CN110616084A - Process for producing crude white oil - Google Patents
Process for producing crude white oil Download PDFInfo
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- CN110616084A CN110616084A CN201810639711.1A CN201810639711A CN110616084A CN 110616084 A CN110616084 A CN 110616084A CN 201810639711 A CN201810639711 A CN 201810639711A CN 110616084 A CN110616084 A CN 110616084A
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- hydrocracking
- oil
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- crude white
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G65/00—Treatment of hydrocarbon oils by two or more hydrotreatment processes only
- C10G65/02—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/14—White oil, eating oil
Abstract
The present disclosure relates to a process for producing a crude white oil, the process comprising the steps of: a. feeding the coal tar distillate into a hydrofining reaction zone to contact with a hydrofining catalyst for a hydrofining reaction to obtain a hydrofining product, and performing product separation on the hydrofining product to obtain naphtha, first crude white oil and first hydrogenation tail oil; b. and enabling at least part of the first hydrogenation tail oil to enter a hydrocracking reaction zone to contact with a hydrocracking catalyst for hydrocracking reaction to obtain a hydrocracking product, and performing product separation on the hydrocracking product to obtain naphtha, second crude white oil and second hydrogenation tail oil. The method can convert the low-quality and low-cost coal tar distillate into a crude white oil product with high added value.
Description
Technical Field
The present disclosure relates to a process for producing a crude white oil.
Background
The crude white oil is used as raw material for producing finished white oil such as industrial white oil and cosmetic white oil, and the finished white oil can be obtained by deep hydrofining and fraction cutting of the crude white oil. The finished white oil has wide application in industrial production, cosmetics, foods and medicines. With the development of economy and the improvement of living standard, the consumption demand and quality requirement of people on white oil products are gradually increased. The properties of the crude white oil, which is one of the raw materials for producing the white oil product, are closely related to the quality of the white oil product. In order to ensure the stability of the quality of the finished white oil, the national energy agency promulgates the quality standard of 'crude white oil' (NB/SH/T0914-2015) in 2015 10 months, which brings certain challenges to enterprises producing the crude white oil.
The method for producing the white oil mainly comprises a sulfonic acid method and a hydrogenation method. The sulfonic acid method for producing white oil has the defects of low yield, three wastes generation, bad operation environment and the like, and is replaced by a hydrogenation method at present. The prior method for producing crude white oil products has few reports in documents, and the hydrogenation method for producing white oil mainly comprises a one-stage method and a two-stage method, which are specifically as follows.
CN1178824A discloses a method for producing white oil by a hydrogenation method, which is to process naphthenic base straight-run oil by a single-stage series high-pressure hydrogenation method to produce white oil under the condition that the hydrogen partial pressure is 13-16 MPa.
CN101343558B discloses a production method of high-viscosity industrial white oil, which adopts hydrocracking medium lubricating oil base oil with the aromatic hydrocarbon content of less than 20 weight percent as a raw material to produce the high-viscosity industrial white oil through first-stage catalytic hydrogenation.
CN101429457A discloses a method for producing white oil by distillate oil hydrogenation, which is characterized in that the distillate oil is sequentially subjected to hydrotreating, gas-liquid separation, dewaxing reaction and supplementary refining under the condition of 8-20MPa to obtain a qualified white oil product.
CN1075547C discloses a method for producing industrial white oil by a hydrogenation method. The method takes lubricating oil base oil or distillate oil with the aromatic hydrocarbon content of less than 30 weight percent as a raw material, and produces the industrial white oil through first-stage hydrogenation under the pressure of 10-30 MPa.
According to the method, the high-quality raw oil with low impurity content is required to be adopted for producing the white oil by adopting the one-stage process under the prior art, the requirements on the properties of the raw materials can be properly relaxed by adopting the two-stage process, but in general, the source of the raw materials for producing the white oil is greatly limited, and the process cost is influenced.
Disclosure of Invention
It is an object of the present disclosure to provide a process for producing crude white oil that can convert low quality, inexpensive coal tar distillate into a high value added crude white oil product.
To achieve the above object, the present disclosure provides a method of producing a crude white oil, comprising the steps of:
a. feeding the coal tar distillate into a hydrofining reaction zone to contact with a hydrofining catalyst for a hydrofining reaction to obtain a hydrofining product, and performing product separation on the hydrofining product to obtain naphtha, first crude white oil and first hydrogenation tail oil;
b. and enabling at least part of the first hydrogenation tail oil to enter a hydrocracking reaction zone to contact with a hydrocracking catalyst for hydrocracking reaction to obtain a hydrocracking product, and performing product separation on the hydrocracking product to obtain naphtha, second crude white oil and second hydrogenation tail oil.
Optionally, in the step a, the coal tar distillate is a distillate with a dry point of 400-500 ℃ in medium-low temperature coal tar whole distillate; the total content of aromatic hydrocarbons and colloids in the coal tar distillate is 50-98 wt%.
Optionally, in the step a, the distillation end point of the naphtha is not higher than 180 ℃, and the distillation range of the first crude white oil is 150-370 ℃;
the initial boiling point of the first hydrogenation tail oil is 300-370 ℃, and the aromatic hydrocarbon content is not higher than 40 wt%, preferably not higher than 30 wt%.
Optionally, in the step b, the distillation end point of the naphtha is not higher than 180 ℃, and the distillation range of the second crude white oil is 150-370 ℃;
the initial boiling point of the second hydrogenation tail oil is 300-370 ℃, and the aromatic hydrocarbon content is not higher than 40 wt%, preferably not higher than 30 wt%.
Optionally, in the step b, 10 to 100 wt% of the first hydrogenated tail oil enters a hydrocracking reaction zone and contacts with a hydrocracking catalyst to perform a hydrocracking reaction.
Optionally, the method further comprises: and circulating 10-100 wt% of the second hydrogenation tail oil into the hydrocracking reaction zone to carry out the hydrocracking reaction.
Optionally, the method further comprises: the hydrofinished product of step a and the hydrocracked product of step b share a single product separation system.
Optionally, the method further comprises: and fractionating the first crude white oil and/or the second crude white oil to obtain No. 3 crude white oil and No. 5 crude white oil.
Optionally, in step a, the hydrofinishing catalyst comprises a first carrier and a first metal component loaded on the first carrier, wherein the first metal component is a group VIII metal and/or a group VIB metal; the VIII group metal is cobalt and/or nickel, and the VIB group metal is molybdenum and/or tungsten;
preferably, the hydrofinishing catalyst comprises, on a dry weight basis of the hydrofinishing catalyst: 45-89 wt% of a first carrier, 1-10 wt% of the group VIII metal, and 10-45 wt% of the group VIB metal.
Alternatively, in step a, the reaction conditions of the hydrofining reaction zone include: the hydrogen partial pressure is 5.0-20.0 MPa, preferably 8.0-17.0 MPa; the reaction temperature is 300-450 ℃, and preferably 330-420 ℃; the volume ratio of hydrogen to oil is 400-2000 Nm3/m3Preferably 500 to 1500Nm3/m3(ii) a The liquid hourly space velocity is 0.1-3.0 h-1Preferably 0.3 to 2.0 hours-1。
Optionally, in step b, the hydrocracking catalyst comprises a second support and a second metal component supported on the second support; the second carrier comprises inorganic oxide, amorphous silica-alumina and a molecular sieve, wherein the inorganic oxide is silica and/or alumina, and the molecular sieve is a Y-type molecular sieve and/or a beta-type molecular sieve; the second metal component is a VIII group metal and/or a VIB group metal; the VIII group metal is cobalt and/or nickel, and the VIB group metal is molybdenum and/or tungsten;
preferably, the hydrocracking catalyst comprises, on a dry weight basis, the following: 30-72 wt% of alumina, 10-52 wt% of amorphous silica-alumina, 1-30 wt% of molecular sieve, 15-35 wt% of the group VIB metal, and 2-8 wt% of the group VIII metal.
Alternatively, in step b, the reaction conditions of the hydrocracking reaction zone comprise: the hydrogen partial pressure is 5.0-20.0 MPa, preferably 8.0-17.0 MPa; the reaction temperature is 300-420 ℃, and preferably 320-400 ℃; the volume ratio of hydrogen to oil is 400-2000 Nm3/m3Preferably 500 to 1500Nm3/m3(ii) a The liquid hourly space velocity is 0.3-0.8 h-1Preferably 0.5 to 3.0 hours-1。
Optionally, the volume ratio of the hydrofining catalyst to the hydrocracking catalyst is 1 (0.2-10).
According to the technical scheme, the inferior and cheap coal tar distillate is used as the raw material, and the crude white oil product meeting the quality standard is produced through the hydrofining reaction and the hydrocracking reaction, so that the problem of harsh requirements on the raw material in the prior art is solved. The method disclosed by the invention can widen the raw material source for producing the crude white oil, has high added value of products and has remarkable economic benefit.
Additional features and advantages of the disclosure will be set forth in the detailed description which follows.
Drawings
The accompanying drawings, which are included to provide a further understanding of the disclosure and are incorporated in and constitute a part of this specification, illustrate embodiments of the disclosure and together with the description serve to explain the disclosure without limiting the disclosure. In the drawings:
FIG. 1 is a schematic flow diagram of one embodiment of a method provided by the present disclosure.
Description of the reference numerals
2 hydrofining reactor
4 high pressure separator
7 low pressure separator
11 fractionating tower
17 hydrocracking reactor
20 cycle hydrogen compressor
1, 3, 5, 6, 8-10, 12-16, 18, 19, 21-23 pipelines
Detailed Description
The following detailed description of specific embodiments of the present disclosure is provided in connection with the accompanying drawings. It should be understood that the detailed description and specific examples, while indicating the present disclosure, are given by way of illustration and explanation only, not limitation.
The present disclosure provides a method of producing a crude white oil, the method comprising the steps of:
a. feeding the coal tar distillate into a hydrofining reaction zone to contact with a hydrofining catalyst for a hydrofining reaction to obtain a hydrofining product, and performing product separation on the hydrofining product to obtain naphtha, first crude white oil and first hydrogenation tail oil;
b. and enabling at least part of the first hydrogenation tail oil to enter a hydrocracking reaction zone to contact with a hydrocracking catalyst for hydrocracking reaction to obtain a hydrocracking product, and performing product separation on the hydrocracking product to obtain naphtha, second crude white oil and second hydrogenation tail oil.
The method adopts the low-quality and cheap coal tar distillate as the raw material, and produces the crude white oil product which meets the quality standard through the hydrofining reaction and the hydrocracking reaction, thereby solving the problem of harsh requirements on the raw material in the prior art.
According to the disclosure, in the step a, the coal tar fraction can be distillate oil with a dry point of 400-500 ℃ in full fraction of medium-low temperature coal tar (with a dry distillation temperature of 450-800 ℃), such as phenol oil fraction and naphthaleneOil fraction, anthracene oil fraction, wash oil fraction, coal diesel fraction, and the like. The content of impurities in the coal tar distillate is generally high, and specifically, the total content of aromatic hydrocarbons and colloids in the coal tar distillate can be 50-98 wt%. The present disclosure is not particularly limited with respect to other properties of the coal tar distillate, for example, the coal tar distillate may have a density (20 ℃) of 0.95 to 1.17g/cm3The sulfur content may be 0.05 to 0.5 wt%, the nitrogen content may be 0.2 to 1.5 wt%, and the like.
According to the disclosure, in the step a, the coal tar distillate may be mixed with a hydrogen-containing material flow and then enter the hydrorefining reaction zone, and then a desulfurization reaction, a denitrification reaction, and a partial aromatic saturation reaction are performed under the action of a hydrorefining catalyst, so as to obtain a hydrorefining product. The hydrogen-containing stream may be a mixture containing fresh hydrogen and recycle hydrogen separated from the hydrofinished product.
In step a, the hydrofinishing catalyst may be of conventional kind well known to those skilled in the art in light of the present disclosure, and the present disclosure is not particularly limited. For example, the hydrofinishing catalyst may include a first support and a first metal component supported on the first support; the first support may be silica, alumina or silica-alumina; the first metal component may be a group VIII metal and/or a group VIB metal. Further, the group VIII metal may be cobalt and/or nickel, and the group VIB metal may be molybdenum and/or tungsten. Still further, the hydrofinishing catalyst may include, based on the dry weight of the hydrofinishing catalyst: 45-89 wt.% alumina, 1-10 wt.% of the group VIII metal, and 10-45 wt.% of the group VIB metal.
According to the present disclosure, in step a, the reaction conditions of the hydrofinishing reaction zone may include: the hydrogen partial pressure is 5.0-20.0 MPa, preferably 8.0-17.0 MPa; the reaction temperature is 300-450 ℃, and preferably 330-420 ℃; the volume ratio of hydrogen to oil is 400-2000 Nm3/m3Preferably 500 to 1500Nm3/m3(ii) a The liquid hourly space velocity is 0.1-3.0 h-1Preferably 0.3 to 2.0h-1。
In accordance with the present disclosure, the step of subjecting the hydrofinished product to product separation in step a is conventional in the art. For example, the hydrorefining product enters a high-pressure separator for oil-gas separation, the liquid-phase material flow separated from the bottom of the high-pressure separator enters a low-pressure separator for further oil-gas separation, and the liquid-phase material flow separated from the low-pressure separator enters a fractionating tower for separating the target product according to different distillation ranges. Wherein the end point of the naphtha is not higher than 180 ℃, and the distillation range of the first crude white oil can be 150-370 ℃. The first hydrogenated tail oil may have a first boiling point of 300 to 370 ℃ and an aromatic content of not more than 40% by weight, preferably not more than 30% by weight.
According to the disclosure, at least part or all of the first hydrogenated tail oil obtained in the step a enters a hydrocracking reaction zone and contacts with a hydrocracking catalyst with good ring-opening performance, which is beneficial to further conversion to obtain a crude white oil product. And b, taking the total amount of the first hydrogenation tail oil obtained in the step a as a reference, wherein the amount of the first hydrogenation tail oil entering the hydrocracking reactor can be 10-100 wt%, that is, in the step b, 10-100 wt% of the first hydrogenation tail oil enters a hydrocracking reaction zone and contacts with a hydrocracking catalyst to carry out hydrocracking reaction. The weight ratio of the first hydrogenation tail oil entering the hydrocracking reaction zone to the coal tar distillate can be 0.8-3.0.
According to the present disclosure, in step b, the hydrocracking catalyst may include a second support and a second metal component supported on the second support. The second carrier may include an inorganic oxide, amorphous silica-alumina, and a molecular sieve, wherein the inorganic oxide may be silica and/or alumina, and the molecular sieve may be a Y-type molecular sieve and/or a β -type molecular sieve. The second metal component may be a group VIII metal and/or a group VIB metal; the group VIII metal may be cobalt and/or nickel and the group VIB metal may be molybdenum and/or tungsten.
In a preferred embodiment of the present disclosure, the hydrocracking catalyst comprises, on a dry weight basis of the hydrocracking catalyst: 30-72 wt% of alumina, 10-52 wt% of amorphous silica-alumina, 1-30 wt% of molecular sieve (Y-type molecular sieve and/or beta-type molecular sieve), 15-35 wt% of the group VIB metal, and 2-8 wt% of the group VIII metal. The adoption of the hydrocracking catalyst is beneficial to further improving the quality of crude white oil products.
According to the present disclosure, the volume ratio of the hydrorefining catalyst to the hydrocracking catalyst can be varied within a wide range, and for example, can be 1 (0.2 to 10).
According to the present disclosure, in step b, the reaction conditions of the hydrocracking reaction zone may include: the hydrogen partial pressure is 5.0-20.0 MPa, preferably 8.0-17.0 MPa; the reaction temperature is 300-420 ℃, and preferably 320-400 ℃; the volume ratio of hydrogen to oil is 400-2000 Nm3/m3Preferably 500 to 1500Nm3/m3(ii) a The liquid hourly space velocity is 0.3-0.8 h-1Preferably 0.5 to 3.0 hours-1。
The step of product separation of the hydrocracked product in step b is also conventional in the art in light of this disclosure, and reference may be made to product separation of the hydrofinished product in step a, and will not be described herein again. Wherein the final boiling point of the naphtha is not higher than 180 ℃, and the distillation range of the second crude white oil can be 150-370 ℃. The second hydrogenated tail oil may have a primary boiling point of 300 to 370 ℃ and an aromatic content of not more than 40% by weight, preferably not more than 30% by weight.
According to the present disclosure, the second hydrogenated tail oil obtained in step b may be continuously recycled to further increase the yield of the crude white oil product, i.e., the method may further comprise: and circulating 10-100 wt% of the second hydrogenation tail oil into the hydrocracking reaction zone to carry out the hydrocracking reaction. The weight ratio of the second hydrogenation tail oil entering the hydrocracking reaction zone to the coal tar distillate can be 0.8-3.0.
In a preferred embodiment of the present disclosure, the method may further include: the hydrofinished product of step a and the hydrocracked product of step b share a single product separation system. That is, the hydrocracked product from step b is mixed with the hydrofinished product from step a, and then the resulting mixture is subjected to product separation. It will be understood by those skilled in the art that in this case, the first crude white oil and the second crude white oil are substantially the same material, and the first hydrogenated tail oil and the second hydrogenated tail oil are also substantially the same material, and the feed to the hydrocracking reaction zone is the hydrogenated tail oil separated from the mixture of the hydrotreated product obtained from the hydrotreating reaction zone and the hydrocracked product obtained from the hydrocracking reaction zone.
According to the present disclosure, to further obtain a crude white oil product satisfying different needs, the method may further comprise: and fractionating the first crude white oil and/or the second crude white oil to obtain No. 3 crude white oil and No. 5 crude white oil. Wherein the product properties of the No. 3 crude white oil and the No. 5 crude white oil meet the requirements of the quality standard of crude white oil (NB/SH/T0914-2015), namely, the aromatic hydrocarbon content of the No. 3 crude white oil is not more than 15 volume percent, and the kinematic viscosity at 40 ℃ is 1 to E<3mm2(ii)/s, flash point (closed) is not less than 38 ℃, Saibote color number is not less than + 20; the No. 5 crude white oil has an aromatic hydrocarbon content of not more than 15 wt%, and a kinematic viscosity of 3 to E at 40 DEG C<6mm2And/s, the flash point (closed) is not more than 70 ℃, the pour point is not more than 3 ℃, and the Saybolt color number is not less than + 20.
The process flow of one embodiment of the method of the present disclosure is briefly described below in conjunction with fig. 1 to further illustrate the present disclosure. Those skilled in the art will appreciate that many of the equipment, such as pumps, heat exchangers, compressors, etc., have been omitted from fig. 1, and the present disclosure is not limited in any way thereby.
As shown in fig. 1, the coal tar fraction is mixed with the recycle gas from the pipeline 22 through the pipeline 1, and then enters the hydrofining reactor 2 to contact with the hydrofining catalyst for the hydrofining reaction, and the obtained hydrofining product enters the high-pressure separator 4 through the pipeline 3 for oil-gas separation. The gas separated by the high pressure separator 4 enters a recycle hydrogen compressor 20 through a line 19, and the outlet gas of the recycle hydrogen compressor 20 is mixed with fresh hydrogen from a line 21 and then recycled to the inlets of the hydrorefining reactor 2 and the hydrocracking reactor 17 through a line 22 and a line 23, respectively. The liquid phase material separated from the bottom of the high-pressure separator 4 flows through a pipeline 5 to enter a low-pressure separator 7 for further oil-gas separation, and the first sulfur-containing sewage is led out through a pipeline 6. The gas separated in the low-pressure separator 7 is discharged from the apparatus through a line 10, the liquid phase stream is passed through a line 8 to a fractionating tower 11, and the second sulfur-containing waste water is discharged through a line 9. Naphtha separated from the top of a fractionating tower 11 is led out of the device through a pipeline 12, a pipeline 13 is used for extracting No. 3 crude white oil fraction, a pipeline 14 is used for extracting No. 5 crude white oil fraction, a small part of hydrogenated tail oil fraction separated from the bottom is thrown out through a pipeline 15, a large part of hydrogenated tail oil fraction enters a hydrocracking reactor 17 through a pipeline 16 and circulating hydrogen from a pipeline 23 to carry out hydrocracking reaction, and an obtained hydrocracking product is mixed with a hydrofined product from the pipeline 3 through a pipeline 18 and then enters a high-pressure separator 4.
The following examples further illustrate the present disclosure, but are not intended to limit the same.
In the examples, a hydrofining catalyst D having a product number of RN-410, a hydrofining catalyst E having a product number of RJW-3, a hydrocracking catalyst F having a product number of RHC-3, and a hydrocracking catalyst G having a product number of RHC-132 were produced by catalyst ChangLing division of petrochemical Co., Ltd., China.
Table 1 shows properties of the coal tar distillate feedstocks used in the examples and comparative examples.
TABLE 1
Example 1
Coal tar distillate feedstock a is processed according to the scheme shown in figure 1. The raw material A firstly enters a hydrofining reaction zone to contact with a hydrofining catalyst D for hydrofining reaction, and naphtha (the distillation range is less than 165 ℃), crude white oil (the distillation range is 165-350 ℃) and hydrogenation tail oil (the initial distillation point is 350 ℃ and the aromatic hydrocarbon content is 12.4 wt%) are separated from hydrofining products. 90 weight percent of the hydrogenated tail oil enters a hydrocracking reaction zone (the weight ratio of the hydrogenated tail oil entering the hydrocracking reaction zone to the raw material A is 1.7) to contact with a hydrocracking catalyst F for hydrocracking reaction, and products are separated after the hydrocracking products and the hydrofining products are mixed. The crude white oil obtained is further fractionated to obtain crude white oil No. 3 and crude white oil No. 5. The reaction conditions, product yields and product properties are shown in table 2.
Comparative example 1
This comparative example is presented to illustrate a process for processing coal tar feedstock a using a conventional hydrofinishing route.
The feed A was contacted with a hydrorefining catalyst D to carry out a hydrorefining reaction, and the hydrorefined product was separated into naphtha (distillation range <165 ℃) and a crude white oil fraction of the same distillation section as in example 1. The reaction conditions, product yields and product properties are shown in table 2.
As can be seen from Table 2, the same quality of the crude white oil fraction as in example 1 does not meet the standard quality requirements at the same total space velocity.
Example 2
Coal tar distillate feedstock B is processed with reference to the flow scheme shown in figure 1. The raw material B firstly enters a hydrofining reaction zone to contact with a hydrofining catalyst E for a hydrofining reaction, and naphtha (the distillation range is less than 165 ℃), crude white oil (the distillation range is 165-350 ℃) and hydrogenation tail oil (the initial distillation point is 350 ℃ and the aromatic hydrocarbon content is 14.9 wt%) are separated from a hydrofining product. 75 weight percent of the hydrogenated tail oil enters a hydrocracking reaction zone (the weight ratio of the hydrogenated tail oil entering the hydrocracking reaction zone to the raw material B is 1.3) to contact with a hydrocracking catalyst F for hydrocracking reaction, and products are separated after the hydrocracking products and the hydrofining products are mixed. The crude white oil obtained is further fractionated to obtain crude white oil No. 3 and crude white oil No. 5. The reaction conditions, product yields and product properties are shown in table 2.
Example 3
Coal tar distillate feedstock C is processed with reference to the flow scheme shown in figure 1. The raw material C firstly enters a hydrofining reaction zone to contact with a hydrofining catalyst E for a hydrofining reaction, and naphtha (the distillation range is less than 165 ℃), crude white oil (the distillation range is 165-350 ℃) and hydrogenation tail oil (the initial distillation point is 350 ℃ and the aromatic hydrocarbon content is 13.6 weight percent) are separated from a hydrofining product. 99 weight percent of the hydrogenated tail oil enters a hydrocracking reaction zone (the weight ratio of the hydrogenated tail oil entering the hydrocracking reaction zone to the raw material C is 1.5) to contact with a hydrocracking catalyst G for hydrocracking reaction, and products are separated after the hydrocracking products and the hydrofining products are mixed. The crude white oil obtained is further fractionated to obtain crude white oil No. 3 and crude white oil No. 5. The reaction conditions, product yields and product properties are shown in table 2.
TABLE 2
| Item | Example 1 | Comparative example 1 | Example 2 | Example 3 | Quality index I |
| Raw oil name | Starting materials A | Starting materials A | Raw material B | Raw material C | |
| Hydrorefining catalyst | D | D | E | E | |
| Hydrocracking catalyst | F | / | F | G | |
| Volume ratio of refining/cracking catalyst | 70:30 | 100:0 | 70:30 | 65:35 | |
| Process conditions in the hydrorefining reaction zone | |||||
| Partial pressure of hydrogen reacted/MPa | 13.0 | 13.0 | 15.0 | 15.0 | |
| Reaction temperature/. degree.C | 370 | 365 | 380 | 375 | |
| Volume space velocity/(h)-1) | 0.8 | 0.6 | 0.6 | 0.5 | |
| Volume ratio of hydrogen to oil/(Nm)3/m3) | 1200 | 1200 | 1500 | 1500 | |
| Hydrocracking reaction zone process conditions | |||||
| Partial pressure of hydrogen reacted/MPa | 13.0 | / | 15.0 | 15.0 | |
| Reaction temperature/. degree.C | 390 | / | 400 | 390 | |
| Volume space velocity/(h)-1) | 1.9 | / | 1.4 | 0.9 | |
| Volume ratio of hydrogen to oil/(Nm)3/m3) | 1200 | / | 1500 | 1500 | |
| Product properties of No. 3 crude white oil (distillation range 165-240℃) | |||||
| Yield/% | 32.4 | 20.4 | 35.0 | 38.8 | |
| Kinematic viscosity (40 ℃ C.)/(mm)2/s) | 1.220 | 1.441 | 1.363 | 1.397 | 1～<3 |
| Flash point (closed)/°c | 48 | 50 | 47 | 48 | ≥38 |
| color/Saybolt color number | ＞+30 | ＞+30 | ＞+30 | ＞+30 | ≥+20 |
| Aromatic hydrocarbon content-Volume% | 11.5 | 17.3 | 13.2 | 9.5 | ≤15 |
| Product properties of No. 5 crude white oil (distillation range 240-350 ℃), and | |||||
| yield/% | 34.2 | 39.7 | 27.5 | 25.2 | |
| Kinematic viscosity (40 ℃ C.)/(mm)2/s) | 3.280 | 3.473 | 3.352 | 3.401 | 3～＜6 |
| Flash point (closed)/°c | 133 | 130 | 131 | 131 | ≥70 |
| Pour point/. degree.C | -15 | -18 | -18 | -18 | ≤3 |
| color/Saybolt color number | ＞+30 | 26.0 | ＞+30 | +30 | ≥+20 |
| Aromatic content/weight% | 11.2 | 16.9 | 12.7 | 12.4 | ≤15 |
Quality index I: refers to the quality index of crude white oil (NB/SH/T0914-
From the results of the above examples, it can be seen that various types of coal tar distillates can be processed by the method provided by the present disclosure to produce qualified number 3 and number 5 crude white oil products; and the qualified No. 3 and No. 5 crude white oil products cannot be produced by adopting the same raw materials to carry out the conventional hydrofining process.
The preferred embodiments of the present disclosure are described in detail with reference to the accompanying drawings, however, the present disclosure is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present disclosure within the technical idea of the present disclosure, and these simple modifications all belong to the protection scope of the present disclosure.
It should be noted that, in the foregoing embodiments, various features described in the above embodiments may be combined in any suitable manner, and in order to avoid unnecessary repetition, various combinations that are possible in the present disclosure are not described again.
In addition, any combination of various embodiments of the present disclosure may be made, and the same should be considered as the disclosure of the present disclosure, as long as it does not depart from the spirit of the present disclosure.
Claims (13)
1. A process for producing a crude white oil, comprising the steps of:
a. feeding the coal tar distillate into a hydrofining reaction zone to contact with a hydrofining catalyst for a hydrofining reaction to obtain a hydrofining product, and performing product separation on the hydrofining product to obtain naphtha, first crude white oil and first hydrogenation tail oil;
b. and enabling at least part of the first hydrogenation tail oil to enter a hydrocracking reaction zone to contact with a hydrocracking catalyst for hydrocracking reaction to obtain a hydrocracking product, and performing product separation on the hydrocracking product to obtain naphtha, second crude white oil and second hydrogenation tail oil.
2. The method of claim 1, wherein in the step a, the coal tar distillate is a distillate with a dry point of 400-500 ℃ in a medium-low temperature coal tar whole distillate; the total content of aromatic hydrocarbons and colloids in the coal tar distillate is 50-98 wt%.
3. The process according to claim 1, wherein in step a, the end point of the naphtha is not higher than 180 ℃, and the distillation range of the first crude white oil is 150-370 ℃;
the initial boiling point of the first hydrogenation tail oil is 300-370 ℃, and the aromatic hydrocarbon content is not higher than 40 wt%, preferably not higher than 30 wt%.
4. The method according to claim 1, wherein in step b, the distillation end point of the naphtha is not higher than 180 ℃, and the distillation range of the second crude white oil is 150-370 ℃;
the initial boiling point of the second hydrogenation tail oil is 300-370 ℃, and the aromatic hydrocarbon content is not higher than 40 wt%, preferably not higher than 30 wt%.
5. The method according to claim 1, wherein in the step b, 10 to 100 wt% of the first hydrogenated tail oil enters a hydrocracking reaction zone and contacts with a hydrocracking catalyst to perform a hydrocracking reaction.
6. The method of claim 1, wherein the method further comprises: and circulating 10-100 wt% of the second hydrogenation tail oil into the hydrocracking reaction zone to carry out the hydrocracking reaction.
7. The method of claim 1, wherein the method further comprises: the hydrofinished product of step a and the hydrocracked product of step b share a single product separation system.
8. The method of claim 1, wherein the method further comprises: and fractionating the first crude white oil and/or the second crude white oil to obtain No. 3 crude white oil and No. 5 crude white oil.
9. The process of claim 1, wherein in step a, the hydrofinishing catalyst comprises a first support and a first metal component supported on the first support, the first metal component being a group VIII metal and/or a group VIB metal; the VIII group metal is cobalt and/or nickel, and the VIB group metal is molybdenum and/or tungsten;
preferably, the hydrofinishing catalyst comprises, on a dry weight basis of the hydrofinishing catalyst: 45-89 wt% of a first carrier, 1-10 wt% of the group VIII metal, and 10-45 wt% of the group VIB metal.
10. The process of claim 1, wherein in step a, the reaction conditions of the hydrofinishing reaction zone comprise: the hydrogen partial pressure is 5.0-20.0 MPa, preferably 8.0-17.0 MPa; the reaction temperature is 300-450 ℃, and preferably 330-420 ℃; the volume ratio of hydrogen to oil is 400-2000 Nm3/m3Preferably 500 to 1500Nm3/m3(ii) a The liquid hourly space velocity is 0.1-3.0 h-1Preferably 0.3 to 2.0 hours-1。
11. The process of claim 1, wherein in step b, the hydrocracking catalyst comprises a second support and a second metal component supported on the second support; the second carrier comprises inorganic oxide, amorphous silica-alumina and a molecular sieve, wherein the inorganic oxide is silica and/or alumina, and the molecular sieve is a Y-type molecular sieve and/or a beta-type molecular sieve; the second metal component is a VIII group metal and/or a VIB group metal; the VIII group metal is cobalt and/or nickel, and the VIB group metal is molybdenum and/or tungsten;
preferably, the hydrocracking catalyst comprises, on a dry weight basis, the following: 30-72 wt% of alumina, 10-52 wt% of amorphous silica-alumina, 1-30 wt% of molecular sieve, 15-35 wt% of the group VIB metal, and 2-8 wt% of the group VIII metal.
12. The process of claim 1, wherein in step b, the reaction conditions of the hydrocracking reaction zone comprise: the hydrogen partial pressure is 5.0-20.0 MPa, preferably 8.0-17.0 MPa; the reaction temperature is 300-420 ℃, and preferably 320-400 ℃; the volume ratio of hydrogen to oil is 400-2000 Nm3/m3Preferably 500 to 1500Nm3/m3(ii) a The liquid hourly space velocity is 0.3-0.8 h-1Preferably 0.5 to 3.0 hours-1。
13. The method of claim 1, wherein the volume ratio of the hydrofining catalyst to the hydrocracking catalyst is 1 (0.2-10).
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| CN101294107A (en) * | 2007-04-24 | 2008-10-29 | 中国石油化工股份有限公司 | Method for preparing fuel oil with coal oil hydrogenation |
| CN103450937A (en) * | 2013-09-13 | 2013-12-18 | 王树宽 | Method for producing low-condensation-point diesel oil and liquid paraffin by using coal tar |
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