CN113337308A - Multi-element dispersant slurry of heavy oil suspension bed hydrogenation catalyst - Google Patents
Multi-element dispersant slurry of heavy oil suspension bed hydrogenation catalyst Download PDFInfo
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- CN113337308A CN113337308A CN202110611499.XA CN202110611499A CN113337308A CN 113337308 A CN113337308 A CN 113337308A CN 202110611499 A CN202110611499 A CN 202110611499A CN 113337308 A CN113337308 A CN 113337308A
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- suspension bed
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- bed hydrogenation
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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
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
- C10G45/14—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing with moving solid particles
- C10G45/16—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing with moving solid particles suspended in the oil, e.g. slurries
Abstract
A slurry of a multi-element dispersant of a heavy oil suspension bed hydrogenation catalyst is prepared by mixing molybdenum sulfide microcrystal, organic acid and oil blend, wherein the organic acid at least contains palm oil, and the oil blend is high aromatic middle distillate oil which is completely mutually soluble with the palm oil; compared with the single use of palm oil, the use of the mixed liquid prepared from the palm oil and the low-value high-aromatic-hydrocarbon middle distillate oil not only has low diluent price, but also can reduce the organic oxygen content of the dispersant, reduce the hydrogen consumption and water yield of the dispersant in the hydrogenation process and reduce the loss rate under the condition of keeping the dispersant and the catalyst stably dispersed; when the distillate oil in the high aromatic hydrocarbon is subjected to the fractional distillation of the oil generated by the hydrogenation of the heavy oil suspension bed, the method is more economical; the high aromatic hydrocarbon middle distillate oil has the functions of hydrogen transfer agent, hydrogen donor or asphaltene solvent.
Description
Technical Field
The invention relates to a multi-element dispersant slurry of a heavy oil suspension bed hydrogenation catalyst, which is prepared by mixing molybdenum sulfide microcrystal, organic acid and oil blend, wherein the organic acid at least contains palm oil, and the oil blend is high aromatic medium distillate oil which is completely mutually soluble with the palm oil; compared with the single use of palm oil, the use of the mixed liquid prepared from the palm oil and the low-value high-aromatic-hydrocarbon middle distillate oil not only has low diluent price, but also can reduce the organic oxygen content of the dispersant, reduce the hydrogen consumption and water yield of the dispersant in the hydrogenation process and reduce the loss rate under the condition of keeping the dispersant and the catalyst stably dispersed; when the distillate oil in the high aromatic hydrocarbon is subjected to the fractional distillation of the oil generated by the hydrogenation of the heavy oil suspension bed, the method is more economical; the high aromatic hydrocarbon middle distillate oil has the functions of hydrogen transfer agent, hydrogen donor or asphaltene solvent.
Background
The invention relates to a preparation method of a slurry of a catalyst for a hydrogenation reaction of a heavy oil suspended bed and a method for a hydrogenation reaction process of adding the slurry into the heavy oil suspended bed, aiming at reducing the cost of diluent oil, reducing the risk of flow fluctuation in the adding process and reducing the yield of worthless byproducts of the diluent oil in the hydrogenation reaction process of the heavy oil suspended bed.
Palm oil is an oxygen-containing compound containing saturated fatty acid and unsaturated fatty acid, contains about 44% of palmitic acid (hexadecanoic acid), 5% of stearic acid (octadecanoic acid), 40% of oleic acid (octadecenoic acid), 10% of linoleic acid (octadecadienoic acid) and 0.4% of linolenic acid (octadecatrienoic acid), and can be almost completely hydrodeoxygenated at high temperature and high hydrogen pressure in the presence of a catalyst after entering a suspension bed hydrogenation process, namely hydrogen is consumed to produce moisture, and the price of generated hydrocarbons is lower than that of palm oil.
Chinese patent application No. 202011249413.5 discloses a dispersant for a heavy oil suspension bed hydrogenation catalyst, which uses palm oil and utilizes the polarity of organic acid to disperse molybdenum sulfide microcrystal into slurry; however, palm oil is not only high in price, but also rich in organic oxygen, and in the heavy oil suspension bed hydrogenation reaction process, under the conditions of high temperature, high hydrogen partial pressure and the presence of a suspension bed hydrogenation catalyst, the organic oxygen can consume hydrogen to generate water, and the price of hydrocarbons generated by palm oil hydrogenation is far lower than that of palm oil, so that processing loss is formed; in addition, palm oil contains olefins and deteriorates with long-term heat. The aim of the invention is to reduce the amount of palm oil used and the corresponding loss.
The idea of the invention is: a slurry of a multi-element dispersant of a heavy oil suspension bed hydrogenation catalyst is prepared by mixing molybdenum sulfide microcrystal, organic acid and oil blend, wherein the organic acid at least contains palm oil, and the oil blend is high aromatic middle distillate oil which is completely mutually soluble with the palm oil; compared with the single use of palm oil, the use of the mixed liquid prepared from the palm oil and the low-value high-aromatic-hydrocarbon middle distillate oil not only has low diluent price, but also can reduce the organic oxygen content of the dispersant, reduce the hydrogen consumption and water yield of the dispersant in the hydrogenation process and reduce the loss rate under the condition of keeping the dispersant and the catalyst stably dispersed; when the distillate oil in the high aromatic hydrocarbon is subjected to the fractional distillation of the oil generated by the hydrogenation of the heavy oil suspension bed, the method is more economical; the high aromatic hydrocarbon middle distillate oil has the functions of hydrogen transfer agent, hydrogen donor or asphaltene solvent.
The method of the invention is not reported.
The invention aims to provide a multi-element dispersant slurry of a heavy oil suspension bed hydrogenation catalyst.
Disclosure of Invention
The invention relates to a multi-element dispersant slurry of a heavy oil suspension bed hydrogenation catalyst, which is characterized in that:
a slurry of a multi-element dispersant of a heavy oil suspension bed hydrogenation catalyst is prepared by mixing molybdenum sulfide microcrystal, organic acid and oil blend, wherein the oil blend is high aromatic middle distillate oil which is completely mutually soluble with palm oil;
injecting the slurry of the multi-element dispersant of the heavy oil suspension bed hydrogenation catalyst into a heavy oil suspension bed hydrogenation reaction process for use;
the oil preparation at least contains a fraction with a normal boiling point of 350-500 ℃, and the weight concentration of aromatic hydrocarbon is not lower than 35%;
the weight concentration of oil distribution of the slurry of the multi-element dispersant of the heavy oil suspension bed hydrogenation catalyst is not lower than 35 percent;
the slurry of the polynary dispersant of the heavy oil suspension bed hydrogenation catalyst has no precipitation under the conditions that the temperature is 20-80 ℃ and the standing time is 3.5 minutes;
the flash point of the slurry of the multielement dispersant of the heavy oil suspension bed hydrogenation catalyst is higher than 120 ℃;
the weight content of molybdenum sulfide microcrystal in the slurry of the multielement dispersant of the heavy oil suspension bed hydrogenation catalyst is 1-20%;
the molybdenum sulfide microcrystal mainly comprises microcrystal with the particle length of less than 3 microns; the length of the particle refers to the maximum length of the particle in any direction.
In the present invention, the organic acid generally contains at least palm oil.
In the invention, usually, the slurry of the multi-element dispersant of the heavy oil suspension bed hydrogenation catalyst is injected into a heavy oil suspension bed hydrogenation reaction process for use, middle distillate oil obtained by separating oil generated by the heavy oil suspension bed hydrogenation reaction is used as oil blending, and the oil blending is mixed with molybdenum sulfide microcrystal and organic acid mixed oil and then stored in a slurry buffer tank; the slurry buffer tank uses nitrogen or hydrogen or fuel gas to isolate air; the slurry in the slurry buffer tank is pressurized by a circulating pump of the slurry buffer tank and then returns to the liquid level at the upper part of the slurry buffer tank, the mixed state of the liquid materials in the slurry buffer tank is kept, and the sedimentation of particles is prevented;
transferring the multi-element dispersant slurry of the heavy oil suspension bed hydrogenation catalyst in the slurry buffer tank into a slurry filling tank; the bottom oil of the slurry filling tank is pressurized by a circulating pump of the slurry filling tank and then returns to the liquid level at the upper part of the slurry filling tank, the mixing state of the liquid materials in the slurry filling tank is kept, and the sedimentation of particles is prevented; the slurry filling tank uses nitrogen or hydrogen or fuel gas to isolate air;
slurry of a polynary dispersant of a heavy oil suspension bed hydrogenation catalyst in a slurry filling tank is pressurized by a reaction feeding agent adding pump and then is injected into a heavy oil suspension bed hydrogenation reaction process for use; a flow meter is arranged on a conveying pipeline from an outlet of the reaction feeding agent adding pump to the hydrogenation reaction process of the heavy oil suspended bed; the reaction feeding agent adding pump adopts a positive displacement pump.
According to the invention, the molybdenum sulphide crystallites, in general, consist essentially of crystallites having a particle length of 0.3 nm to 300 nm, or of crystallites having a particle length of 0.3 nm to 100 nm, or of crystallites having a particle length of 0.3 nm to 50 nm, or of crystallites having a particle length of 0.3 nm to 10 nm.
The initial boiling point of the oil preparation of the slurry of the multi-element dispersant of the heavy oil suspension bed hydrogenation catalyst is usually higher than 290 ℃ and usually higher than 350 ℃.
In the invention, the dosage of the slurry of the multi-element dispersant of the heavy oil suspension bed hydrogenation catalyst is generally one million to six million parts of the weight of fresh heavy oil in the heavy oil suspension bed hydrogenation reaction process.
The slurry of the multielement dispersant of the heavy oil suspension bed hydrogenation catalyst can be prepared by high-concentration catalyst slurry and oil blending.
In the invention, the oil is selected from one or more of catalytic cracking oil, delayed coking oil and heavy oil suspension bed hydrogenation oil.
In the invention, the slurry of the multielement dispersant of the heavy oil suspension bed hydrogenation catalyst is injected into the heavy oil suspension bed hydrogenation reaction process for use;
generally, the heavy oil refers to bottom oil of an atmospheric fractionating tower or bottom oil of a vacuum distillation tower, and the weight concentration of the fraction with the conventional boiling point of above 550 ℃ is not lower than 70%.
According to the invention, in general, the multi-element dispersant slurry of the heavy oil suspension bed hydrogenation catalyst has the oil distribution weight concentration of more than 50% or more than 70% or more than 90%; the smaller the particle length of the molybdenum sulfide microcrystal is, the larger the weight concentration of the oil is.
Detailed Description
The invention relates to a multi-element dispersant slurry of a heavy oil suspension bed hydrogenation catalyst, which is characterized in that:
a slurry of a multi-element dispersant of a heavy oil suspension bed hydrogenation catalyst is prepared by mixing molybdenum sulfide microcrystal, organic acid and oil blend, wherein the oil blend is high aromatic middle distillate oil which is completely mutually soluble with palm oil;
injecting the slurry of the multi-element dispersant of the heavy oil suspension bed hydrogenation catalyst into a heavy oil suspension bed hydrogenation reaction process for use;
the oil preparation at least contains a fraction with a normal boiling point of 350-500 ℃, and the weight concentration of aromatic hydrocarbon is not lower than 35%;
the weight concentration of oil distribution of the slurry of the multi-element dispersant of the heavy oil suspension bed hydrogenation catalyst is not lower than 35 percent;
the slurry of the polynary dispersant of the heavy oil suspension bed hydrogenation catalyst has no precipitation under the conditions that the temperature is 20-80 ℃ and the standing time is 3.5 minutes;
the flash point of the slurry of the multielement dispersant of the heavy oil suspension bed hydrogenation catalyst is higher than 120 ℃;
the weight content of molybdenum sulfide microcrystal in the slurry of the multielement dispersant of the heavy oil suspension bed hydrogenation catalyst is 1-20%;
the molybdenum sulfide microcrystal mainly comprises microcrystal with the particle length of less than 3 microns; the length of the particle refers to the maximum length of the particle in any direction.
In the present invention, the organic acid generally contains at least palm oil.
In the invention, usually, the slurry of the multi-element dispersant of the heavy oil suspension bed hydrogenation catalyst is injected into a heavy oil suspension bed hydrogenation reaction process for use, middle distillate oil obtained by separating oil generated by the heavy oil suspension bed hydrogenation reaction is used as oil blending, and the oil blending is mixed with molybdenum sulfide microcrystal and organic acid mixed oil and then stored in a slurry buffer tank; the slurry buffer tank uses nitrogen or hydrogen or fuel gas to isolate air; the slurry in the slurry buffer tank is pressurized by a circulating pump of the slurry buffer tank and then returns to the liquid level at the upper part of the slurry buffer tank, the mixed state of the liquid materials in the slurry buffer tank is kept, and the sedimentation of particles is prevented;
transferring the multi-element dispersant slurry of the heavy oil suspension bed hydrogenation catalyst in the slurry buffer tank into a slurry filling tank; the bottom oil of the slurry filling tank is pressurized by a circulating pump of the slurry filling tank and then returns to the liquid level at the upper part of the slurry filling tank, the mixing state of the liquid materials in the slurry filling tank is kept, and the sedimentation of particles is prevented; the slurry filling tank uses nitrogen or hydrogen or fuel gas to isolate air;
slurry of a polynary dispersant of a heavy oil suspension bed hydrogenation catalyst in a slurry filling tank is pressurized by a reaction feeding agent adding pump and then is injected into a heavy oil suspension bed hydrogenation reaction process for use; a flow meter is arranged on a conveying pipeline from an outlet of the reaction feeding agent adding pump to the hydrogenation reaction process of the heavy oil suspended bed; the reaction feeding agent adding pump adopts a positive displacement pump.
According to the invention, the molybdenum sulphide crystallites, in general, consist essentially of crystallites having a particle length of 0.3 nm to 300 nm, or of crystallites having a particle length of 0.3 nm to 100 nm, or of crystallites having a particle length of 0.3 nm to 50 nm, or of crystallites having a particle length of 0.3 nm to 10 nm.
The initial boiling point of the oil preparation of the slurry of the multi-element dispersant of the heavy oil suspension bed hydrogenation catalyst is usually higher than 290 ℃ and usually higher than 350 ℃.
In the invention, the dosage of the slurry of the multi-element dispersant of the heavy oil suspension bed hydrogenation catalyst is generally one million to six million parts of the weight of fresh heavy oil in the heavy oil suspension bed hydrogenation reaction process.
The slurry of the multielement dispersant of the heavy oil suspension bed hydrogenation catalyst can be prepared by high-concentration catalyst slurry and oil blending.
In the invention, the oil is selected from one or more of catalytic cracking oil, delayed coking oil and heavy oil suspension bed hydrogenation oil.
In the invention, the slurry of the multielement dispersant of the heavy oil suspension bed hydrogenation catalyst is injected into the heavy oil suspension bed hydrogenation reaction process for use;
generally, the heavy oil refers to bottom oil of an atmospheric fractionating tower or bottom oil of a vacuum distillation tower, and the weight concentration of the fraction with the conventional boiling point of above 550 ℃ is not lower than 70%.
According to the invention, in general, the multi-element dispersant slurry of the heavy oil suspension bed hydrogenation catalyst has the oil distribution weight concentration of more than 50% or more than 70% or more than 90%; the smaller the particle length of the molybdenum sulfide microcrystal is, the larger the weight concentration of the oil is.
Claims (10)
1. A multi-element dispersant slurry of a heavy oil suspension bed hydrogenation catalyst is characterized in that:
a slurry of a multi-element dispersant of a heavy oil suspension bed hydrogenation catalyst is prepared by mixing molybdenum sulfide microcrystal, organic acid and oil blend, wherein the oil blend is high aromatic middle distillate oil which is completely mutually soluble with palm oil;
injecting the slurry of the multi-element dispersant of the heavy oil suspension bed hydrogenation catalyst into a heavy oil suspension bed hydrogenation reaction process for use;
the oil preparation at least contains a fraction with a normal boiling point of 350-500 ℃, and the weight concentration of aromatic hydrocarbon is not lower than 35%;
the weight concentration of oil distribution of the slurry of the multi-element dispersant of the heavy oil suspension bed hydrogenation catalyst is not lower than 35 percent;
the slurry of the polynary dispersant of the heavy oil suspension bed hydrogenation catalyst has no precipitation under the conditions that the temperature is 20-80 ℃ and the standing time is 3.5 minutes;
the flash point of the slurry of the multielement dispersant of the heavy oil suspension bed hydrogenation catalyst is higher than 120 ℃;
the weight content of molybdenum sulfide microcrystal in the slurry of the multielement dispersant of the heavy oil suspension bed hydrogenation catalyst is 1-20%;
the molybdenum sulfide microcrystal mainly comprises microcrystal with the particle length of less than 3 microns; the length of the particle refers to the maximum length of the particle in any direction.
2. The method of claim 1, further comprising:
the organic acid at least contains palm oil.
3. The method of claim 1, further comprising:
injecting the slurry of the multi-element dispersant of the heavy oil suspension bed hydrogenation catalyst into a heavy oil suspension bed hydrogenation reaction process for use, separating medium distillate oil obtained by oil generated by the heavy oil suspension bed hydrogenation reaction and using the medium distillate oil as oil blending, mixing the oil blending with molybdenum sulfide microcrystal and organic acid mixed oil and storing the mixed oil in a slurry buffer tank; the slurry buffer tank uses nitrogen or hydrogen or fuel gas to isolate air; the slurry in the slurry buffer tank is pressurized by a circulating pump of the slurry buffer tank and then returns to the liquid level at the upper part of the slurry buffer tank, the mixed state of the liquid materials in the slurry buffer tank is kept, and the sedimentation of particles is prevented;
transferring the multi-element dispersant slurry of the heavy oil suspension bed hydrogenation catalyst in the slurry buffer tank into a slurry filling tank; the bottom oil of the slurry filling tank is pressurized by a circulating pump of the slurry filling tank and then returns to the liquid level at the upper part of the slurry filling tank, the mixing state of the liquid materials in the slurry filling tank is kept, and the sedimentation of particles is prevented; the slurry filling tank uses nitrogen or hydrogen or fuel gas to isolate air;
slurry of a polynary dispersant of a heavy oil suspension bed hydrogenation catalyst in a slurry filling tank is pressurized by a reaction feeding agent adding pump and then is injected into a heavy oil suspension bed hydrogenation reaction process for use; a flow meter is arranged on a conveying pipeline from an outlet of the reaction feeding agent adding pump to the hydrogenation reaction process of the heavy oil suspended bed; the reaction feeding agent adding pump adopts a positive displacement pump.
4. The method of claim 1, further comprising:
the molybdenum sulfide microcrystal mainly comprises microcrystal with the particle length of 0.3 to 300 nanometers, or mainly comprises microcrystal with the particle length of 0.3 to 100 nanometers, or mainly comprises microcrystal with the particle length of 0.3 to 50 nanometers, or mainly comprises microcrystal with the particle length of 0.3 to 10 nanometers.
5. The method of claim 1, further comprising:
the initial boiling point of the oil blending of the slurry of the multi-element dispersant of the heavy oil suspension bed hydrogenation catalyst is higher than 290 ℃ or higher than 350 ℃.
6. The method of claim 1, further comprising:
the dosage of the slurry of the multielement dispersant of the heavy oil suspension bed hydrogenation catalyst is one million to six million of the weight of fresh heavy oil in the heavy oil suspension bed hydrogenation reaction process.
7. The method of claim 1, further comprising:
the slurry of the multielement dispersant of the heavy oil suspension bed hydrogenation catalyst is prepared by high-concentration catalyst slurry and oil blending.
8. The method of claim 1, further comprising:
the oil is one or more of catalytic cracking oil, delayed coking oil and heavy oil suspension bed hydrogenation oil.
9. The method of claim 1, further comprising:
injecting the slurry of the multi-element dispersant of the heavy oil suspension bed hydrogenation catalyst into a heavy oil suspension bed hydrogenation reaction process for use;
the heavy oil refers to bottom oil of an atmospheric fractionating tower or bottom oil of a vacuum distillation tower, and the weight concentration of the fraction with the conventional boiling point of above 550 ℃ is not lower than 70%.
10. The method of claim 1, further comprising:
the weight concentration of oil distribution of the slurry of the multi-element dispersant of the heavy oil suspension bed hydrogenation catalyst is more than 50 percent or more than 70 percent or more than 90 percent; the smaller the particle length of the molybdenum sulfide microcrystal is, the larger the weight concentration of the oil is.
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| CN202110611499.XA CN113337308A (en) | 2021-05-26 | 2021-05-26 | Multi-element dispersant slurry of heavy oil suspension bed hydrogenation catalyst |
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| CN202110611499.XA CN113337308A (en) | 2021-05-26 | 2021-05-26 | Multi-element dispersant slurry of heavy oil suspension bed hydrogenation catalyst |
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| CN103265971A (en) * | 2013-05-15 | 2013-08-28 | 煤炭科学研究总院 | Heterogeneous coal tar suspension bed hydrogenation method |
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| CN105296002A (en) * | 2015-11-17 | 2016-02-03 | 中国五环工程有限公司 | Method for producing fuel oils by hydrogenation after coal tar cleaning and phenol extraction and system thereof |
| CN106867573A (en) * | 2015-12-10 | 2017-06-20 | 辽宁石油化工大学 | A kind of method of suspension bed hydrogenation catalyst high efficiency dispersion |
| CN108264935A (en) * | 2016-12-30 | 2018-07-10 | 北京华石联合能源科技发展有限公司 | A kind of floating bed hydrogenation system for handling heavy oil |
| CN109701561A (en) * | 2019-01-17 | 2019-05-03 | 煤炭科学技术研究院有限公司 | Distributed nano molybdenum disulfide catalyst and its preparation method and application |
| CN112391197A (en) * | 2020-11-10 | 2021-02-23 | 洛阳瑞泽石化工程有限公司 | Suspension bed residual oil hydrocracking system and method |
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2021
- 2021-05-26 CN CN202110611499.XA patent/CN113337308A/en not_active Withdrawn
Patent Citations (8)
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|---|---|---|---|---|
| US20140166541A1 (en) * | 2012-12-14 | 2014-06-19 | Julie Chabot | Hydroprocessing co-catalyst compositions and methods of introduction thereof into hydroprocessing units |
| CN103265971A (en) * | 2013-05-15 | 2013-08-28 | 煤炭科学研究总院 | Heterogeneous coal tar suspension bed hydrogenation method |
| WO2014183429A1 (en) * | 2013-05-15 | 2014-11-20 | 煤炭科学研究总院 | Heterogeneous suspension-bed hydrogenation method for coal-based oil product |
| CN105296002A (en) * | 2015-11-17 | 2016-02-03 | 中国五环工程有限公司 | Method for producing fuel oils by hydrogenation after coal tar cleaning and phenol extraction and system thereof |
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| CN108264935A (en) * | 2016-12-30 | 2018-07-10 | 北京华石联合能源科技发展有限公司 | A kind of floating bed hydrogenation system for handling heavy oil |
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