifically designed to produce intermediate and high grade oil products, the former via conduit 54 and the latter via conduit 5.
6. The amount of intermediate oil furfural ruffinate is about 55% by volume of the feed, and the amount of high oil roughinate is about 45% by volume of the feed. Roughinate flows in conduits 54 and 56
A dewaxed oil product is solvent dewaxed with MEK and recovered by conduit 58 and a high grade oil is produced by conduit 60, and the intermediate oil in conduit 58 is optionally hydrotreated. This material is about 104 dewaxing material. The premium oil roughinate in conduit 60 is subjected to a hydrorefining process to remove aromatics and produce a stable turbine oil. The hydrorefined high oil is recovered via conduit 62 as 108 dewaxed material (300 seconds neutral) for formulation. Conduit 10
The 100 seconds neutral oil fraction collected from the vacuum distillation column is subjected to furfural extraction treatment and the roughinate portion of about 54% by volume of the 100 seconds neutral oil feed is transferred to conduit 64.
and separates into two oil streams in conduits 66 and 68, each oil stream in conduits 66 and 68 being solvent dewaxed with MEK. In this process, approximately 78% by volume of the oil feed in conduit 66 is transferred to conduit 7.
Approximately 83% by volume of the feed oil in conduit 68 is recovered as a dewaxed high oil formulation component through conduit 72. The dewaxed (100 seconds neutral) oil product recovered by conduit 70 is 106 and the high oil in conduit 72 is treated under hydrorefining conditions before being recovered as a 110 dewaxed product by conduit 74. to stabilize the oil. In the combined process described herein, the combined extraction phase is collected by conduit 76 and the combined wax phase is collected by conduit 78. To simplify understanding of the complex processing arrangement of this invention using known processing techniques,
The various furfural extraction steps, MEK solvent dewaxing steps, and hydrogenation steps are simply represented as rectangular block diagrams. However, especially for improved vacuum distillation recovery fractions and subsequent processing fractions,
It should be appreciated that the combination of overall treatments as described herein provides significant benefits. More specifically, by implementing the process concept of the present invention, it is possible to produce an equivalent amount of the desired product, formulation product, by 477 Kl (3000 barrels) less than using the prior art. It turns out that a huge amount of crude oil can be saved. For example, the improved design of vacuum distillation column and operation of this invention reduced crude oil 1
If 2,460 Kl (15,469 barrels (BCD)) is fed per calendar day, the fractions listed in Table 2 below will be obtained.

【table】

Table 1 An important side benefit obtained by implementing the process concept of this invention is the production of more selective components for the production of asphalt. More specifically, paving and industrial asphalts of all grades can be produced either directly from lubricating oil byproducts by either formulation and formulation followed by oxidation. In a particular aspect, asphalts with asphalt penetrations of 65, 90 and 200 are used in the following lubricating oil streams: (see block process diagram in Figure 1) vacuum distillation column residue (stream 8);
It can be prepared by combining some or all of the vacuum distillation column overflush (stream 26), the propane deasphalt (stream 36), and the furfural extraction stream (stream 76). The ability to formulate asphalt from lubricating oil byproducts is a valuable side benefit of the process of the present invention for the following reasons. (1) The cost of transporting, storing, and processing specific asphalt raw materials during block refining operations is eliminated. (2) The quality of lubricating oil by-products will improve from heavy oil to asphalt. (3) 149-260℃, which must be mixed with several of these high-viscosity lubricant by-product streams in order to meet heavy oil specifications.
There is no need to downgrade kerosene (300-500〓). Selective formulation alone or selective formulation followed by oxidation of these by-product streams can produce asphalt of very good quality. For example, high 90 penetration quality asphalt can be made by selective blending and oxidation of vacuum distillation column residue, vacuum distillation column overflush, and propane deasphalt stream to have the properties shown in Table 3. Table 3 Centistokes (cs) at viscosity 70℃ (158〓) 485 Penetration (77/100/5) 86 Viscosity - Penetration 41700 Softening point [℃ (〓)] 45℃ (113〓) Rotating thin film Furnace test elongation 15℃ (59〓) 85 1.6mm (1/16″) Thin film furnace test elongation
25°C (77〓) > 140 From the information presented here it can be observed that a large number of asphalts can be manufactured by simply compounding to meet the viscosity-penetration regulations (which only exist in Australia) as specified below. . These asphalts are of fairly low grade and not all of them pass the prescribed tests. Additionally, selective oxidation of various formulations can be performed to suit various penetration and viscosity requirements. The Australian Road Research Board (ARRB) Asphalt Regulation was chosen as the criterion for evaluation in order to illustrate the utility and value of using this route for asphalt production. These regulations are currently the strictest in the entire world.
Recognizes asphalt manufacturers that asphalt that passes this ARRS specification for a particular penetration grade will easily pass less stringent regulations in other countries around the world, including the United States. It is being The technology developed here therefore has worldwide utility in other lubricating oil refineries and is even more valuable to asphalt manufacturers as the use of light feedstocks increases significantly in the future. As described in Table 3, pavement grade R65, R90 and
Asphalt products, including those of R200, differ in commercial importance, with R90 grades accounting for a larger proportion of the market. Current road asphalt has been largely produced from Kuwaiti crude oil, which produces asphalt that meets very strict regulations. However, with the recent depletion of this material, there is a significant economic incentive to develop other sources of asphalt. Tables 4 and 5 below set out the relatively strict Australian regulations for the above grades of asphalt. Among these regulations, the most difficult one for asphalt to satisfy is: (1) Viscosity - penetration condition - this value is 70℃ (158〓)
It is obtained by multiplying the viscosity (Stokes) at 25°C (77〓) by the penetration value at 25°C (77〓). (2) Thin film test (TFOT) conditions - There are three test methods for this. (a) 3.2mm (1/8″) Thin Film Furnace Test (TFOT) – A 3.2mm (1/8″) film of asphalt (50cc sample) was heated in a cylindrical flat bottom dish at 163°C (325°) for 5 hours. Heat. The weight change, penetration and often also the elongation of the thus oxidized sample are measured. (b) 1.6 mm (1/16") Thin Film Furnace Test (TFOT) - The same test conditions were used in this test as in the 3.2 mm (1/8") TFOT. However, as indicated in the test name, a thinner film sample (25 cc) was used and the test oxidation conditions were more severe. (c) Rotating Thin Film Furnace Test (RTFOT) - This test also
Perform at 163°C (325〓) but use a shorter period (125 hours). As indicated in the test name, the sample container is constantly rotated during the oxidation period to ensure a more uniform oxidation of the entire asphalt sample.

【table】

[Table] Table 5 Current ARRB provisions required by specific states The provisions listed in Table 4 are common to all states. The following test conditions are mandatory in the specific areas listed below. : South Australia (Main Roads Authority) Asphalt R90 - Viscosity - Penetration 40,000 - 60,000 (Within these limits, a range of 10,000 of 43,000 - 53,000 was specified for products produced by Aramco, and before that change Rotating thin film furnace test (RFOT) according to California test method 346-C specified in March 1966, followed by elongation test at 15°C (5 cm/min) Minimum Elongation conditions 20cm Asphalt R200−Viscosity−Penetration 30000−
60000 New South Wales (Main Roads Authority) Asphalt R90−Viscosity−Penetration 40000−
60000 thin film furnace test (1.6mm), then 25℃
Elongation in (ASTMD1754/D113) Minimum elongation condition 60cm Asphalt R200−Viscosity−Penetration 32000−
60000 Other States In addition to the requirements in Table 1, Viscosity-Penetration 40000-60000 (for R90) Viscosity-Penetration 32000-60000 (for R200) To proceed with the combined process of this invention Warm,
A program was conducted to evaluate five lube oil refining byproducts described below. The vacuum distillation column (VT) bottoms stream, propane deasphalted (PD) tar or solvent deasphalted tar, vacuum distillation column (VT) overflush, and two furfural extraction phases are described in Table 6.

[Table] The production of R90 grade asphalt is performed using 10% by weight PD (propane deasphalt) tar as described in Table 6.
An attempt was made by combining it with VT residual flow. This formulation (A57) was within the penetration specifications for R90 grade asphalt, but was lower than the minimum viscosity-penetration requirement of 40,000 as set forth in Tables 4 and 5. Increasing the PD tar concentration to 15% by weight (formulation A58) results in an asphalt that satisfies the penetration requirements and has an improved viscosity-penetration value of about 40406. PD
Attempts to formulate products with improved viscosity-penetration values by increasing tar concentration were unsuccessful because the resulting formulations were below the minimum penetration specification. 60 wt% VT residue (vacuum distillation column residue), 30 wt% PD tar and 10 wt%
Preparations containing overflush fluid (preparations
A71) was built. This formulation (A71) also did not satisfy the penetration conditions and the viscosity-penetration conditions. Reducing the overflush fluid concentration to 5% (formulation A72) results in a penetration of 100, which is the highest value for the R90 product. The viscosity-penetration value is lower than the lowest value of 40000. 2 overflush liquid
Reduced to wt% (formulation A96) to R90
It no longer satisfies the minimum penetration regulations. concoction
Replacing a portion of the PD tar of R96 with softer vacuum distillation column residue (formulation A74) resulted in an asphalt that was within the penetration specifications of R90 and also met the viscosity-penetration specifications. . Same result with PD tar 35
% by weight and formulation A73 containing 5% by weight of overflush liquid was also obtained. From the foregoing it is clear that by simply mixing the various streams according to the process of this invention, an acceptable asphalt meeting the desired specifications can be produced. Attempts were made to oxidize various formulations of streams in order to obtain asphaltic materials with even better physical properties. In an attempt to make R90 specification asphalt, a formulation consisting of 90% by weight VT residue and 10% by weight overflush fluid was made and subjected to oxidizing conditions. The results obtained are summarized in Table 7.

[Table] 59〓 after rotating thin film furnace test (RTFOT) by oxidation of the above formulation to the specified penetration range of R90.
Asphalt was produced that met strict specifications except for elongation at (15°C). As observed in Table 7, formulation F8-8 satisfies strict specifications, including 1/16" TFOT and viscosity-penetration conditions. Reformulation of second sample of F8-8 Oxidation of the above formulation to the R90 material penetration range resulted in an asphalt that met all of the strict specifications except for the RTFOT elongation at 59㎓. It should be recalled that RTFOT elongation is required in Australia and a few other countries. Therefore, as shown by the 1/16" TFOT result, this asphalt is will satisfy known conditions.

【table】

Table: Each of the asphalts in Table 8 contains a significant amount (30% by weight) of PD tar. 15wt% VT
Overflash, 55 wt% VT residue and
The F8-20 formulation containing 30% by weight PD tar is
RTFOT elongation and viscosity-penetration conditions were not satisfied. However, in this case, as stated above, this asphalt would meet the requirements of asphalt users outside Australia. This reduces the overflush concentration to 10% by weight (formulation
F8-9), the RTFOT elongation was improved, but the viscosity-penetration conditions were not satisfied. Reduced overflush to 8% by weight (formulation F8−
(31) and this formulation was oxidized to meet R90 specifications. Formulation (F8-31) met all of the stringent R90 specifications described herein. Formulation containing 7% by weight overflesh (F10−10)
It also has a viscosity-penetration value of 40296 and satisfies the viscosity-penetration regulations. Formulations containing 5% by weight overflush (F10-11) meet the minimum specified value.
It gave a viscosity-penetration value of less than 40,000. Namely, from Table 8, asphalt containing 8% by weight of VT overflesh, 30% by weight of PD tar and VT residue as a remainder (formulation F8-31) and 7% by weight of overflesh.
It can be seen that F10-10 is a satisfactory asphalt. However, when the viscosity-penetration specification is reduced to less than 40,000, other formulations also yield satisfactory R90 asphalts, as seen in Table 8. The effect of varying PD tar concentration from 30% by weight was studied and reported in Table 9.

【table】

[Table] Reducing the PD tar concentration (formulations F9-24 and F9-25) results in asphalts that satisfy the ARRB elongation requirements. A PD tar concentration of 10% by weight satisfies the viscosity-penetration conditions, but produces asphalt with an elongation lower than the required minimum elongation. PD
Increased tar concentration to PD tar 40% by weight, VT
The tar containing 40% by weight residue and VT overflush (formulation F9-27) was excellent.
This produces asphalt that has RTFOT elongation but does not meet the viscosity-penetration specifications. Evaluation of combining furfural extract with PD tar and VT residue and oxidizing the resulting formulation to a predetermined grade can provide another option for the use of VT overflush fluid.
For example Bright Stock Furfural extract 10% by weight, PD tar 30% by weight and VT residue 60% by weight
After oxidation, the formulation containing R90 satisfied the specified conditions for the R90 rating described herein. Similar results can be obtained by using 840〓~1040 instead of bright stock in the above formulation.
It was also obtained by replacing the heavy neutral furfural extraction fraction boiling with 〓. The production of R200 grade asphalt was studied by blending VT overflush with VT residue to meet the penetration limit value for R200 products. From this study it was determined that 5% to 10% VT overflush can be used in the formulation to meet the R200 product penetration specifications.
To confirm this range more clearly, overflush liquid 7.5%, 8% and 8.5% by weight
Formulations A54, A82 and A83 containing
Tested. The data obtained are listed in Table 10 below.

【table】

[Table] From the data in Table 10, formulations A54 and A84 are
It is observed that it gives an initial penetration value very close to the limit value for the R200 penetration specification. but
A82 was found to be a satisfactory formulation. An alternative method of producing R200 grade asphalt was discovered during the course of experimentation. This leaves VT overflush 10% by weight (original penetration is 235)
and then oxidizing the formulation to R200 penetration specifications. The production of R65 penetration grade asphalt was also investigated. The first attempt in this study was to develop VT to achieve this grade of penetration regulation (60-70 penetration).
It consists of preparing the residue and PD tar.
The data in Table 11 shows that formulation A97 containing 30% by weight PD tar and formulation A98 containing 35% by weight PD tar meet the requirements for R65 grade products. That is, R65 grade asphalt is PD tar and VT obtained as described in this specification.
by first compounding the residue to meet the penetration specifications for this grade.

【table】

[Table] The formulation range for producing R65 asphalt can be determined from the penetration composition plot shown in Figure 2. This plot shows that the PD tar concentration can be increased from a minimum of 29 wt.% to a maximum of 37.5 wt.%, with a preferred range of 31 wt.% to 35 wt.%. It has also been found that formulation F8-7, consisting of 90% by weight VT residue and 10% by weight VT overflush, satisfies the R65 penetration specification when aerated to the R65 penetration rating. Oxidation of the asphaltic material described above is accomplished by air blowing. It is known from prior experience that air blowing changes the properties of this asphalt. Air blowing is normally accomplished at temperatures within the range of 400° to 500°. The reaction achieved by this air blowing is one of dehydrogenation followed by polymerization or condensation. Air blowing is accomplished by passing the pretreated feed through the column countercurrently with the air flow. It is to be understood that, having thus described the invention generally and discussed specific embodiments thereof, no undue limitations should be placed on the embodiments other than as provided in the claims. Should. The outline of this invention is as follows. (1) A pressure below 50 mmHg adjusted to separate multiple different relatively narrow boiling range lube oil base oil fractions from the overflash fraction of the initial fraction higher than 1000〓 and from the vacuum distillation residue fraction. The reduced amount of crude oil is processed through a low pressure drop vacuum distillation column maintained at a low pressure drop, and each of the relatively narrow boiling range fractions is processed through multiple solvent extraction steps to remove undesirable aromatics and waxes. , the overflush fraction, mixed with a selected portion of said residual fraction, is passed through a propane deasphalt step to remove the raffinate phase and asphalt, sufficient to yield a lubricant formulation fraction of average and premium grades. A method for producing a plurality of different lubricating oil stocks and high boiling by-products from a reduced amount of crude oil, the process comprising forming a ruffinate phase and solvent extracting the ruffinate phase to produce an improved bright stock. (2) The method according to item (1), wherein the lubricating oil basic fraction is sequentially passed through a furfural solvent extraction step and a methyl ethyl ketone solvent extraction step. (3) The process of paragraph (1) or (2), wherein the different base fractions are separated to produce a quantity of premium grade lubricating oil, and at least the premium grade material is hydrorefined. (4) Any of the above, wherein the vacuum distillation column is operated to produce a 100 second neutral fraction and at least one other fraction boiling between the 100 second neutral fraction and the overflush fraction. The method described in paragraph 1. (5) operating the vacuum distillation column to produce a 100 second neutral fraction, a 250 second neutral fraction, and other fractions that boil at a lower temperature than the overflush material;
The method according to any one of the preceding items. (6) The pressure of the vacuum distillation column does not exceed 40 mmHg and
A method according to any one of the preceding paragraphs, operating at a pressure drop of less than 15 mmHg. (7) The method according to any one of the above items, wherein the vacuum distillation column is a packed distillation column. (8) The method according to any one of the above items, wherein the raffinate product of the propane deasphalting step is hydrorefined after furfural solvent extraction and methyl ethyl ketone solvent extraction. (9) The recovered high-boiling byproducts are the vacuum distillation column overflush fraction, the vacuum distillation column residue separated from the overflush fraction, and/or the mixture of the vacuum distillation column residue and the overflush fraction by solvent desorption. A method according to any one of the preceding clauses, comprising tar obtained by grinding. (10) The method according to item (9) above, wherein asphalt is produced by blending two or more of the substances. (11) The overflush fraction boils at about 995〓 at its 5% distillation point and about 1198〓 at its 95% distillation point, as described in paragraph (9) or (10). Method. (12) Asphalt is any one of paragraphs (9) to (11) consisting of a mixture of vacuum distillation column residue, propane deasphalted tar, and less than 10% overflush fraction.
The method described in section. (13) Asphalt is the residue of the vacuum distillation column and 5~
A process according to paragraph (9) or (10), comprising a formulation of 10% by weight overflush fraction. (14) Asphalt is the residue of the vacuum distillation column and 7.5~
A process according to any one of paragraphs (9) to (11), comprising a formulation of 8% by weight overflush fraction. (15) Asphalt remains in the vacuum distillation column and approx.
～Item (9) consisting of a preparation of about 35% by weight of tar～
The method described in paragraph (11). (16) The method of item (15) above, wherein the formulation contains about 31-35% by weight tar. (17) The method according to any one of items (9) to (11), wherein the asphalt comprises about 90% by weight of vacuum distillation column residue and about 10% by weight of overflush. (18) The method according to any one of items (9) to (17), wherein the asphalt is subjected to an oxidation treatment to modify its properties. (19) A method for producing a lubricating oil stock essentially as shown in FIG. (20) A method for producing asphalt substantially as shown in FIGS. 1 and 2. (21) Lubricating oil stock manufactured according to each of the above items. (22) The method described in any one of paragraphs (9) to (21). Asphalt manufactured by.

[Brief explanation of the drawing]

Figure 1 is a diagrammatic layout in the form of a block process diagram representing the combination of processing steps of this invention, and Figure 2 is a diagrammatic layout of the process for producing R65 grade asphalt.
FIG. 3 is a diagram showing the relationship between the proportion of PD tar in a mixture of VT residue and PD tar and the penetration degree. In the diagram: 2... (crude oil feed) conduit, 4... vacuum distillation column, 6... (gas oil discharge) conduit, 8... (residue) conduit, 10... (100 seconds neutral oil) conduit, 12
...(100 seconds neutral oil excess) Conduit, 14...(300
Neutral oil) conduit, 16... (300 seconds neutral oil)
Conduit, 18... (300 seconds neutral oil premium grade) Conduit, 20... (700 seconds neutral oil) Conduit, 22...
(700 seconds neutral oil average grade) conduit, 24... (700 seconds neutral oil premium grade) conduit, 26... (overflush) conduit, 32... Propane deasphalt equipment, 3
4...(heavy oil) pipe, 36...(asphalt) pipe, 42...bright stock, 48...
(700 seconds neutral oil average grade) Lubricating oil preparation product, 52...
(700 seconds neutral premium grade compounding product) Conduit, 58
...(300 seconds neutral medium grade compounding product) Conduit, 62...
...(300 seconds neutral premium grade compounding product) conduit,
70... (100 seconds neutral oil medium grade preparation product) conduit,
74... (100 seconds neutral oil premium grade formulation product) conduit, 76... (aromatic removal) conduit, 78...
...(Row phase) conduit.

Claims (1)

[Claims] 1 The atmospheric distillation residue is converted into lubricating base oil fractions of multiple types with different boiling point ranges in a vacuum distillation packed column in which the pressure at the bottom of the vacuum distillation column is maintained at 50 mmHg or less and the pressure drop within the column is 15 mmHg or less. , first distillate 535
Separated from other fractions boiling above °C and vacuum distillation residues, each of the lubricating base oil fractions of a number of different boiling point ranges is processed through multiple solvent extraction steps to remove undesirable aromatics and waxes. removing the fraction to produce a lubricating oil formulation fraction, mixing the other fraction with the vacuum distillation residue and treating it in a propane deasphalting step to produce a ruffinate phase and an asphalt phase;
A method for producing a plurality of different lubricating base oils and higher boiling by-products from atmospheric distillation residues, comprising solvent extraction of the ruffinate phase to produce bright stocks.