CN112745928A - Treatment method of catalytic slurry oil - Google Patents
Treatment method of catalytic slurry oil Download PDFInfo
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- CN112745928A CN112745928A CN201911044242.XA CN201911044242A CN112745928A CN 112745928 A CN112745928 A CN 112745928A CN 201911044242 A CN201911044242 A CN 201911044242A CN 112745928 A CN112745928 A CN 112745928A
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- oil
- hydrogen
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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
- C10G67/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only
- C10G67/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen 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
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
- C10G2300/205—Metal content
Abstract
The invention discloses a method for treating catalytic slurry oil, which sequentially comprises the following steps: the first step is as follows: a molecular distillation pretreatment procedure, namely introducing the catalytic oil slurry into a first-stage molecular distiller, and collecting light component oil and heavy component oil; the second step is that: a hydrogenation pretreatment procedure, wherein metal impurities and oxides in the light oil are removed through heating to obtain hydrogenated oil; the third step: hydrogenating aromatic hydrocarbon saturation and cracking procedures, wherein fractions with the distillation range of more than or equal to 360 ℃ after hydrogenated oil treatment are contacted with a hydrogenation catalyst to saturate and partially crack aromatic rings of the fractions to obtain mixed hydrogen oil; the fourth step: supplementing a refining procedure, wherein the distillate with the distillation range of more than or equal to 360 ℃ after the mixed hydrogen oil is treated is contacted with a hydrogenation catalyst again at high temperature and high pressure, so that the olefin in the oil product is fully saturated, and catalytic hydrogen oil is obtained; the fifth step: the environment-friendly aromatic oil is finally obtained through the fractionation procedure, and the method has the advantage of higher environment-friendly aromatic oil conversion rate.
Description
Technical Field
The invention relates to the field of chemical industry, in particular to a method for treating catalytic slurry oil.
Background
The catalytic slurry oil is residual oil produced by heavy oil catalytic cracking equipment of an oil refinery, has unstable properties, contains about 20-30% of saturated hydrocarbon, about 50-70% of aromatic hydrocarbon, polycyclic aromatic hydrocarbon, 10% of colloid and asphaltene and about 1% of catalyst powder, wherein the component rich in the aromatic hydrocarbon is widely applied to rubber and modified asphalt, but the aromatic oil contains a large amount of carcinogenic polycyclic aromatic hydrocarbon, thereby harming human health and environment.
The content of polycyclic aromatic hydrocarbon in the environment-friendly aromatic oil is extremely low, the environment is friendly, and the substitution of the traditional aromatic oil is a necessary trend. With the gradual deepening of environmental protection instructions of European Union in China and the stricter environmental protection requirements of China, the demand of environment-friendly aromatic oil in industry is greatly increased, and the development and production of the aromatic oil are reluctant.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a treatment method for generating environment-friendly aromatic oil by subjecting catalytic slurry oil to a hydrogenation process, wherein the conversion rate of the environment-friendly aromatic oil generated by the method is high.
The technical scheme adopted by the invention for solving the technical problems is as follows: the method for treating the catalytic slurry oil is characterized by sequentially comprising the following steps of: the first step is as follows: a molecular distillation pretreatment procedure, namely introducing the catalytic oil slurry into a primary molecular distiller under the conditions of high temperature and high pressure, and collecting light component oil and heavy component oil; the second step is that: a hydrogenation pretreatment procedure, wherein the light component oil is heated and contacts with a hydrogenation catalyst at high temperature and high pressure to remove metal impurities and oxides in the light component oil to obtain hydrogenated oil; the third step: hydrogenating aromatic hydrocarbon saturation and cracking procedures, wherein fractions with the distillation range of more than or equal to 360 ℃ after hydrogenated oil treatment are contacted with a hydrogenation catalyst under the conditions of high temperature and high pressure to saturate and partially crack aromatic rings of the fractions so as to obtain mixed hydrogen oil;
the fourth step: supplementing a refining procedure, wherein the distillate with the distillation range of more than or equal to 360 ℃ after the mixed hydrogen oil is treated is contacted with a hydrogenation catalyst again at high temperature and high pressure, so that the olefin in the oil product is fully saturated, and catalytic hydrogen oil is obtained; the fifth step: and (3) a fractionation procedure, namely separating the catalytic hydrogen oil in a distillation tower to obtain various types of environment-friendly aromatic oil.
The further preferable scheme of the invention is as follows: the molecular distillation pretreatment procedure further comprises introducing the formed heavy component oil into a secondary molecular still under conditions of high temperature and high pressure.
The further preferable scheme of the invention is as follows: the first-stage molecular distiller is in absolute pressure of 10Pa and at the temperature of 120 ℃, the second-stage molecular distiller is in absolute pressure of 10Pa and at the temperature of 300 ℃, and is in contact with a hydrogenation catalyst, the metal impurities are nickel, vanadium, iron, aluminum, sodium and the like, and the oxides are sulfides, nitrides and oxides.
The further preferable scheme of the invention is as follows: the hydrogenation pretreatment procedure is carried out at the hydrogen partial pressure of 4-10MPa, the reaction temperature of 300--1Under the conditions of (a).
The further preferable scheme of the invention is as follows: the saturation and cracking procedures of the hydrogenated aromatic hydrocarbon are performed at the hydrogen partial pressure of 6-18MPa, the reaction temperature of 330--1Under the conditions of (a).
The further preferable scheme of the invention is as follows: the supplementary refining procedure is carried out at the hydrogen partial pressure of 6-15MPa, the reaction temperature of 300--1Under the conditions of (a).
The further preferable scheme of the invention is as follows: the fractionation procedure was carried out at a temperature of 360 ℃.
The method comprises three hydrogenation steps under different reaction conditions, can increase the reaction efficiency of the catalytic slurry oil and hydrogen, and has higher conversion rate of the environment-friendly aromatic hydrocarbon.
Drawings
FIG. 1 is a flow chart of the present invention.
Detailed Description
The invention is described in further detail below with reference to the accompanying examples.
A method of treating a catalytic slurry oil comprising:
step one, molecular distillation pretreatment procedure: collecting light components and heavy components from the catalytic oil slurry in a first-stage molecular distiller under the conditions of absolute pressure of 10Pa and temperature of 120 ℃, and then collecting light components oil and heavy components from a heavy-component second-stage molecular distiller under the conditions of absolute pressure of 10Pa and temperature of 300 ℃, wherein the heavy components oil is not subjected to hydrotreating due to the property relation of the heavy components oil;
step two, a hydrogenation pretreatment procedure: the first step, the light component oil is heated and mixed with hydrogen in front of a heating furnace, the hydrogen partial pressure is 4-10MPa, the reaction temperature is 300--1Under the condition of (1), the catalyst is contacted with a hydrogenation catalyst to remove nickel, vanadium, iron, aluminum, sodium and the like in the catalystMetal, sulfide, nitride and oxide to obtain hydrogenated oil;
step three, hydrogenation aromatic hydrocarbon saturation and cracking procedure: the second step is equal to the fraction with the distillation range of more than or equal to 360 ℃ after the hydrogenated oil treatment, the hydrogen partial pressure is 6-18MPa, the reaction temperature is 330--1Under the condition of (1), contacting with a hydrogenation catalyst to saturate and partially crack aromatic rings;
step four, supplementing a refining procedure: treating the fraction with distillation range not less than 360 ℃ after the hydrogenated oil obtained in the third step, wherein the hydrogen partial pressure is 6-15MPa, the reaction temperature is 300-410 ℃, the hydrogen-oil ratio is 400-1200, and the space velocity is 0.8-2.5h-1Under the condition of (1), the catalyst is contacted with a hydrogenation catalyst to fully saturate olefin in an oil product;
step five, fractionation procedure: separating the hydrogenated oil obtained in the fourth step in a fractionating tower at the temperature of 360 ℃ to obtain various grades of environment-friendly aromatic oil;
the following examples are included to demonstrate the distribution and properties of the final product formed under the steps and conditions required by the present invention.
The first embodiment is as follows:
carrying out pretreatment to separate effective components at the temperature of 360-550 ℃, and carrying out hydrotreating on the effective components to ensure that the effective components meet the environment-friendly aromatic hydrocarbon oil standard, wherein the first property is the property of catalytic oil slurry; the second table shows the hydrogenation reaction operating conditions; table three shows the properties of the product produced by the present invention. The yield (yield/%) of the environment-friendly aromatic hydrocarbon can reach 70.6 percent and 73.2 percent respectively
Table one, catalytic slurry properties:
table two, hydroprocessing conditions:
table three, product distribution and properties:
the second embodiment is as follows:
carrying out pretreatment to separate effective components at the temperature of 360-550 ℃, and carrying out hydrotreating on the effective components to ensure that the effective components meet the environment-friendly aromatic hydrocarbon oil standard, wherein the first property is the property of catalytic oil slurry; the second table shows the hydrogenation reaction operating conditions; the third is product distribution and properties.
Table one, catalytic slurry properties:
table two, hydroprocessing conditions:
table three, product distribution and properties:
the above detailed description of the method for treating catalytic oil slurry provided by the present invention is provided, and the principle and the embodiment of the present invention are explained by applying specific examples, and the above description of the examples is only used to help understanding the present invention and the core idea. It should be noted that, for those skilled in the art, it is possible to make various improvements and modifications to the present invention without departing from the principle of the present invention, and those improvements and modifications also fall within the scope of the claims of the present invention.
Claims (7)
1. The method for treating the catalytic slurry oil is characterized by sequentially comprising the following steps of:
the first step is as follows: a molecular distillation pretreatment procedure, namely introducing the catalytic oil slurry into a primary molecular distiller under the conditions of high temperature and high pressure, and collecting light component oil and heavy component oil;
the second step is that: a hydrogenation pretreatment procedure, wherein the light component oil is heated and contacts with a hydrogenation catalyst at high temperature and high pressure to remove metal impurities and oxides in the light component oil to obtain hydrogenated oil;
the third step: hydrogenating aromatic hydrocarbon saturation and cracking procedures, wherein fractions with the distillation range of more than or equal to 360 ℃ after hydrogenated oil treatment are contacted with a hydrogenation catalyst under the conditions of high temperature and high pressure to saturate and partially crack aromatic rings of the fractions so as to obtain mixed hydrogen oil;
the fourth step: supplementing a refining procedure, wherein the distillate with the distillation range of more than or equal to 360 ℃ after the mixed hydrogen oil is treated is contacted with a hydrogenation catalyst again at high temperature and high pressure, so that the olefin in the oil product is fully saturated, and catalytic hydrogen oil is obtained;
the fifth step: and (3) a fractionation procedure, namely separating the catalytic hydrogen oil in a distillation tower to obtain various types of environment-friendly aromatic oil.
2. The method of claim 1, wherein the step of pretreating by molecular distillation further comprises introducing the reformed heavy fraction oil into a secondary molecular still under high temperature and pressure conditions.
3. The method according to claim 2, wherein the primary molecular still is at an absolute pressure of 10Pa and a temperature of 120 ℃, the secondary molecular still is at an absolute pressure of 10Pa and a temperature of 300 ℃, and is in contact with the hydrogenation catalyst, the metal impurities are nickel, vanadium, iron, aluminum, sodium and the like, and the oxides are sulfides, nitrides and oxides.
4. The method as claimed in claim 1, wherein the pre-treatment procedure is performed at a hydrogen partial pressure of 4-10MPa, a reaction temperature of 300-410 ℃, a hydrogen-oil ratio of 200-800, and a space velocity of 0.5-2.0h-1Under the conditions of (a).
5. The method as claimed in claim 1, wherein the hydrogenation aromatics saturation and cracking process is performed at a hydrogen partial pressure of 6-18MPa, a reaction temperature of 330--1Under the conditions of (a).
6. The method as claimed in claim 1, wherein the additional refining process is performed at a hydrogen partial pressure of 6-15MPa, a reaction temperature of 300-410 ℃, a hydrogen-oil ratio of 400-1200, and a space velocity of 0.8-2.5h-1Under the conditions of (a).
7. The method as claimed in claim 1, wherein the fractionation procedure is carried out at a temperature of 360 ℃.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201911044242.XA CN112745928A (en) | 2019-10-30 | 2019-10-30 | Treatment method of catalytic slurry oil |
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| CN201911044242.XA CN112745928A (en) | 2019-10-30 | 2019-10-30 | Treatment method of catalytic slurry oil |
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| CN201911044242.XA Pending CN112745928A (en) | 2019-10-30 | 2019-10-30 | Treatment method of catalytic slurry oil |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102719266A (en) * | 2012-07-03 | 2012-10-10 | 宁波博汇石油化工有限公司 | Heavy oil short-path distillation (molecular distillation) continuous production process |
| CN104004540A (en) * | 2014-05-29 | 2014-08-27 | 嘉诚(福建)石油化工有限公司 | Method and device for separating heavy aromatics from catalytic cracking oil slurry |
| CN104593065A (en) * | 2013-11-04 | 2015-05-06 | 中国石油化工股份有限公司 | Production method for environment-friendly rubber filling oil |
| CN109486526A (en) * | 2018-12-29 | 2019-03-19 | 大连隆星新材料有限公司 | High melting point paraffin or microwax molecular distillation continuous production processes |
-
2019
- 2019-10-30 CN CN201911044242.XA patent/CN112745928A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102719266A (en) * | 2012-07-03 | 2012-10-10 | 宁波博汇石油化工有限公司 | Heavy oil short-path distillation (molecular distillation) continuous production process |
| CN104593065A (en) * | 2013-11-04 | 2015-05-06 | 中国石油化工股份有限公司 | Production method for environment-friendly rubber filling oil |
| CN104004540A (en) * | 2014-05-29 | 2014-08-27 | 嘉诚(福建)石油化工有限公司 | Method and device for separating heavy aromatics from catalytic cracking oil slurry |
| CN109486526A (en) * | 2018-12-29 | 2019-03-19 | 大连隆星新材料有限公司 | High melting point paraffin or microwax molecular distillation continuous production processes |
Non-Patent Citations (1)
| Title |
|---|
| 李斌等: "高芳烃油浆制备芳烃软化剂的研究", 《石油炼制与化工》 * |
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Application publication date: 20210504 |