CN101434860B - Conversion method for hydrogenation of heavy and residual oil suspension bed - Google Patents
Conversion method for hydrogenation of heavy and residual oil suspension bed Download PDFInfo
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- CN101434860B CN101434860B CN 200710158360 CN200710158360A CN101434860B CN 101434860 B CN101434860 B CN 101434860B CN 200710158360 CN200710158360 CN 200710158360 CN 200710158360 A CN200710158360 A CN 200710158360A CN 101434860 B CN101434860 B CN 101434860B
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Abstract
The invention discloses a conversion method of heavy and residual oil suspension bed hydrogenation. The method comprises the steps as follows: a feeding flow containing hydrogen and heavy and residual oil passes through a honeycomb-shaped or similar structure integrated reactor of a hydrogenation catalyst; the linear speed of liquid and gas in a hollow tower is controlled and a taylor flow is formed in the structural integrated reactor; and as the gas and the liquid are uniformly distributed in each passage, better gas-liquid distribution can be formed, the catalytic efficiency of the reactor can be greatly improved, and the running period can be effectively prolonged.
Description
Technical field
The present invention relates to a kind of method for transformation of heavy, hydrogenation of residual oil suspended bed.
Background technology
Along with crude oil in the world wide heaviness and poor qualityization gradually, and to the increase of lightweight oil demand, so the lighting processing technology research of poor quality, heavy oil product come into one's own.In inferior, heavy oil product lighting technology, the suspension bed technology since process simply, the transformation efficiency advantages of higher becomes the important directions of research.Because floating bed hydrogenation adopts disposable catalyzer or additive, need not to consider the problem of catalyst deactivation, so can process the BO inferior that heavy metal, sulphur, nitrogen content are very high and carbon residue is also very high, has very big meliority.Heavy oil floating bed hydrogenation technology is generally used oil soluble or water-soluble disperse type catalyzer, like CN95118354.0, CN96102880.7, US4637870, US5039392 etc.
But for the suspension bed technology, because reactor drum is mainly the sky core structure, the gas of reaction mass, liquid two are difficult for being uniformly dispersed mutually; Along with material moves in reactor drum; The gas phase micro-bubble is easy to assemble for than air pocket, causes in twos can not fully to contact mutually, and liquid phase heavy oil product raw material is in local non-hydro response behaviour; Be prone to take place side reactions such as coking, be unfavorable for the stable long-term operation that reacts.
Summary of the invention
To the deficiency of prior art, the present invention provides a kind of heavy, hydrogenation of residual oil suspended bed method for transformation, improves the dispersing uniformity of reaction mass, in the steady running cycle of further improving the floating bed hydrogenation conversion process, can improve the hydrocracking quality product simultaneously.
The present invention is heavy, the hydrogenation of residual oil suspended bed method comprises following content: disperse type catalyzer is distributed in the raw oil; Under hydrogen existence and floating bed hydrogenation conversion condition; Raw oil and hydrogen are through having the honeycomb fashion one-piece construction catalyzer or the filler of parallel channels, the channel parallel of the mobile direction of reaction mass and honeycomb fashion one-piece construction catalyzer or filler.
In the inventive method, adopt honeycomb fashion one-piece construction catalyzer or filler,, one or more honeycomb fashion one-piece construction catalyzer or filler are set in reactor drum according to the scale of reactor drum and the size of honeycomb structured catalyst configurations or filler.Honeycomb fashion one-piece construction filler can be processed by usual method for this area temperature-resistant material commonly used, and channel diameter is generally 1～200mm, preferred 2～10mm.The material that has catalytic hydrogenation activity in the filler passage surface-coated; Can become honeycomb fashion one-piece construction catalyzer; The hydrogenation activity component is generally one or more among Mo, W, Ni, the Co; With active metal oxide (weight) content in every liter of honeycomb fashion one-piece construction catalyzer is 1～20g, can contain auxiliary agents such as P, B, Zr, Si or Zr, and general the employing has close-burning component and hydrogenation activity applies honeycomb fashion one-piece construction filler jointly during coating; Dry then, roasting gets final product the method that aforesaid method is well known to those skilled in the art.
When using honeycomb fashion one-piece construction catalyzer, in certain running period, can not use or use less disperse type catalyzer in the reaction feed, because the Catalytic Hydrogenation Properties of honeycomb fashion one-piece construction catalyzer is stronger at this moment.Along with the prolongation in fortune cycle, honeycomb fashion one-piece construction catalyst activity reduction when a little, need progressively be added disperse type catalyzer in reaction feed.
In the inventive method floating bed hydrogenation conversion process, operational condition and disperse type catalyzer can confirm that be generally reaction pressure like reaction conditions: 2～30MPa better is 8～15MPa by the existing general knowledge in this area; Temperature of reaction is 300～500 ℃, better is 400～420 ℃; Liquid hourly space velocity is 0.2～8.0h
-1, be preferably 1～2h
-1Hydrogen to oil volume ratio is 100～3000, better is 500～1000.Void tower gas line speed is generally 1.0～200mm/s greater than 1.0mm/s; The void tower liquid linear velocity is generally 0.5～100mm/s greater than 0.5mm/s.Disperse type catalyzer can be water-soluble catalyst, oil-soluble catalyst, solid powder th-1 catalyst etc.; Of prior art CN95118354.0, CN96102880.7, US4637870, US5039392 etc.; Add-on is generally 10～10000 μ g/g (in metal) in raw oil, is preferably 30～500 μ g/g.
Owing to use honeycomb fashion one-piece construction catalyzer or filler, solved the two dispersive problems that contact, so the reaction mass flow pattern can be upwards to flow, also can flow downward, also can horizontal flow, enlarged operating method.
The present invention is heavy, the method for transformation of hydrogenation of residual oil suspended bed can be operated as follows; Raw oil and hydrogen are through having the honeycomb fashion one-piece construction catalyzer of parallel channels, and the channel parallel of mobile direction of reaction mass and honeycomb fashion one-piece construction catalyzer is at initial stage running period; Do not use or use less disperse type catalyzer in the reaction feed; Along with the prolongation in fortune cycle, in reaction feed, progressively add disperse type catalyzer, above-mentioned identical under other condition.
The inventive method has following advantage:
1, the inventive method is provided with honeycomb fashion one-piece construction catalyzer or filler in outstanding newborn bed bioreactor; This catalyzer or filler cause the passage dislocation between the honeycomb-like part of adjacent contact; When the incoming flow thigh passes passage, producing has control with limited turbulent flow with mix, and realizes getting into the homogeneity of gas-liquid material in catalyzer or the filler.
2, in the inventive method; Use the operating method fundamental difference of packed bed reactor of operating method and conventional granular catalyzer and random catalyst filling of the reactor drum of this catalyzer; Because gas and liquid are evenly distributed in each passage, the geometrical feature of the parallel channels that promptly cellular integer catalyzer is unique can form reasonable gas-liquid and distribute; Not existing gas microbubbles to assemble the formation air pocket causes gas-liquid two-phase to connect inadequate problem; Eliminated the local non-hydro response behaviour of existing suspension bed reaction process, made temperature of reactor more even, the wetting zone with stagnant liquid of part significantly reduces; The overall reactor volumetric efficiency is improved, and can improve the catalytic efficiency (of reactor drum greatly.Thereby solved the problem that suspension bed hydrogenation process can not the LP steady running.
3, owing to the contact efficiency that has improved the two phase reaction material, and the concerted catalysis effect of honeycombed catalyst, make quality heavy, hydrogenation of residual oil suspended bed conversion reaction product that further raising arranged.
Description of drawings
Fig. 1 is the schematic perspective view of the cellular monolith honeycomb reactor part of the present invention.
Embodiment
A kind of detailed process of method of the present invention may further comprise the steps: heavy, residual oil are handled with the structure-type monolith honeycomb reactor of honeycomb configuration in (1); Comprise in the reaction vessel two sections or more the section structure-type honeycombed catalyst section; Each section comprises the passage of the honeycomb of many parallel open; The wall surface of catalytic activity is contained on the border of passage; Conduit wall is from the entrance extension to the outlet, and passage all is parallel to a common stream moving axis through reactor drum, is connected to be communicated with the end-to-end mode of mobile between two sections or the multistage catalyzer; Material flow is directly through inlet; Second catalyst section is connected with first catalyst section to be communicated with the end-to-end mode of mobile; First catalyst section and second catalyst section each have an opening for feed and a discharge port; Passage in second section catalyst section and the passage in first catalyst section are provided with deflection; Make most of passages of at least the first catalyst section have facing to the open exit end of at least one conduit wall section, and at least two openings that adjoin passage in the second catalyst section bed ingress.(2) can or need not add water-soluble or the oil soluble metal catalyzer, counterweight, residual oil be handled.Perhaps, progressively add water-soluble or the oil soluble metal catalyzer along with the passing of running time.
The inventive method is applicable to all heavy inferior oil handling utilizations such as weight, residual oil, coal tar, oil-sand.Below in conjunction with accompanying drawing and concrete embodiment practical implementation process of the present invention and effect are elaborated.
Embodiment 1
Under the situation of not adding disperse type catalyzer, utilize the structure-type monolith honeycomb reactor of honey-combed to make an experiment, Ni, Mo isoreactivity metal component contain NiO 5g in the interior wall loading of honeycomb on every liter of honeycomb structured catalyst configurations, contain MoO
312g, the hydrogenation activity component is mixed with fixed attention with white lake and is coated on the honey-combed filler, and dry then, roasting makes.Feedstock property is seen table 1, and table 2 is experiment back gained data.
Select the immobilized catalyst honeycomb of cylindrical aluminum oxide of diameter 50mm, length 600cm to make an experiment, each channel diameter 4mm, channel wall thickness is 0.05mm.
Table 1 raw oil character
| Project | Residual oil 1 | Residual oil 2 | Residual oil 3 | Residual oil 4 |
| Density (20 ℃), Kgm -3 | 1002 | 995 | 987 | 978 |
| Sulphur, wt% | 4.2 | 3.5 | 4.1 | 2.9 |
| Nitrogen, μ gg -1 | 5899 | 4214 | 3748 | 7845 |
| Carbon residue, wt% | 18.2 | 15.4 | 14.2 | 16.7 |
| Nickel+vanadium, μ gg -1 | 241.7 | 287.8 | 268.1 | 198.9 |
Table 2 embodiment 1 weight, hydrogenation of residual oil suspended bed result
| Embodiment | 1-1 | 1-2 | 1-3 | 1-4 |
| Raw material | Residual oil 1 | Residual oil 2 | Residual oil 2 | Residual oil 4 |
| Temperature, ℃ | 410 | 410 | 420 | 420 |
| Pressure, MPa | 10 | 10 | 10 | 10 |
| Hydrogen-oil ratio | 600 | 700 | 500 | 800 |
| Air speed, h -1 | 1.0 | 1.0 | 1.0 | 1.0 |
| Product, wt% | ||||
| Petroleum naphtha | 6.2 | 8.5 | 12.95 | 5.3 |
| Diesel oil | 25.9 | 26.7 | 28.84 | 21.4 |
| Wax oil | 39.3 | 41.6 | 37.16 | 49.7 |
| Tail oil | 28.6 | 23.2 | 21.05 | 23.6 |
Embodiment 2
Each channel diameter 6mm, wall thickness are 0.2mm, and structure is identical with embodiment 1 with active metallic content.Add paucidisperse type catalyzer, disperse type catalyzer is CN97121844.7 embodiment 2 said catalyzer, and add-on is by metal weight.
Table 3 embodiment 2 weights, hydrogenation of residual oil suspended bed result
| Embodiment | 2-1 | Comparative example 1 | 2-2 | 2-3 | 2-4 |
| Raw material | Residual oil 3 | Residual oil 3 | Residual oil 2 | Residual oil 2 | Residual oil 4 |
| Reaction pressure, MPa | 12 | 12 | 8 | 10 | 8 |
| Temperature of reaction, ℃ | 435 | 435 | 435 | 438 | 436 |
| The catalyzer add-on, μ gg -1 | 50 | 50 | 30 | 30 | 30 |
| Liquid product distributes, wt% | |||||
| Atmospheric distillate | 31.50 | 29.07 | 43.51 | 32.60 | 46.27 |
| Vacuum distillate | 41.40 | 31.46 | 40.90 | 49.04 | 40.33 |
| Tail oil | 26.88 | 39.13 | 14.70 | 18.30 | 12.70 |
| Toluene insolubles, wt% | 0.12 | 2.94 | 0.29 | 0.06 | 0.21 |
Comparative example 1 does not just use the honeycomb solid catalyst by the condition identical with embodiment 2-1, compares.Can find out that from table 3 toluene insolubles in the inventive method reaction product (being the coking material) content significantly reduces, coking is the major influence factors of suspended-bed reactor steady running, so the inventive method can effectively prolong the steady running cycle.
Embodiment 3
Each channel diameter is 2mm, and wall thickness is 0.2mm, utilizes pottery for the structure-type monobloc(k)type filler of the honey-combed of material makes an experiment, and does not contain active metal component.Add the disperse type catalyzer of a little, disperse type catalyzer is identical with embodiment 2, and consumption is 50 μ g/g.
Table 4 embodiment 3 weights, hydrogenation of residual oil suspended bed result
| Embodiment | 3-1 | ?3-2 | ?3-3 | ?3-4 |
| Raw material | Residual oil 3 | Residual oil 3 | Residual oil 4 | Residual oil 4 |
| Reaction pressure, MPa | 7 | ?8 | ?9 | ?8 |
| Temperature of reaction, ℃ | 435 | ?435 | ?438 | ?436 |
| Liquid product distributes, wt% | ||||
| Petroleum naphtha | 3.7 | ?8.5 | ?7.5 | ?4.7 |
| Diesel oil | 45.5 | ?47.4 | ?43.57 | ?41.27 |
| Wax oil | 39.3 | ?38.4 | ?34.15 | ?36.50 |
| Tail oil | 11.5 | ?5.7 | ?14.78 | ?17.53 |
Table 5 embodiment 2-1 and the contrast of comparative example 1 reaction product quality
| Embodiment 2-1 | Comparative example 1 | |||
| S，μg/g | N，μg/g | S，μg/g | N，μg/g | |
| Atmospheric distillate | 47 | 234 | 300 | 1400 |
| Vacuum distillate | 374 | 765 | 1100 | 3700 |
| Tail oil | 1043 | 1840 | 2250 | 4400 |
Can find out from table 5, adopt the inventive method and can further improve the hydroconversion reactions product quality.
Claims (7)
1. a weight, hydrogenation of residual oil suspended bed method for transformation; Comprise: disperse type catalyzer is distributed in the raw oil; Under hydrogen existence and floating bed hydrogenation conversion condition; Raw oil and hydrogen are through having the honeycomb fashion one-piece construction catalyzer or the filler of parallel channels, the channel parallel of the mobile direction of reaction mass and honeycomb fashion one-piece construction catalyzer or filler;
Wherein honeycomb fashion one-piece construction filler is processed with temperature-resistant material, and channel diameter is 1～200mm, at the material that the filler passage surface-coated has catalytic hydrogenation activity, can become honeycomb fashion one-piece construction catalyzer;
Described disperse type catalyzer is water-soluble catalyst, oil-soluble catalyst or solid powder th-1 catalyst, is 10～10000 μ g/g in the add-on of metal in raw oil;
Described floating bed hydrogenation conversion condition is: reaction pressure is 2～30MPa, and temperature of reaction is 300～500 ℃, and liquid hourly space velocity is 0.2～8.0h
-1, hydrogen to oil volume ratio is 100～3000.
2. according to the described method of claim 1, it is characterized in that described honeycomb fashion one-piece construction catalyzer or filler are provided with one or more in reactor drum.
3. according to the described method of claim 1; It is characterized in that described honeycomb fashion one-piece construction catalyzer contains the hydrogenation activity component; The hydrogenation activity component is one or more among Mo, W, Ni and the Co, is 1～20g in the content of active metal oxide weight in every liter of honeycomb fashion one-piece construction catalyzer.
4. according to the described method of claim 1, it is characterized in that described floating bed hydrogenation conversion condition is: reaction pressure is 8～15MPa, and temperature of reaction is 400～420 ℃, and liquid hourly space velocity is 1～2h
-1, hydrogen to oil volume ratio is 500～1000.
5. according to the described method of claim 1, it is characterized in that void tower gas line speed is 1.0～200mm/s, the void tower liquid linear velocity is 0.5～100mm/s.
6. according to the described method of claim 1, it is characterized in that described disperse type catalyzer add-on is 30～500 μ g/g.
7. a weight, hydrogenation of residual oil suspended bed method for transformation; Raw oil and hydrogen are through having the honeycomb fashion one-piece construction catalyzer of parallel channels; Disperse type catalyzer is not used or used less to the channel parallel of mobile direction of reaction mass and honeycomb fashion one-piece construction catalyzer at initial stage running period, in the reaction feed; Along with the prolongation of running period, in reaction feed, progressively add disperse type catalyzer;
Wherein honeycomb fashion one-piece construction catalyzer is: honeycomb fashion one-piece construction filler is processed with temperature-resistant material, and channel diameter is 1～200mm, at the material that the filler passage surface-coated has catalytic hydrogenation activity, promptly becomes honeycomb fashion one-piece construction catalyzer;
Described disperse type catalyzer is water-soluble catalyst, oil-soluble catalyst or solid powder th-1 catalyst, is 10～10000 μ g/g in the add-on of metal in raw oil;
Described floating bed hydrogenation conversion condition is: reaction pressure is 2～30MPa, and temperature of reaction is 300～500 ℃, and liquid hourly space velocity is 0.2～8.0h
-1, hydrogen to oil volume ratio is 100～3000.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5039392A (en) * | 1990-06-04 | 1991-08-13 | Exxon Research And Engineering Company | Hydroconversion process using a sulfided molybdenum catalyst concentrate |
| CN1162620A (en) * | 1996-04-16 | 1997-10-22 | 中国石油化工总公司 | Process for hydrogenation of heavy and residual oil by midium pressure suspension bed |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5039392A (en) * | 1990-06-04 | 1991-08-13 | Exxon Research And Engineering Company | Hydroconversion process using a sulfided molybdenum catalyst concentrate |
| CN1162620A (en) * | 1996-04-16 | 1997-10-22 | 中国石油化工总公司 | Process for hydrogenation of heavy and residual oil by midium pressure suspension bed |
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