CN101942324A - Heavy oil slurry bed hydrogenation method - Google Patents
Heavy oil slurry bed hydrogenation method Download PDFInfo
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- CN101942324A CN101942324A CN200910012503XA CN200910012503A CN101942324A CN 101942324 A CN101942324 A CN 101942324A CN 200910012503X A CN200910012503X A CN 200910012503XA CN 200910012503 A CN200910012503 A CN 200910012503A CN 101942324 A CN101942324 A CN 101942324A
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Abstract
The invention discloses a heavy oil slurry bed hydrogenation method, in particular a slurry bed heavy oil hydrogenation process using a water-soluble catalyst. The method comprises the following processes of: first, directly dispersing part of the water-soluble catalyst in a heavy oil raw material; then, mixing part of the water-soluble catalyst and an emulsifying agent to obtain a mixture and adding the mixture into the heavy oil raw material; and finally, mixing the raw material mixed with the catalyst and hydrogen to obtain a mixture, adding the mixture into a slurry bed hydrogenation reactor; and performing a hydrocracking reaction under reaction conditions. By adopting the processes of the invention, the catalyst can be dispersedly in the heavy oil raw materials uniformly, so the components such as alkane, arene, colloid and asphaltine forming heavy oil are fully contacted with the catalyst so as to improve the hydrogenation modification reaction effect, inhibit the generation of coke and improve the yield of intermediate oil.
Description
Technical field
The present invention relates to a kind of heavy oil suspended bed hydrogenation method, particularly adopt the suspended bed hydrogenation method of water-soluble catalyst processing inferior heavy oil raw material.
Background technology
Floating bed hydrogenation is a kind of important chemical reaction process, has a wide range of applications in refining of petroleum and chemical industry, and especially in the lighting process of heavy oil, the floating bed hydrogenation technology has unique advantage.In the floating bed hydrogenation process, the dispersion of catalyzer in heavy oil is particularly important, catalyzer if can uniform and stablely be distributed in the stock oil, fully contact with each component of forming heavy oil feedstock, can increase effective contact area of stock oil and catalyzer, give full play to the hydrogenation activity of catalyzer, suppress the generation of coke.Initial floating bed hydrogenation technology is used solid powder th-1 catalyst, its granular size is tens to thousands of microns, because granules of catalyst is bigger, make it can not be evenly distributed in the stock oil, hydrogenation activity is lower, the hydrogenation effect is undesirable, because the add-on of catalyzer is big, also brings certain difficulty for following process simultaneously.People developed oil soluble and water-soluble catalyst again afterwards, and oil-soluble catalyst has toxicity, and active component content is low, thereby limited its use.The water-soluble catalyst preparation is simple, has no side effect, and add-on is few, and domestic and international many companies are carrying out the research and development of water-soluble catalyst at present.But also there is scattering problem in water-soluble catalyst in stock oil.Usually water-soluble catalyst is directly added in the heavy oil feedstock at present, these water-soluble catalysts are bigger at the particle that raw material forms, and disperse insufficiently, and the carrying out of having limited hydrogenation reaction is as described in CN96102879.3.
US5916432 is presented under the certain pressure and joins in the deep fat with the aqueous solution of atomizing nozzle with ammonium molybdate, and the moisture in the drop is removed with the flash distillation of water vapour form, obtains being distributed in the granules of catalyst in the oil.Simultaneously nitrogen is passed in the head tank, removes the oxygen in the jar and the water vapour and the ammonia of generation.Mention in embodiment in dispersion process and can add the tensio-active agent sodium sulfosuccinate, its add-on is 0.088m%.But this technological process is comparatively complicated, and the catalyzer median size that is distributed in the stock oil is 10 microns, and granules of catalyst is bigger, influences its hydrogenation effect, causes light oil yield lower.Heteroatoms sodium has been introduced in the adding of sodium ion tensio-active agent on the other hand, for following process is brought certain difficulty.
Summary of the invention
At the deficiencies in the prior art, the invention provides a kind of heavy oil suspended bed hydrogenation method, the inventive method overcomes existing suspension bed hydrogenation process catalyzer and disperses inhomogeneous and particle is bigger, thereby cause pressing down the bad shortcoming of burnt effect, making that the catalyzer drop is uniform and stable is distributed in the heavy oil feedstock, fully contact with each component in the raw material, improve the hydrogenation effect.
Show after deliberation, when directly adding water-soluble suspension bed hydrogenation catalyst in the heavy oil feedstock, because of containing a spot of macromole polar material, heavy oil self (as contains sulphur, nitrogen, heteroatomic bituminous matter such as oxygen and metal and colloid), can form milk sap with water-soluble catalyst, but the final granules of catalyst that forms is bigger, and fully by bituminous matter in the heavy oil and the absorption of heavy glial component, and the alkane in the heavy oil, the chance that aromatic hydrocarbons and lightweight glial component contact with catalyzer seldom, so in the suspension bed heavy-oil hydrogenation reaction process of taking as the leading factor with thermo-cracking, the hydrogenation effect of whole heavy oil is not really desirable, the transition cracking can take place in alkane component, and the colloid that aromatic hydrocarbons and part fully do not contact with catalyzer is in thermal process reactor, form free radical separately, because not activating hydrogen in time combines with macromolecular radical, and condensation reaction takes place easily.If each component in the heavy oil is all contacted closely with catalyzer, make that catalyzer is uniform and stable to be distributed in the whole heavy oil feedstock, form the littler microemulsion of drop, the little granules of catalyst that arrives several microns then can be provided in reaction process, increase effective contact area of stock oil and catalyzer greatly, can significantly improve the hydrogenation effect of catalyzer, reduce catalyst levels.
At above-mentioned research, the present invention proposes a kind of heavy oil suspended bed hydrogenation method, process comprises: with water-soluble suspension bed hydrogenation catalyst separated into two parts, wherein a part directly joins in the heavy oil feedstock with aqueous solution form, a part joins in the heavy oil feedstock with the aqueous solution form that contains tensio-active agent in addition, mix the back and under the heavy oil floating bed hydrogenation condition, react, from react the back logistics, reclaim various reaction product.
In the inventive method, the water-soluble suspension bed hydrogenation catalyst addition sequence of two portions is any, can add a part earlier, add a part in addition after mixing again, also can add simultaneously by two portions, the preferred aqueous catalyst solution that does not contain tensio-active agent that adds earlier mixes the back and adds the aqueous catalyst solution that contains tensio-active agent.Directly the catalyzer that joins (part that does not contain tensio-active agent) in the heavy oil feedstock with aqueous solution form accounts for 5%～80% of total catalyst add-on by weight.
In the inventive method, heavy oil feedstock can be the manageable heavy feed stock of any suspension bed hydrogenation process, generally includes in the inferior raw materials such as long residuum, vacuum residuum, deasphalted oil, oil sands bitumen, consistency crude oil and gelatin liquefaction heavy oil one or more.Water-soluble suspension bed catalyzer can adopt the existing various water-soluble suspension bed catalyzer in this area, as being the two kinds of metals in periodic table of elements VIB, VIIB and the group VIII metal or the heteropolyacid salt aqueous solution of several metals, as phospho-molybdic acid nickel, phospho-wolframic acid nickel etc.; In weight metal, the total add-on of above-mentioned water-soluble suspension bed catalyzer in raw material is 20～3000 μ g/g, is preferably 100～1000 μ g/g.
In the inventive method, tensio-active agent is the tensio-active agent of this area routine, is preferably nonionic surface active agent, comprise tween, Pan of department, OP, among a kind of or several among the OE etc., its add-on is 50～5000 μ g/g in heavy oil feedstock, is preferably 200～2000 μ g/g; By this area ordinary method, for increasing the dispersion effect of catalyzer, can also make cosurfactant simultaneously, as in lower alcohol or the rudimentary ether etc. one or more, concrete as n-hexyl alcohol, Pentyl alcohol, n-hexyl ether, n-amylethers etc., its add-on account for 50～5000 μ g/g in heavy oil feedstock, be preferably 100～1000 μ g/g; Emulsification method comprises mechanical stirring or adopts colloidal mill, ultrasonic emulsator or homogenizer etc.
In the inventive method, heavy oil feedstock floating bed hydrogenation reaction conditions can require specifically to determine according to feedstock property and reaction, is 6～30MPa as reaction pressure, better is 10～20MPa; Temperature of reaction is 380～500 ℃, better is 410～460 ℃; Liquid hourly space velocity is 0.2～4.0h
-1, be preferably 1～2h
-1Hydrogen to oil volume ratio (under the standard pressure) is 100～2000, better is 300～1500.
Advantage of the present invention is:
1, the part water-soluble catalyst is directly joined in the heavy oil feedstock, can make bituminous matter and heavy colloid isopolarity material and the mutual adsorption of polar water-soluble catalyst in the heavy oil, under reaction conditions, can suppress bituminous matter and colloid condensation green coke.
2, will add in the heavy oil feedstock again behind water-soluble catalyst and the tensio-active agent uniform mixing, can guarantee that lightweight colloid, aromatic hydrocarbons and alkane component fully combine in water-soluble catalyst and the heavy oil, prevent under hydrogenation conditions the further condensation green coke of the further cracking of alkane component and aromatic hydrocarbons and part gelationus.
3, adopt and to add the adding mode in batches of heavy oil feedstock after direct adding of water-soluble catalyst and the emulsification again, can accomplish really that catalyzer contacts with the close of each component of heavy oil, avoided in the raw material part component to be rich in catalyzer and other components lack the phenomenon of catalyzer and take place, thereby the carrying out that helps each component hydrogenation reaction in the heavy oil feedstock, suppress the generation of coke simultaneously, help increasing the yield of intermediate oil.
Embodiment
A kind of detailed process of heavy oil suspended bed hydrogenation method of the present invention is as follows:
A) the part water-soluble catalyst is directly joined heavy oil feedstock with aqueous solution form (not containing tensio-active agent);
B) remainder water-soluble catalyst and tensio-active agent and cosurfactant are mixed the back and add in the heavy oil feedstock that is mixed with the part catalyzer of step a), fully mixedly make its uniform and stable distribution in stock oil;
C) heavy oil feedstock that will be mixed with catalyzer is sent into reactor, carries out hydrocracking reaction under reaction conditions;
D) reaction back logistics enters fractionation plant, obtains gasoline fraction and diesel oil distillate and hydrogenation tail oil, and wherein hydrogenation tail oil can loop back reactor.
Further specify the solution of the present invention and technique effect below by embodiment and comparative example.
Embodiment 1
The aqueous solution of a certain amount of concentration is 9.2% (calculating by weight metal in the catalyzer) phospho-molybdic acid nickel directly adds in the heavy oil feedstock, adopts the mode of magnetic agitation then, and catalyzer is dispersed in the heavy oil feedstock (main character sees Table 1); Join in the above-mentioned heavy oil feedstock behind the aqueous solution of (calculating) the phospho-molybdic acid nickel that with part concentration is 9.2% again and tensio-active agent tween 85 and the cosurfactant n-hexyl alcohol thorough mixing by weight metal in the catalyzer, adopt the high shear stirring mode that aqueous catalyst solution is dispersed in the heavy oil feedstock, then the mixing raw material that obtains and hydrogen are mixed into the high-temperature high-voltage reaction device and carry out hydrogenation reaction, reaction back product obtains gasoline fraction through the normal pressure distillation, diesel oil distillate and hydrogenation tail oil, wherein operational condition and test-results are listed in table 2 and table 3 respectively.
Comparative example 1
Basic identical with embodiment 1 process of the test, difference is that catalyzer all adopts the mode of direct adding to mix with raw material, does not use tensio-active agent and cosurfactant.Wherein operational condition and test-results are listed in table 2 and table 3 respectively.
Comparative example 2
Basic identical with embodiment 1 process of the test, difference is that required whole water-soluble catalysts all with after tensio-active agent and cosurfactant mix mix with heavy oil feedstock again.Wherein operational condition and test-results are listed in table 2 and table 3 respectively.
The heavy oil feedstock character of test usefulness sees Table 1.Wherein the coke growing amount of test-results characterizes with toluene insolubles.
Embodiment 2～4
According to embodiment 1 described process, adopt the condition described in the table 4, reaction result sees Table 5.
Table 1 heavy oil feedstock character
Table 2 embodiment 1 and comparative example operational condition
Table 3 embodiment 1 and comparative example test-results
Table 4 embodiment 2～4 operational conditions
Table 5 embodiment 2～4 tests the result
Claims (10)
1. heavy oil suspended bed hydrogenation method, it is characterized in that: with water-soluble suspension bed hydrogenation catalyst separated into two parts, wherein a part directly joins in the heavy oil feedstock with aqueous solution form, a part joins in the heavy oil feedstock with the aqueous solution form that contains tensio-active agent in addition, mix the back and under the heavy oil floating bed hydrogenation condition, react, from react the back logistics, reclaim various reaction product.
2. in accordance with the method for claim 1, it is characterized in that: the water-soluble suspension bed hydrogenation catalyst of two portions adds the fashionable part that adds earlier, adds a part in addition after mixing again, and perhaps two portions add simultaneously.
3. in accordance with the method for claim 1, it is characterized in that: the water-soluble suspension bed hydrogenation catalyst of two portions adds fashionable, adds the aqueous catalyst solution that does not contain tensio-active agent earlier, mixes the back and adds the aqueous catalyst solution that contains tensio-active agent.
4. it is characterized in that in accordance with the method for claim 1: directly the catalyzer that joins in the heavy oil feedstock with aqueous solution form accounts for 5%～80% of total catalyst add-on by weight.
5. it is characterized in that in accordance with the method for claim 1: heavy oil feedstock comprises one or more in long residuum, vacuum residuum, deasphalted oil, oil sands bitumen, consistency crude oil and the gelatin liquefaction heavy oil.
6. it is characterized in that in accordance with the method for claim 1: water-soluble suspension bed catalyzer is the two kinds of metals in periodic table of elements VIB, VIIB and the group VIII metal or the heteropolyacid salt aqueous solution of several metals.
7. according to claim 1 or 6 described methods, it is characterized in that: water-soluble suspension bed catalyzer is phospho-molybdic acid nickel or phospho-wolframic acid nickel.
8. according to claim 1 or 6 described methods, it is characterized in that: in weight metal, the total add-on of water-soluble suspension bed catalyzer in raw material is 20～3000 μ g/g.
9. in accordance with the method for claim 1, it is characterized in that: tensio-active agent is a nonionic surface active agent, and add-on is 50～5000 μ g/g in heavy oil feedstock.
10. in accordance with the method for claim 1, it is characterized in that: heavy oil feedstock floating bed hydrogenation reaction conditions is, reaction pressure is 6～30MPa, and temperature of reaction is 380～500 ℃, and liquid hourly space velocity is 0.2～4.0h
-1, hydrogen to oil volume ratio is 100～2000.
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| CN200910012503.XA CN101942324B (en) | 2009-07-09 | 2009-07-09 | Heavy oil slurry bed hydrogenation method |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104560159A (en) * | 2013-10-28 | 2015-04-29 | 中国石油化工股份有限公司 | Slurry bed residual oil hydrogenation method |
| CN110824026A (en) * | 2018-08-10 | 2020-02-21 | 中国石油化工股份有限公司 | Evaluation method of contact agent for heavy oil contact cracking |
| CN112592731A (en) * | 2020-10-10 | 2021-04-02 | 中国科学院青岛生物能源与过程研究所 | Method for producing second-generation biodiesel by liquid catalyst |
| CN115261061A (en) * | 2022-08-08 | 2022-11-01 | 徐文忠 | Non-fixed bed hydrogenation synergistic deslagging process |
-
2009
- 2009-07-09 CN CN200910012503.XA patent/CN101942324B/en active Active
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104560159A (en) * | 2013-10-28 | 2015-04-29 | 中国石油化工股份有限公司 | Slurry bed residual oil hydrogenation method |
| CN104560159B (en) * | 2013-10-28 | 2016-08-17 | 中国石油化工股份有限公司 | A kind of slurry bed system residual hydrogenation method |
| CN110824026A (en) * | 2018-08-10 | 2020-02-21 | 中国石油化工股份有限公司 | Evaluation method of contact agent for heavy oil contact cracking |
| CN110824026B (en) * | 2018-08-10 | 2023-09-05 | 中国石油化工股份有限公司 | Evaluation method of contact agent for heavy oil contact cracking |
| CN112592731A (en) * | 2020-10-10 | 2021-04-02 | 中国科学院青岛生物能源与过程研究所 | Method for producing second-generation biodiesel by liquid catalyst |
| CN115261061A (en) * | 2022-08-08 | 2022-11-01 | 徐文忠 | Non-fixed bed hydrogenation synergistic deslagging process |
| CN115261061B (en) * | 2022-08-08 | 2023-09-15 | 徐文忠 | Non-fixed bed hydrogenation synergistic deslagging process |
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