CN104888860B - A kind of naphthenate catalyst, preparation method and its usage - Google Patents
A kind of naphthenate catalyst, preparation method and its usage Download PDFInfo
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Abstract
The invention belongs to the technical field of catalyst in oil-refining chemical technique, and in particular to naphthenate catalyst, preparation method and its usage for inferior heavy oil slurry bed system hydrocracking process.The active component of the catalyst is Ni and/or Mo, and wherein Ni metal qualities content is that 5%~8%, Mo metal qualities content is 4%~7%, and active component thinks that particle diameter exists in 1 μm~100 μm of transient metal sulfide form with sulphur source.(1) the naphthenate catalyst addition prepared by the present invention is few, and use cost is low, and synthetic method is simple, and raw material is cheap and easily-available, suitable for large-scale industrial production；(2) dispersion effect in heavy oil feedstock of the naphthenate catalyst prepared by the present invention is good, and tenor is high, hydrogenation activity is high, and it is good to press down burnt performance, reacts and solid particle is substantially free of in tail oil, light oil yield is high.
Description
Technical field
The invention belongs to the technical field of catalyst in oil-refining chemical technique, and in particular to add for inferior heavy oil slurry bed system
Naphthenate catalyst, the preparation method and its usage of hydrogen process.
Background technology
The trend cleaned with crude oil heaviness, in poor quality and product requirement is increasingly sharpened, and heavy-oil hydrogenation technology is gradual
As the emphasis of research.Heavy-oil slurry hydrocracking process can handle high-sulfur, high metal, height to the wide adaptability of raw material
Carbon residue and highly viscous inferior heavy oil, and there is higher light oil yield, and as the one of domestic and international institute active development now
The new heavy oil lighting technique of kind.The main flow of heavy oil slurry bubble bed hydrocracking process is, by the catalyst of fine and even
Or additive is scattered in feedstock oil, then with hydrogen mix, heated in heating furnace latter and enter reactor, in high temperature, height
Cracking reaction occurs for pressure, and in the process, hydrogen and catalyst not only suppress green coke to a large extent, also with one
It is a little to promote HDM, desulfurization, the effect of denitrification reaction.At present, because heavy-oil slurry is hydrocracked water-soluble catalyst
Dispersing technology is complicated, high energy consumption, is unfavorable for industrial application.Therefore, the preparation of high efficient oil dissolubility catalyst is for heavy oil
The industrialization promotion of slurry bed system hydrocracking process is particularly important.
Naphthenate is a kind of oil soluble metal salt, meets heavy-oil slurry and is hydrocracked to the oil-soluble base of catalyst
This requirement, but it is currently used primarily in terebine, chemical catalyst, lube oil additive, stabilizer for plastics, tire bonding
Agent, timber preservative, plant growth regulator etc., market demand is smaller, the reality not used as Oil Refinery Industry catalyst
Example.Further, since at present naphthenate synthesis technique more fall behind, having product, tenor is relatively low, hydrogenation activity compared with
It is low, oil-soluble effect is poor, prepare cost it is higher the shortcomings of, be not suitable as heavy-oil slurry hydrocracking catalyst.Therefore,
A kind of novel method for synthesizing of metal naphthenate class is proposed, to improve the tenor of naphthenate and oil-soluble, is allowed to suitable
Together in the oil-soluble catalyst being hydrocracked as inferior heavy oil slurry bed system.
The content of the invention
The invention provides a kind of naphthenate catalyst, preparation method and its usage, solves current naphthenate
Synthesis technique more falls behind, and having product, tenor is relatively low, and hydrogenation activity is relatively low, oil-soluble effect is poor, prepares cost
The shortcomings of higher, the problems such as being not suitable as heavy-oil slurry hydrocracking catalyst.
In order to solve the above technical problems, the technical solution adopted by the present invention is：
A kind of naphthenate catalyst, the active component of the catalyst is Ni and/or Mo, and wherein Ni metal qualities content is
5%~8%, Mo metal quality content are 4%~7%, and active component thinks transition gold of the particle diameter at 1 μm~100 μm with sulphur source
Belong to sulphided form to exist.
The invention provides a kind of preparation method of naphthenate catalyst, described active component is nickel, preparation method
It is as follows：
(1) aphthenic acids and distilled water are added in reaction vessel, adds highly basic after being heated to 55 DEG C~75 DEG C, be in temperature
Reaction is carried out at 80 DEG C~100 DEG C 1~5 hour；
(2) after reaction terminates, transition metal salt is added in reactor, carried out at being 70 DEG C~100 DEG C in temperature anti-
Should, 1~6 hour reaction time；
(3) reaction terminates, and aqueous phase is separated after product is stood, gained oil-phase product is naphthenate catalyst.
Further, a preferred embodiment of the present invention is：Aphthenic acids, highly basic, the mol ratio of transition metal salt three are：
0.6~1.4:1:0.3~0.7.
Further, a preferred embodiment of the present invention is：Described highly basic is one in sodium hydroxide, potassium hydroxide material
The combination of kind or two kinds of materials.
Further, a preferred embodiment of the present invention is：Described transition metal salt is transition metal sulfate, transition gold
Belong to the combination of one or both of villaumite material.
Invention further provides a kind of preparation method of naphthenate catalyst, described active component is molybdenum, preparation side
Method is as follows：
(1) oxalic acid and distilled water are added in reaction vessel, after heating for dissolving, adds molybdenum source and reacted, the reaction time
For 1~3 hour；
(2) after reaction terminates, the aphthenic acids of addition, reacted 3~5 hours at 200 DEG C~300 DEG C；
(3) stop reaction, pour into while hot in beaker, stand, produce naphthenate catalyst.
Further, a preferred embodiment of the present invention is：Oxalic acid, molybdenum source, the mass ratio of aphthenic acids three are：1~5:1:5
~10.
Further, a preferred embodiment of the present invention is：Molybdenum source be molybdenum trioxide, sodium molybdate, one kind in ammonium molybdate or
The combination of several materials.
Naphthenate catalyst prepared by the present invention is used for the method that inferior heavy oil slurry bed system is hydrocracked, naphthenate
Tenor in catalyst is 50~2000 μ g/g in the ratio of heavy oil feedstock.
Further, a preferred embodiment of the present invention is：The condition that inferior heavy oil slurry bed system is hydrocracked is reaction temperature
420 DEG C~460 DEG C, hydrogen partial pressure is 12MPa~23MPa, and fresh feed air speed is 0.2h-1~1.5h-1, hydrogen-oil ratio be 500~
1200:1。
Beneficial effects of the present invention：
(1) the naphthenate catalyst addition prepared by the present invention is few, and use cost is low, and synthetic method is simple, former
Expect it is cheap and easily-available, suitable for large-scale industrial production；
(2) dispersion effect in heavy oil feedstock of the naphthenate catalyst prepared by the present invention is good, and tenor is high, hydrogenation
Active high, it is good to press down burnt performance, reacts and solid particle is substantially free of in tail oil, light oil yield is high.
Embodiment
Below in conjunction with the specific embodiment of the invention, technical scheme is clearly and completely described, shown
So, described embodiment is only part of the embodiment of the present invention, rather than whole embodiments.Based on the reality in the present invention
Example is applied, the every other embodiment that those of ordinary skill in the art are obtained under the premise of creative work is not made, is all belonged to
In the scope of protection of the invention.
Embodiment 1
A kind of naphthenate catalyst, the active component of the catalyst is Ni, wherein Ni tenors be 6%, activity into
Divide and think that particle diameter exists in 1 μm~100 μm of transient metal sulfide form with sulphur source,
Its preparation method is as follows：
(1) take and distilled water is added in 0.05mol aphthenic acids, after heating is sufficiently mixed uniformly, in 55-75 DEG C of condition of temperature
Under, add 0.04mol sodium hydroxides and react 4h at 60 DEG C~100 DEG C；
(2) after reaction terminates, in addition 0.002mol nickel sulfates to reactor, carried out at being 80 DEG C~100 DEG C in temperature
Reaction, 2 hours reaction time；
(3) reaction terminates, and aqueous phase is separated after product is stood, gained oil-phase product is naphthenate catalyst.
Nickel metal quality content is 6.02% in prepared catalyst.
Embodiment 2
Substantially the same manner as Example 1, difference is：Transition metal salt uses nickel chloride, the reaction time in (1) step
For 1h, the reaction time in (2) step is 6h, and nickel metal quality content is 5.84% in prepared catalyst.
Embodiment 3
Substantially the same manner as Example 1, difference is：Aphthenic acids, highly basic, the mol ratio of transition metal salt three are：
1.4:1:0.3, highly basic uses potassium hydroxide, the reaction time in (1) step is 5h, and the reaction time in (2) step is 1h,
Nickel metal quality content is 5.01% in prepared catalyst
Embodiment 4
Substantially the same manner as Example 2, difference is：Aphthenic acids, highly basic, the mol ratio of transition metal salt three are：
0.6:1:0.7, highly basic uses mass ratio 1:1 potassium hydroxide and the mixture of sodium hydroxide, nickel gold in prepared catalyst
It is 8.02% to belong to mass content.
Embodiment 5
A kind of naphthenate catalyst, the active component of the catalyst is Mo, wherein Mo metal qualities content be 4%~
7%, active component thinks that particle diameter exists in 1 μm~100 μm of transient metal sulfide form with sulphur source, and its preparation method is such as
Under：
(1) take 12.6g oxalic acid and distilled water to add in container, after heating for dissolving, add 4.8g molybdenum trioxides and reacted,
Reaction time is 2 hours, then
(2) after reaction terminates, addition is preheated to 200-300 DEG C of 42g aphthenic acids, alkanoic acid, reacts 4 at 200~300 DEG C
Hour；
(3) stop reaction, pour into while hot in beaker, stand, produce naphthenate catalyst.
Molybdenum mass content is 5.72% in prepared catalyst.
Embodiment 6
Substantially the same manner as Example 5, difference is：Oxalic acid, molybdenum source, the mass ratio of aphthenic acids three are：1:1:10, molybdenum
Source is sodium molybdate, and the reaction time in (1) step is 1h, and the reaction time in (2) step is 5h, molybdenum in prepared catalyst
Metal quality content is 7.01%.
Embodiment 7
Substantially the same manner as Example 5, difference is：Oxalic acid, molybdenum source, the mass ratio of aphthenic acids three are：5:1:5, molybdenum
Source is ammonium molybdate, and the reaction time in (1) step is 3h, and the reaction time in (2) step is 3h, molybdenum in prepared catalyst
Metal quality content is 4.02%.
Embodiment 8~11, the present embodiment are-No. 380 fuel oil of Venezuela using raw material, and its property is shown in Table 1.In high pressure
The conversion situation of feedstock oil under the conditions of different catalysts additions, reaction pressure, temperature and time is investigated on kettle, experimental result is shown in
Table 2.
As shown in Table 2, oil-soluble metal naphthenate class catalyst provided by the invention has that dispersion effect is good, disperses work
The advantages of skill is simple to operate, and hydrogenation activity is high, the burnt performance of suppression is good.The catalyst is applied to inferior heavy, the floating bed hydrogenation of residual oil
In cracking process, in the case of addition (in terms of metal)≤200 μ g/g of catalyst, that is, there is higher suppression Jiao's performance,
Coking yield ＜ 2.0m% ,≤500 DEG C of liquid product yields can reach more than 80m%.
The residual oil slurry bed system Hydrocracking Raw Oil property of table 1
The heavy-oil slurry hydrocracking reaction result of table 2
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all essences in the present invention
God any modification, equivalent substitution and improvements made etc., should be included in the scope of the protection with principle.
Claims (9)
- A kind of 1. preparation method of naphthenate catalyst, it is characterised in that：Active component is with sulphur source with particle diameter in 1 μm~100 μ M transient metal sulfide form is present, and described active component is nickel, and Ni metal qualities content is 5%~8%, preparation side Method is as follows：(1) aphthenic acids and distilled water are added in reaction vessel, highly basic is added after being heated to 55 DEG C~75 DEG C, be 80 DEG C in temperature Reaction 1~5 hour is carried out at~100 DEG C；(2) after reaction terminates, nickel metal salt is added in reactor, is reacted, reacted at being 70 DEG C~100 DEG C in temperature 1~6 hour time；(3) reaction terminates, and aqueous phase is separated after product is stood, gained oil-phase product is naphthenate catalyst.
- 2. the preparation method of naphthenate catalyst according to claim 1, it is characterised in that：Aphthenic acids, highly basic, nickel gold Category salt three mol ratio be：0.6~1.4:1:0.3~0.7.
- 3. the preparation method of naphthenate catalyst according to claim 1 or 2, it is characterised in that：Described highly basic is The combination of one or both of sodium hydroxide, potassium hydroxide material material.
- 4. the preparation method of naphthenate catalyst according to claim 1 or 2, it is characterised in that：Described nickel metal Salt is the combination of one or both of nickel metal sulfate, nickel metal chloride material.
- A kind of 5. preparation method of naphthenate catalyst, it is characterised in that：Active component is with sulphur source with particle diameter in 1 μm~100 μ M transient metal sulfide form is present, and described active component is molybdenum, and Mo metal qualities content is 4%~7%, preparation side Method is as follows：(1) oxalic acid and distilled water being added in reaction vessel, after heating for dissolving, adds molybdenum source and reacted, the reaction time is 1~ 3 hours；(2) after reaction terminates, aphthenic acids is added, is reacted 3~5 hours at 200 DEG C~300 DEG C；(3) stop reaction, pour into while hot in beaker, stand, produce naphthenate catalyst.
- 6. the preparation method of naphthenate catalyst according to claim 5, it is characterised in that：Oxalic acid, molybdenum source, aphthenic acids The mass ratio of three is：1~5:1:5~10.
- 7. the preparation method of the naphthenate catalyst according to claim 5 or 6, it is characterised in that：Molybdenum source is three oxidations The combination of one or more of materials in molybdenum, sodium molybdate, ammonium molybdate.
- 8. the naphthenate catalyst prepared by claim any one of 1-6 is used for the side that inferior heavy oil slurry bed system is hydrocracked Method, it is characterised in that：Tenor in naphthenate catalyst is 50~2000 μ g/g in the ratio of heavy oil feedstock.
- 9. the method that inferior heavy oil slurry bed system according to claim 8 is hydrocracked, it is characterised in that：Inferior heavy oil slurry The condition of bed hydroprocessing cracking is 420 DEG C~460 DEG C of reaction temperature, and hydrogen partial pressure is 12MPa~23MPa, and fresh feed air speed is 0.2h-1~1.5h-1, hydrogen-oil ratio is 500~1200:1.
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| CN108273558B (en) * | 2018-02-11 | 2019-07-23 | 北京石油化工学院 | Catalytic cracking catalyst and its preparation method and application |
| CN108355711B (en) * | 2018-02-11 | 2019-07-23 | 北京石油化工学院 | A kind of catalytic cracking catalyst and its preparation method and application |
| CN108329514B (en) * | 2018-02-11 | 2019-12-17 | 北京石油化工学院 | Method for processing waste plastics and cellulose |
| CN108219815B (en) * | 2018-02-11 | 2019-09-17 | 北京石油化工学院 | The method for the treatment of of waste plastics and cellulose |
| CN115678683A (en) * | 2022-10-20 | 2023-02-03 | 中国科学院青岛生物能源与过程研究所 | Method for producing hydrogenated oil from waste oil |
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| CN102909080A (en) * | 2011-08-03 | 2013-02-06 | 中国石油大学(华东) | Oil-soluble binary compound catalyst for hydrocracking high-sulfur low-quality heavy-oil slurry bed |
| CN102911715A (en) * | 2011-08-03 | 2013-02-06 | 中国石油大学(华东) | Multifunctional oil soluble complexing agent for hydrocracking of high-sulfur poor-quality heavy oil slurry reactor |
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| CN102909080A (en) * | 2011-08-03 | 2013-02-06 | 中国石油大学(华东) | Oil-soluble binary compound catalyst for hydrocracking high-sulfur low-quality heavy-oil slurry bed |
| CN102911715A (en) * | 2011-08-03 | 2013-02-06 | 中国石油大学(华东) | Multifunctional oil soluble complexing agent for hydrocracking of high-sulfur poor-quality heavy oil slurry reactor |
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