Patent Grant
8864981
The present invention is generally directed to methods of producing rubber processing oil (RPO) with low polycyclic aromatics content and, in particular, to techniques whereby deasphalted residual oil (DAO) and aromatics-rich extracts from DAO are used as blending stock to improved the properties of mixed feedstocks that are used to produce environmentally qualified RPO on a consistent basis.
Rubber processing oils are used as plasticizers or extenders in the production of rubber. RPO is normally co-produced in the lube oil refining process, including the extraction process. In the extraction process, the raffinate phase is refined to produce the base stock for lube oil blending while the extract phase is further processed to produce the RPO. Conventional techniques produce RPO with polycyclic aromatics (PCA) content of 5 wt % or higher. While the European Union has mandated that the PCA content in RPO (as measured by Method IP346) to be less than 3 wt %, the RPO must still be rich in aromatics in order soften rubber components during processing. In particular, the environmentally approved RPO must exhibit a total aromatics (TA) content of more than 50 wt %, a PCA of less than 3 wt %, an aniline point that is lower than 80° C., a kinematic viscosity from 15 to 30 mm2/s at 100° C., and a flash point that is higher than 250° C.
Maintaining RPO quality while reducing its PCA content to comply with the new environmental regulations has been the goal of intense research. Techniques to reduce the PCA such as by selecting suitable feedstocks for blending or employing additional processing to produce acceptable RPO are described, for example, in U.S. Pat. No. 7,186,876 to Manton et al., EP 0 417 980 A1 to Glenz, U.S. Pat. No. 5,846,405 to Aldous et al., U.S. Pat. application. No. 2005/0272850 to Jois et al, U.S. Pat. No. 6,878,263 to Kaimai et al., U.S. Pat. application. No. 2009/0020453 to Tanaka et al., and U.S. Pat. application. No. 2001/0045377 to Morishima et al. These techniques are not completely satisfactory because the RPOs produced have high PCA contents and/or high aniline points or the processes require stringent operating conditions and/or complex, expensive equipment.
The present invention is based in part on the recognition that, although DAO alone is not a reliable feedstock to produce acceptable RPO, DAO and the aromatics-rich extract that is derived from DAO have low PCA contents, relatively low aniline points, and high flash points as compared to other sources of feedstock. These attributes make them suitable blending stocks to improve the properties of mixed feedstocks that consistently produce environmentally qualified RPO through an extraction process operating under low solvent-to-oil ratios and moderate extraction temperatures.
The DAO as a blending feedstock is preferably prepared by initially distilling a petroleum crude oil under atmospheric pressure to generate a bottom residual oil, which then undergoes vacuum distillation to yield a bottom residual oil. DAO is subsequently produced by removing the asphalt from the vacuum bottom residual oil through extraction with propane or other light paraffin solvent to reduce the carbon residue to less than 2 wt %. The extract of the DAO extraction, the other blending feedstock, is preferably generated as a co-product in the production of the bright stock of lubricating oil.
Either the DAO or the extract of the DAO is mixed with the extract from a petroleum fraction boiling in lube oil range, which is, preferably, co-produced in the production of the lube base oil. The mixed feedstock is then fed to a lower portion of a liquid-liquid extractor column to counter-currently contact an extractive solvent, which is introduced into an upper portion of the extractor. A raffinate stream, that is withdrawn from the top of the extractor, is stripped to remove the solvent to produce the environmentally qualified RPO product having the following properties: (1) PCA of less than 3 wt % (method IP346), (2) total aromatics (TA) of more than 50 wt % (method IP391) or aromatic carbons (% CA) of more than 20 wt % (method D2140), (3) aniline point that is lower than 80° C. (method D611), (4) kinematic viscosity from 15 to 30 mm2/s at 100° C. (by method D445), and (5) flash point that is higher than 250° C. (method D92).
In one aspect, the invention is directed to a process for preparing an environmentally safe RPO having the above attributes, which includes the steps of:
In another aspect, the invention is directed to a process for preparing RPO which includes the steps of:
In yet a further aspect, the invention is directed to a process for preparing RPO which includes the steps of:
The invention provides novel feedstock mixtures that are used to produce RPO that complies with recently enacted environmental guidelines. The RPO is produced continuously with the feedstock mixtures or, in the alternative, the feedstock mixtures are processed sequentially in a so-called “blocked out” operation using existing extraction process equipment to minimize capital and operating costs.
The viability of using DAO and aromatics-rich extracts derived from DAO as feedstock sources to produce RPO is supported by an analysis of related experimental data disclosed in the prior art. For example, U.S. Pat. No. 6,248,929 to Kaimai et al, in columns 11 and 12, describes distilling Arabian light crude oil under reduced pressures and thereafter subjecting the residues to propane deasphalting. Reported properties of the DAO are presented in Table 1:
As is evident, the DAO PCA content is quite low (from 1 to 1.3 wt %) and the aniline point is relatively low at 110° C. In addition, the '929 patent reports that the DAO and a comparative distillate fraction, boiling in the lube base oil range (340 to 650° C.) that was derived from the same vacuum distillation of the Arabian light crude were subject to furfural extraction. Table 2 summarizes the physical data for the extracts derived from both feedstocks as reported in Comparative Examples 1-1 and 1-2 of the '929 patent.
As is apparent, the extract from the DAO contains significantly less PCA than the extract from the distillate boiling in the lube base oil range. The present invention recognizes that, with respect to PCA content and aniline point, the extract from the DAO is comparable to or even better than DAO by itself as a blending stock in the production of RPO through an extraction process. Finally, as a result of the high boiling ranges of the DAO and of the extract from DAO, the flash point of the RPO produced from these feed mixtures will also increase.
With the present invention, the DAO as one of the blending stocks of the feed mixtures for producing RPO is preferably prepared by first distilling a petroleum crude oil under atmospheric pressure to generate a bottom residual oil which is then subject to vacuum distillation to obtain a second bottom residual oil. Thereafter, the DAO is generated by removing the asphalt content in the vacuum bottom residual oil through extraction with propane or other light paraffin solvents to reduce the carbon residue to less than 2 wt %.
The extract of DAO, which is the other blending stock, is preferably generated as a co-product in production of the bright stock of the lubricating oil, by contacting the DAO with an extractive solvent in a liquid-liquid extractor under relatively mild conditions.
In a preferred process of producing the RPO, the extract of DAO is mixed with an extract of petroleum fraction boiling in the lube base oil range, which is co-produced in the production of the lube base oil. The mixed feedstock is then fed to lower portion of a liquid-liquid extractor to counter-currently contact with an extractive solvent, which is introduced into the upper portion of the extractor. A raffinate stream is withdrawn from the top of the extractor, which is stripped of solvent to produce the RPO product, while extract stream is removed from the bottom of the extractor for further processing.
In another preferred process for producing the RPO, the DAO is mixed with an extract of a petroleum fraction boiling in the lube base oil range. The mixed feedstock is extracted counter-currently with an extractive solvent in an extractor. The RPO product is yielded from the raffinate stream that is withdrawn from the top of the extractor after the solvent content is removed.
In a third preferred process for producing the RPO, an extract of a petroleum fraction boiling in the lube oil range is extracted counter-currently in an extractor. The raffinate stream that is withdrawn from the top of the extractor is stripped of solvent and then mixed with appropriate amounts of DAO to produce the RPO product.
A method of producing RPO by extracting feed mixtures containing the extract of DAO and the extract of vacuum distillate oils is shown in
Lights or tail gas 2 are removed from the top of vacuum distillation column 101 for proper disposal and a vacuum residue with a boiling range of 500-900° C. is fed from the bottom of column 101 through line 6 into a deasphalt column 102. The vacuum residue is extracted with propane or other light paraffinic solvent, which is fed into column 102 through line 9A, to remove the asphalt and thereby produce deasphalted oil (DAO) that has less than 2 wt % carbon residue. The asphalt-rich raffinate stream is removed via line 9B. The DAO is withdrawn via line 8A as the extract from the top of column 102 and transferred to a stripping column 108 where the DAO and deasphalting solvent are separated.
The treated DAO is fed through line 8B into extractor column 104 where an extractive solvent enters the upper portion of extractor column 104 via line 22 to contact the feed mixture counter-currently. The column top temperature is maintained within a range of 90-150° C. and preferably from 100-140° C. whereas the column bottom temperature is maintained within a range of 70-130° C. and preferably from 80-110° C. The solvent-to-oil (DAO) ratio within column 104 is 1.0-5.0 and preferably 2.0-4.0. The extract yield ranges from 20 to 50%. A raffinate stream 12 is withdrawn from the top of extractor 104 and after solvent is removed from the raffinate and recycled to the extractors, a bright stock for lubricating oil is produced. In the meantime, an extract stream 13 is taken from the bottom of extractor 104.
The extract stream in line 11 (the extract of the vacuum distillate) is mixed with the extract stream in line 13 (the extract of the DAO) at a volume ratio of from 90:10 to 50:50 and preferably from 80:20 to 60:40. The mixed extract 14 is fed to a lower portion of extractor column 105 where the feed is subject to counter-current extraction with an extractive solvent 24 that is introduced into an upper portion of the column. The top temperature of extractor 105 is maintained at a range from 40-100° C. and preferably from 60-90° C. whereas the bottom temperature of the extractor is maintained at a range of 30-70° C. and preferably 40-60° C. The solvent-to-oil volume ratio for the extraction is in the range of 1.0-5.0 and preferably 1.0-3.0.
A raffinate stream 15 is withdrawn from the top of extractor 105 and transferred to a solvent recovery column (SRC) 106 where solvent is stripped from the raffinate. Recovered solvent 17 from the top of SRC 106 is recycled to extractor columns 103, 104 and 105 via lines 21, 22, 23, and 24. The rubber processing oil product 18 that is recovered from the bottom of SRC 106 meets or exceeds the new environmental standards with respect to PCA, aniline point, kinematic viscosity, total aromatics (TA), flash point, and other properties for RPO. An extract stream 16 is withdrawn from the bottom of extractor 105 and transferred to SRC 107 where the solvent is stripped off. Recovered solvent 19 is recycled to extractors 103, 104, and 105 via lines 21, 22, 23, and 24, while a solvent-free extract 20 is recovered from the bottom of SRC 107.
Since the operating conditions for extractor columns 103 and 105 are similar, the continuous process illustrated in
The polar extractive solvent for the process can include, for example, furfural, N-methyl pyrrolidone (NMP), dimethyl sulfoxide (DMSO), propylene carbonate, and mixtures thereof. The preferred solvent is furfural. Suitable extractors for the invention, include, for example, columns with trays, columns with packings, columns with rotating discs, and pulse columns.
A method of producing RPO by extracting feed mixtures containing the DAO and the extract of vacuum distillate oils is shown in
Lights or tail gas 32 are removed from the top vacuum distillation column 201 while vacuum distillation residue 36 is fed from the bottom into a deasphalt column 202. The vacuum residue is extracted with propane or other light paraffinic solvent, which is fed into column 202 through line 39A, to remove the asphalt and thereby produce deasphalted oil (DAO). The asphalt-rich raffinate stream is removed through line 39B. The DAO is withdrawn via line 38A as the extract from the top of column 202 and transferred to a stripping column 208 for solvent removal.
The DAO recovered via line 38B from stripping column 208 is mixed with the extract 41, of the lube range distillate from the bottom of extractor 203, at a volume ratio of from 10:90 to 50:50 and preferably from 20:80 to 40:60. The mixed extract 42 is fed to a lower portion of extractor column 204 and contacts counter-currently an extractive solvent 51, which is introduced through an upper portion. The operating conditions of extractor 204 can be the same as those of extractor column 105 of
A raffinate stream 43 from the top of extractor 204 is stripped of solvent in solvent recovery column (SRC) 205 to yield rubber processing oil 46. Recovered solvent 45 from the top of SRC 205 is recycled via lines 49, 50, and 51. Similarly, an extract stream 44 from the bottom of extractor 204 is stripped of solvent in SRC 206. Recovered solvent 47 from the top of the column is recycled via lines 49, 50 and 51 while a solvent-free extract 48 is recovered from the bottom.
Since the operating conditions for extractor columns 203 and 204 are similar, the continuous process illustrated in
Finally, a method of producing RPO by mixing the DAO with the raffinate from an extraction of the extract of vacuum distillate oils is illustrated in
Lights or tail gas 62 are removed from the top vacuum distillation column 301 while vacuum distillation residue 66 is fed from the bottom into a deasphalt column 302. The vacuum residue is extracted with propane or other light paraffinic solvent, which is fed into column 302 through line 69A, to remove the asphalt and thereby produce a deasphalted oil (DAO) and solvent stream which is withdrawn via line 68A as the extract from the top of column 302 and transferred to a stripping column 307 where the deasphalting solvent is removed. The asphalt-rich raffinate is removed from column 302 through line 69B.
The extract of vacuum distillate oils from the bottom of extractor column 303 is fed via line 71 to a lower portion of extractor column 304 where it is counter-currently extracted by a solvent 81, which is introduced to the upper portion of extractor 304. A raffinate stream 72 is withdrawn from the top of extractor 304 and fed to SRC 305 where solvent 74 is removed. A solvent-free raffinate 75, which is recovered from the bottom of SRC 305, is mixed with the DAO from line 6813 within restricted mixing ratios to produce a rubber producing oil 76. The mixing ratio of the solvent-free raffinate 75 to the DAO 68 is preferably controlled by the aniline point of the blended RPO product. If a lower aniline point for the RPO is desired, then a higher percentage of solvent-free raffinate 75 should be used. An extract stream 73 from the bottom of extractor 304 is stripped of solvent in SRC 306. Recovered solvent 74, 77 from columns 305, 306 is recycled through lines 79, 80, and 81 while a solvent-free extract 78 is recovered from the bottom. To produce qualified RPO with the desired properties, the operating parameters of extractor 304 can be regulated by measuring selected properties of raffinate 72 and establishing appropriate feedback control.
Again, since the operating conditions for extractor columns 303 and 304 are similar, the continuous process illustrated in
The following examples are presented to further illustrate the preferred embodiments of this invention and are not to be considered as limiting the scope of this invention.
In the process illustrated in
To demonstrate that environmentally qualified RPO can be produced from the feed mixture prepared in Example 1, the feed mixture was extracted in the laboratory with furfural. The Treybal experimental extraction method was used to precisely simulate a theoretical 5-stage counter-current extraction scheme, as shown in
As shown in Table 4, RPO with less than 3 wt % of PCA was produced from a mixed feedstock containing 70% extract from the distillate boiling in lube base oil range and 30% extract from a DAO with 56.1% yield at 50° C. and S/O of 1.5. The PCA content in the RPO can be reduced as low as 0.59 wt %, but at much lower RPO yield of 35.5%. Since RPO is produced as the raffinate of this extraction, the yield of RPO was found to be inversely proportional to both the extraction temperature and the solvent-to-oil volume ratio (S/O). Experimental data of the RPO yield from a one-stage laboratory extraction at various solvent-to-oil ratios and temperatures is presented in
Aniline point was not reported since the amount RPO generated from the laboratory extraction experiment was too small for the measurement. However, the aniline point is normally closely related to total aromatic (TA) content. Table 4 shows that the TA of RPO-1 is slightly lower than that of the commercial RPO (54 vs. 63 wt %), which is an indication that the aniline point of RPO-1 should be reasonably close to 80° C., since aniline point of the commercial RPO is only 68° C.
To further demonstrate the effectiveness of the invention, test runs were conducted in a commercial extractor, with throughput capacity of 5,000 barrels per day, to simulate operation of the extraction column 105 in
In this demonstration, the mixed extract is fed via line 14 to the lower portion of the commercial extractor while in a blocked out operation whereby furfural solvent was introduced into an upper portion of the commercial extractor to counter-currently contact the mixed feed. The top temperature of the extractor was varied from 68 to 85° C., while the bottom temperature of the column was set at 50° C. The solvent-to-oil volume ratio for the extraction was in the range of 1.8 to 2.1. A raffinate stream was withdrawn from the top of extractor and then transferred to a solvent recovery column. Solvent was recovered from the top while the RPO product was recovered from the bottom of SRC. The properties of the RPO are presented in Table 5.
From the commercial test run data, the RPO that is produced exhibited critical physical characteristics such as PCA, aniline point, kinematic viscosity, total aromatics (TA), and flash point that met or exceeded the new regulatory standards.
The foregoing has described the principles, preferred embodiment and modes of operation of the present invention. However, the invention should not be construed as limited to the particular embodiments discussed. Instead, the above-described embodiments should be regarded as illustrative rather than restrictive, and it should be appreciated that variations may be made in those embodiments by workers skilled in the art without departing from the scope of present invention as defined by the following claims.
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| Number | Date | Country |
|---|---|---|
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| Number | Date | Country | |
|---|---|---|---|
| 20120181220 A1 | Jul 2012 | US |
