CN104888860A - Naphthenate catalyst, and preparation method and application thereof - Google Patents
Naphthenate catalyst, and preparation method and application thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of catalysts in an oil-refining chemical process and particularly relates to a naphthenate catalyst for a hydrocracking process for an inferior heavy-oil slurry bed, and a preparation method and application of the naphthenate catalyst. The catalyst is characterized in that active components are Ni and/or Mo, wherein the metal mass content of Ni is 5%-8%, the metal mass content of Mo is 4%-7%, and the active components and a sulfur source exist in the form of transition metal sulfide with the particle diameter being 1-100 microns. The naphthenate catalyst prepared by the method disclosed by the invention is relatively small in added amount, low in use cost, and simple in synthesis method, and is suitable for large-scale industrial production; materials are cheap and easy to obtain; and the naphthenate catalyst has the advantages that the dispersing effect in the heavy-oil material is good, the metal content is high, the hydrogenation activity is high, the coke-inhibiting property is good, reaction tail oil does not contain solid particles basically and the light-oil yield is high.
Description
Technical field
The invention belongs to the technical field of catalyst in oil-refining chemical technique, be specifically related to naphthenate catalyst, preparation method and its usage for inferior heavy oil slurry bed system hydrocracking process.
Background technology
The trend cleaned along with crude oil heaviness, in poor quality and product requirement is increasingly sharpened, and heavy-oil hydrogenation technology becomes the emphasis of research gradually.Heavy-oil slurry hydrocracking process is to the wide adaptability of raw material, high-sulfur, high metal, high carbon residue and full-bodied inferior heavy oil can be processed, and there is higher light oil yield, and become a kind of novel heavy oil lighting technique of institute's active development both at home and abroad now.The main flow of heavy oil slurry bubble bed hydrocracking process is, the catalyst of fine and even or additive are scattered in feedstock oil, mix with hydrogen again, reactor is entered in the lump after heating in heating furnace, in high temperature, the raw cracking reaction of elevated pressure, in the process, hydrogen and catalyst be coke inhibiting in sizable degree not only, also has the effect that some promote HDM, desulfurization, denitrification reaction.At present, because heavy-oil slurry hydrocracking water-soluble catalyst dispersing technology is complicated, energy consumption is high, is unfavorable for industrial application.Therefore, the preparation of high efficient oil dissolubility catalyst is very important for the industrialization promotion of heavy-oil slurry hydrocracking process.
Naphthenate is a kind of oil soluble metal salt, meet heavy-oil slurry hydrocracking to the oil-soluble basic demand of catalyst, but be mainly used in terebine, chemical catalyst, lube oil additive, stabilizer for plastics, tyre adhesive, timber preservative, plant growth regulator etc. at present, market demand is less, not as the example that Oil Refinery Industry catalyst uses.In addition, due to the synthesis technique comparatively backwardness of current naphthenate, make product have tenor lower, hydrogenation activity is lower, oil-soluble effect is poor, the shortcomings such as preparation cost is higher, are not suitable as heavy-oil slurry hydrocracking catalyst.Therefore, propose a kind of novel method for synthesizing of metal naphthenate class, to improve tenor and the oil-soluble of naphthenate, make it to be suitable for the oil-soluble catalyst as the hydrocracking of inferior heavy oil slurry bed system.
Summary of the invention
The invention provides a kind of naphthenate catalyst, preparation method and its usage, solve the synthesis technique comparatively backwardness of current naphthenate, product is made to have tenor lower, hydrogenation activity is lower, oil-soluble effect is poor, the shortcomings such as preparation cost is higher, are not suitable as the problems such as heavy-oil slurry hydrocracking catalyst.
For solving the problems of the technologies described above, the technical solution used in the present invention is:
A kind of naphthenate catalyst, the active component of this catalyst is Ni and/or Mo, wherein Ni metal quality content is 5% ~ 8%, Mo metal quality content is 4% ~ 7%, and active component and sulphur source think that particle diameter exists the transient metal sulfide form of 1 μm ~ 100 μm.
The invention provides a kind of preparation method of naphthenate catalyst, described active component is nickel, and preparation method is as follows:
(1) aphthenic acids and distilled water are added in reaction vessel, after being heated to 55 DEG C ~ 75 DEG C, add highly basic, at temperature is 80 DEG C ~ 100 DEG C, carries out reaction 1 ~ 5 hour;
(2), after reaction terminates, transition metal salt is joined in reactor, react at temperature is 70 DEG C ~ 100 DEG C, 1 ~ 6 hour reaction time;
(3) reaction terminates, and water phase separated after being left standstill by product, gained oil-phase product is naphthenate catalyst.
Further, a preferred embodiment of the present invention is: the mol ratio of aphthenic acids, highly basic, transition metal salt three is: 0.6 ~ 1.4:1:0.3 ~ 0.7.
Further, a preferred embodiment of the present invention is: described highly basic is the combination of one or both materials in NaOH, potassium hydroxide material.
Further, a preferred embodiment of the present invention is: described transition metal salt is the combination of one or both materials in transition metal sulfate, transition metal villaumite.
Invention further provides a kind of preparation method of naphthenate catalyst, described active component is molybdenum, and preparation method is as follows:
(1) add in reaction vessel by oxalic acid and distilled water, after heating for dissolving, add molybdenum source and react, the reaction time is 1 ~ 3 hour;
(2), after reaction terminates, the aphthenic acids added, 200 DEG C ~ 300 DEG C reactions 3 ~ 5 hours;
(3) stop reaction, pour into while hot in beaker, leave standstill, obtain naphthenate catalyst.
Further, a preferred embodiment of the present invention is: the mass ratio of oxalic acid, molybdenum source, aphthenic acids three is: 1 ~ 5:1:5 ~ 10.
Further, a preferred embodiment of the present invention is: molybdenum source is the combination of one or more materials in molybdenum trioxide, sodium molybdate, ammonium molybdate.
Naphthenate catalyst prepared by the present invention is used for the method for inferior heavy oil slurry bed system hydrocracking, and the tenor in naphthenate 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 of inferior heavy oil slurry bed system hydrocracking is reaction temperature 420 DEG C ~ 460 DEG C, 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.
Beneficial effect 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, and raw material is cheaply easy to get, and is 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, presses down burnt performance good, and substantially not containing solid particle in reaction tail oil, light oil yield is high.
Detailed description of the invention
Below in conjunction with the specific embodiment of the invention, be clearly and completely described technical scheme of the present invention, obviously, described embodiment is only the present invention's part embodiment, instead of whole embodiments.Based on the embodiment in the present invention, those of ordinary skill in the art, not making the every other embodiment obtained under creative work prerequisite, belong to the scope of protection of the invention.
Embodiment 1
A kind of naphthenate catalyst, the active component of this catalyst is Ni, and wherein Ni tenor is 6%, and active component and sulphur source think that particle diameter exists the transient metal sulfide form of 1 μm ~ 100 μm,
Its preparation method is as follows:
(1) get in 0.05mol aphthenic acids and add distilled water, after heating fully mixes, under temperature 55-75 DEG C of condition, add 0.04mol NaOH and react 4h at 60 DEG C ~ 100 DEG C;
(2), after reaction terminates, add 0.002mol nickelous sulfate in reactor, react at temperature is 80 DEG C ~ 100 DEG C, 2 hours reaction time;
(3) reaction terminates, and water phase separated after being left standstill by product, gained oil-phase product is naphthenate catalyst.
In prepared catalyst, nickel metal quality content is 6.02%.
Embodiment 2
Substantially the same manner as Example 1, difference is: transition metal salt adopts nickel chloride, and the reaction time in (1) step is 1h, and the reaction time in (2) step is 6h, and in prepared catalyst, nickel metal quality content is 5.84%.
Embodiment 3
Substantially the same manner as Example 1, difference is: the mol ratio of aphthenic acids, highly basic, transition metal salt three is: 1.4:1:0.3, highly basic adopts potassium hydroxide, reaction time in (1) step is 5h, reaction time in (2) step is 1h, and in prepared catalyst, nickel metal quality content is 5.01%
Embodiment 4
Substantially the same manner as Example 2, difference is: the mol ratio of aphthenic acids, highly basic, transition metal salt three is: 0.6:1:0.7, highly basic adopts the potassium hydroxide of mass ratio 1:1 and the mixture of NaOH, and in prepared catalyst, nickel metal quality content is 8.02%.
Embodiment 5
A kind of naphthenate catalyst, the active component of this catalyst is Mo, and wherein Mo metal quality content is 4% ~ 7%, and active component and sulphur source think that particle diameter exists the transient metal sulfide form of 1 μm ~ 100 μm, and its preparation method is as follows:
(1) get 12.6g oxalic acid and distilled water adds in container, after heating for dissolving, add 4.8g molybdenum trioxide and react, the reaction time is 2 hours, then
(2) after reaction terminates, the 42g aphthenic acids being preheating to 200-300 DEG C is added, alkanoic acid, 200 ~ 300 DEG C of reactions 4 hours;
(3) stop reaction, pour into while hot in beaker, leave standstill, obtain naphthenate catalyst.
In prepared catalyst, molybdenum mass content is 5.72%.
Embodiment 6
Substantially the same manner as Example 5, difference is: the mass ratio of oxalic acid, molybdenum source, aphthenic acids three is: 1:1:10, molybdenum source is sodium molybdate, reaction time in (1) step is 1h, reaction time in (2) step is 5h, and in prepared catalyst, molybdenum mass content is 7.01%.
Embodiment 7
Substantially the same manner as Example 5, difference is: the mass ratio of oxalic acid, molybdenum source, aphthenic acids three is: 5:1:5, molybdenum source is ammonium molybdate, reaction time in (1) step is 3h, reaction time in (2) step is 3h, and in prepared catalyst, molybdenum mass content is 4.02%.
Embodiment 8 ~ 11, the present embodiment uses raw material to be Venezuela's-No. 380 fuel oil, and its character is in table 1.Autoclave is investigated the conversion situation of feedstock oil under different catalysts addition, reaction pressure, temperature and time condition, and experimental result is in table 2.
As shown in Table 2, it is good that oil-soluble metal naphthenate class catalyst provided by the invention has dispersion effect, and dispersing technology is simple to operate, and hydrogenation activity is high, press down the good advantage of burnt performance.This catalyst application is in the hydrocracking process of suspended bed of inferior heavy, residual oil, when addition (in metal)≤200 μ g/g of catalyst, namely have and higher press down burnt performance, coking yield < 2.0m% ,≤500 DEG C of liquid product yields can reach more than 80m%.
Table 1 residual oil slurry bed system Hydrocracking Raw Oil character
Table 2 heavy-oil slurry hydrocracking reaction result
The foregoing is only preferred embodiment of the present invention, not in order to limit the present invention, within the spirit and principles in the present invention all, any amendment done, equivalent replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (10)
1. a naphthenate catalyst, it is characterized in that: the active component of this catalyst is Ni and/or Mo, wherein Ni metal quality content is 5% ~ 8%, Mo metal quality content is 4% ~ 7%, and active component and sulphur source think that particle diameter exists the transient metal sulfide form of 1 μm ~ 100 μm.
2. a preparation method for naphthenate catalyst according to claim 1, is characterized in that: described active component is nickel, and preparation method is as follows:
(1) aphthenic acids and distilled water are added in reaction vessel, after being heated to 55 DEG C ~ 75 DEG C, add highly basic, at temperature is 80 DEG C ~ 100 DEG C, carries out reaction 1 ~ 5 hour;
(2), after reaction terminates, transition metal salt is joined in reactor, react at temperature is 70 DEG C ~ 100 DEG C, 1 ~ 6 hour reaction time;
(3) reaction terminates, and water phase separated after being left standstill by product, gained oil-phase product is naphthenate catalyst.
3. the preparation method of naphthenate catalyst according to claim 2, is characterized in that: the mol ratio of aphthenic acids, highly basic, transition metal salt three is: 0.6 ~ 1.4:1:0.3 ~ 0.7.
4. the preparation method of the naphthenate catalyst according to Claims 2 or 3, is characterized in that: described highly basic is the combination of one or both materials in NaOH, potassium hydroxide material.
5. the preparation method of the naphthenate catalyst according to Claims 2 or 3, is characterized in that: described transition metal salt is the combination of one or both materials in transition metal sulfate, transition metal villaumite.
6. a preparation method for naphthenate catalyst according to claim 1, is characterized in that: described active component is molybdenum, and preparation method is as follows:
(1) add in reaction vessel by oxalic acid and distilled water, after heating for dissolving, add molybdenum source and react, the reaction time is 1 ~ 3 hour;
(2), after reaction terminates, the aphthenic acids added, 200 DEG C ~ 300 DEG C reactions 3 ~ 5 hours;
(3) stop reaction, pour into while hot in beaker, leave standstill, obtain naphthenate catalyst.
7. the preparation method of naphthenate catalyst according to claim 6, is characterized in that: the mass ratio of oxalic acid, molybdenum source, aphthenic acids three is: 1 ~ 5:1:5 ~ 10.
8. the preparation method of the naphthenate catalyst according to claim 6 or 7, is characterized in that: molybdenum source is the combination of one or more materials in molybdenum trioxide, sodium molybdate, ammonium molybdate.
9. the naphthenate catalyst prepared by any one of claim 2-7 is used for the method for inferior heavy oil slurry bed system hydrocracking, it is characterized in that: the tenor in naphthenate catalyst is 50 ~ 2000 μ g/g in the ratio of heavy oil feedstock.
10. the method for inferior heavy oil slurry bed system according to claim 9 hydrocracking, is characterized in that: the condition of inferior heavy oil slurry bed system hydrocracking is reaction temperature 420 DEG C ~ 460 DEG C, 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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| CN108117882A (en) * | 2018-02-11 | 2018-06-05 | 宁波普前环保科技有限公司 | A kind of method for processing waste plastics and cellulose |
| CN108219815A (en) * | 2018-02-11 | 2018-06-29 | 宁波普前环保科技有限公司 | The method for the treatment of of waste plastics and cellulose |
| CN108273558A (en) * | 2018-02-11 | 2018-07-13 | 宁波普前环保科技有限公司 | Catalytic cracking catalyst and its preparation method and application |
| CN108329514A (en) * | 2018-02-11 | 2018-07-27 | 宁波普前环保科技有限公司 | The method for processing waste plastics and cellulose |
| CN108355711A (en) * | 2018-02-11 | 2018-08-03 | 宁波普前环保科技有限公司 | A kind of catalytic cracking catalyst and its preparation method and application |
| 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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| CN108117882A (en) * | 2018-02-11 | 2018-06-05 | 宁波普前环保科技有限公司 | A kind of method for processing waste plastics and cellulose |
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| CN108273558A (en) * | 2018-02-11 | 2018-07-13 | 宁波普前环保科技有限公司 | Catalytic cracking catalyst and its preparation method and application |
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| 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 |
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| CN108329514B (en) * | 2018-02-11 | 2019-12-17 | 北京石油化工学院 | Method for processing 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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