CN101418223B - Preheating method for residual oil raw material on bubbling bed - Google Patents
Preheating method for residual oil raw material on bubbling bed Download PDFInfo
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- CN101418223B CN101418223B CN 200710157793 CN200710157793A CN101418223B CN 101418223 B CN101418223 B CN 101418223B CN 200710157793 CN200710157793 CN 200710157793 CN 200710157793 A CN200710157793 A CN 200710157793A CN 101418223 B CN101418223 B CN 101418223B
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Abstract
The invention discloses a method for preheating a fluidized bed residual oil. The method comprises the following steps: solids heated to 400 to 800 DEG C and fed residual oil heated to 200 to 350 DEG C are delivered to a reactor to contact each other to undergo heat exchange reaction; and after hear exchange of raw materials, gases are separated by a separation device and liquid materials are delivered to a fluidized bed reactor. Solid subjected to heat exchange with the raw materials returns to a heating device to be heated again to be recycled. The method can ensure long-term operation of devices and avoid coking in a furnace tube caused by an extremely high temperature due to directly heating of raw material oil by the prior heating furnace. The method can be operated intermittently or continuously.
Description
Technical field
The present invention relates to the pre-heating mean of a kind of ebullated bed (processing heavy feed stock) hydrogenator charging, be particularly useful for the pre-heating mean of the high poor residuum of colloid, bituminous matter and metal content.
Background technology
Variation along with petroleum products demand structure in the Devoting Major Efforts To Developing of heavy crude and the world wide, market maintains sustained and rapid growth to the demand of light-weight fuel oil and the demand of heavy fuel oil (HFO) is reduced rapidly, and the deep processing technology of residual oil has become the emphasis of petroleum refining industry's exploitation.The boiling bed residual oil hydrogen addition technology is one of important means of process residual oils raw material.In the technological process of boiling bed residual oil hydrocracking, normal conditions are: residual oil raw material enters ebullated bed reactor after process furnace is heated to certain temperature, and the service temperature of ebullated bed reactor is higher, be generally 420～460 ℃, this need to be higher from the material temperature that process furnace flows out, even reach more than 410 ℃, but also needing to use hot hydrogen carrier further to promote feeding temperature, guarantee enters the satisfied required temperature index of product requirement that reaches of stream temperature of reactor.Usually, adopt process furnace heating petroleum usually to control the furnace outlet temperature and be lower than 360～375 ℃.If excess Temperature, serious cracking and condensation coking reaction can occur in the macromolecular substance in the petroleum and condensed-nuclei aromatics, and the charging quality is poorer, macromolecular substance and condensed-nuclei aromatics cracking condensation coking reaction Shaoxing opera are strong in the raw material, thereby the tube coking that causes process furnace, affect the heat-transfer effect of boiler tube, can not guarantee the stream temperature of furnace outlet requirement, finally cause device to be stopped work; And by the further temperature raising of hot hydrogen carrier, because hot hydrogen carrier thermal capacitance is low, need a large amount of hydrogen, however a large amount of hydrogen enters ebullated bed reactor, has increased the gas holdup of reactor, has reduced liquid and has contained rate, thus affected the effective rate of utilization of reactor.
US.pat.No.RE25, described the concrete steps of boiling bed process in 770: stock oil and hydrogen enter from reactor bottom, by a grid distributor and on divider make uniform gas-liquid distribution, utilize the liquid stream that rises that beds is expanded, and keep good back-mixing, realize isothermal reaction and reduce pressure drop.Beds is expanded the amount of liquid that a part of product circulates to provide enough with an impeller pump.Reactor head establish circulation cup with circulating liquid in gas delivery out to reduce gas entrainment.Every day from reactor head is replenished and the reactor bottom discharging is a small amount of catalyzer keeping certain activity, thereby the more catalyst changeout of needn't stopping work.This patent is exactly to use conventional process furnace that heating raw materials is arrived the required temperature of reaction, this can cause the heating furnace tube coking, impact heating and heat-transfer effect, thereby can not guarantee the stream temperature of furnace outlet, affect the reactivity worth of final boiling bed hydrogenation, and because the furnace tubing coking brings operational safety hidden danger, affect the long period steady running of device.
Summary of the invention
For the deficiencies in the prior art, the invention provides a kind of preheating method of new boiling bed residual oil charging.The pre-heating mean of residual oil raw material on bubbling bed of the present invention may further comprise the steps:
A) solid matter is heated to 400～800 ℃.
B) solid matter and the residual oil raw material after will heating respectively sent into pre-thermal reactor, makes it carry out abundant contact heat-exchanging, and residual oil raw material is heated to specified temperature.
Wherein step a) in said solid matter be heat-carrying inert substance or low activity material, as being in spent catalyst, sandstone, ore and the mine tailing one or more, this solid matter is particulate state.
The feeding temperature of the residual oil raw material step b) is 200～350 ℃.Residual oil raw material can adopt the mode of conventional heating or heat exchange to obtain above-mentioned feeding temperature.In order to suppress the excessive coking of stock oil on solid matter, can in residual oil raw material, mix an amount of hydrogen.The volume of wherein sneaking into hydrogen accounts for 0.1～100v% of residual oil raw material volume, is preferably 10～60v%.
For the hydrogen that mixes in the gas that will produce in the pre-thermal response or the residual oil raw material is removed, pre-heating mean of the present invention can also comprise step c): with step b) heated stream that obtains isolates gaseous matter, liquid portion is sent into and is carried out hydrogenation reaction in the ebullated bed reactor.
The pre-heating mean of boiling bed residual oil charging of the present invention can adopt batch operation, also can adopt the continous way operation.Its operational condition is as follows: the weight ratio of solid matter and residual oil raw material is 2～20, is preferably 5～15, and the logistics outflow temperature of controlling pre-thermal reactor is 320～550 ℃, is preferably 420～480 ℃, the control pressure of pre-thermal reactor: 0～0.5MPa.
Step c) the boiling bed hydrogenation technique condition in is: reaction pressure 6～30MPa, and temperature of reaction is 350～500 ℃, air speed is 0.1～10h
-1, hydrogen to oil volume ratio is 400～2000.The catalyzer that uses is the boiling-bed catalyst of routine, the active ingredient of catalyzer can be in nickel, cobalt, molybdenum or the tungsten one or more, the content of nickel or cobalt is 0.5%～10% (in oxide compound), and the content of molybdenum or tungsten is 1%～20% (in oxide compound).The bulk density of catalyzer is 0.5～0.9g/cm
3, the granules of catalyst diameter is 0.04～1.0mm, specific surface area is 80～300m
2/ g.
With using process furnace in the prior art method that charging is heated to comparatively high temps is compared, outstanding effect of the present invention is:
1, use the high-temp solid material to carry out the boiling bed residual oil heating and can satisfy the required temperature requirement of charging, and under nitrogen atmosphere, the generation that can avoid violent condensation coking to react.
2, use hot solids material heating residual oil raw material, can avoid directly using process furnace that residual oil raw material is heated to above its cracking temperature (＞360 ℃), can slow down or suppress the heating furnace tube coking thus.
3, use the solid matter heating residual oil raw material of heat, can economize the hydrogen carrier that reduces phlegm and internal heat and further promote feeding temperature, thereby avoid gas holdup too high (reduce liquid and contain rate) in the ebullated bed reactor, thereby affect the treatment capacity of quality product and device.
4, adopt the hot solids material to carry out the resid feed heating, have larger temperature operation elasticity.Can adjust neatly the Heating temperature of solid matter according to different reactivity worth requirements, thereby guarantee the temperature requirement index of reaction feed.
5, heat-carrying inert substance or the low activity material cost of the present invention's employing are low, cut down finished cost.
Embodiment
The boiling bed residual oil pre-heating mean of the inventive method introduction can adopt batch operation.Wherein pre-thermal reactor can be the empty tube shape structure of container.
Step b) detailed process is as follows: the solid matter after will heating is transported in the pre-thermal reactor, then residual oil raw material and the mixture of hydrogen are injected pre-thermal reactor and contact with the hot solids material, carry out heat exchange, the charging after the heat exchange is discharged from the bottom of pre-thermal reactor.Wherein the mixture of residual oil raw material and the hydrogen feed entrance point that injects pre-thermal reactor can be located at any position of pre-thermal reactor, preferably is located at top or top and enters pre-thermal reactor in the mode of upper feeding.
Solid matter after the heat exchange can not draw off in pre-thermal reactor, and the mode of directly making charcoal with oxidation in device heats; Also can draw off from pre-thermal reactor, return in the heating unit and heat, the solid matter after the heating loops back pre-thermal reactor and uses.The mode of movement of described solid matter can adopt the suitable way of conveying solid substance catalyzer, such as gravity transfer, gas conveying etc.The heating of the solid matter after drawing off can be adopted the mode of any heat solid in the prior art, and the method that preferably adopts the device external oxidation to make charcoal heats.The mode that draws off solid matter from pre-thermal reactor can adopt existing any mode that draws off solid matter, draws off method etc. such as vacuum sucking-off method, gravity, preferably adopts gravity to draw off method.The concrete shape of the solid matter particle that this batch operation is used can be any shape, consider from aspects such as convenient conveying, solid-liquid heat transfer time and efficient, be preferably sphere, almost spherical or bar shaped, it is 0.6～1.2mm that the granular size of this solid matter is preferably granularity.
Ebullated bed feeding preheating method of the present invention also can adopt the operate continuously mode, can adopt that the inhomogeneous reaction technological process realizes in the prior art, such as moving bed process or boiling bed process.Wherein step b detailed process is as follows:
(1) adopts moving bed process
The solid matter of heating and the mixture of residual oil raw material and hydrogen are added from the preheating reactor head respectively, and carry out abundant contact heat-exchanging reaction.Feed stream after the heat exchange and solid matter are discharged from middle and lower part and the bottom of pre-thermal reactor respectively, and the solid matter that draws off returns in the heating unit and heats, and the solid matter after the heating loops back pre-thermal reactor and uses.
The type of heating that draws off the mode of solid matter and solid matter from reactor is same batch operation all.Take the used solid particulate of moving bed process can be any shape, but consider from aspects such as convenient conveying, solid-liquid heat transfer time and efficient, be preferably sphere, almost spherical.The large I of this solid matter particle determines according to existing moving bed process, and preferred size is 0.2～0.8mm.
(2) adopt boiling bed process
The top of solid matter after the heating from reactor was joined the preheating reaction period, the mode that the mixture of residual oil raw material and hydrogen flows to make progress enters pre-thermal reactor from the bottom of reactor, keep solid matter particle and be in the boiling shape, the hot solids material fully contacts with charging, carries out the heat exchange reaction; Feed stream after the heat exchange is discharged from top or the middle and upper part of pre-thermal reactor, and solid matter is discharged from the pipeline that is deep into preheating reactor bottom or middle and lower part continuously, returns in the heating unit and heats, and the solid matter after the heating loops back pre-thermal reactor and uses.
But draw off the mode of solid matter, the type of heating of solid matter and all operations of adopting by reference moving bed process of mode of movement of solid matter from pre-thermal reactor.Adopt the used solid particulate of boiling bed process to can be any shape, but consider from aspects such as convenient conveying, solid-liquid heat transfer time and efficient, be preferably sphere, almost spherical or bar shaped.The granular size of this solid matter can determine according to existing boiling bed process, and preferred size is 0.2～0.8mm.
Among the present invention, grain graininess can adopt method of sieving to record.
For further specifying the solution of the present invention and effect, enumerate following examples.The per-cent that relates to all is weight percentage.
The residual oil raw material character that test is used is listed in table 1.This residual oil raw material carbon residue is 18.3% as shown in Table 1, and metal content is 328.9 μ g.g
-1, bituminous matter is that 13.4%, S content is 2.5%, is with the unmanageable inferior raw material of ordinary method.
Embodiment 1
The embodiment that this embodiment carries out the residual oil preheating for the pre-thermal reactor that adopts moving-bed type, detailed process is: will be heated to through process furnace 600 ℃ diesel oil hydrogenation spent catalyst (sphere, granularity is 0.6mm) and be preheating to 300 ℃ residual oil raw material and the mixture of hydrogen (wherein hydrogen account for the residual oil raw material volume 30%) add pipeline and raw material from the solid of the preheating reactor head of moving-bed type respectively and add pipeline and enter, wherein the hot solids material adds by gravity, the weight ratio of solid matter and residual oil raw material is 4.3, raw material and the hot solids material contact heat-exchanging time in container is 30 minutes, it is 450 ℃ that the logistics of control preheating reactor exit flows out temperature, and gauge pressure is 0.3MPa.Feed stream after the heat exchange enters tripping device after discharge the bottom from container, isolate gaseous matter after, the liquid stream of heat is boosted by pump, then be mixed into ebullated bed reactor with high pressure hydrogen, under the temperature of reaction of regulation, carry out hydrogenation reaction.Solid matter after the heat exchange is discharged from the bottom of the pre-thermal reactor of moving-bed type, wherein draws off rear solid matter by gravity and returns in the process furnace and heat, and the solid matter after the heating loops back pre-thermal reactor use.The method heating that the type of heating of the solid matter after drawing off adopts the device external oxidation to make charcoal.Logistics behind the ebullating bed reactor obtains gas behind water distilling apparatus,＜350 ℃ of distillates and＞350 ℃ of tail oils, use therein boiling-bed catalyst is the loaded catalyst of nickel-loaded and molybdenum, wherein contain nickel oxide 3wt%, contain molybdenum oxide 8wt%, the catalyzer median size is 0.3mm, and the bulk density of catalyzer is 0.8g/cm
3, specific surface area is 180m
2/ g.
Reaction conditions and the results are shown in Table 2 and table 3.
Embodiment 2
This embodiment is for adopting andnon-continuous operation manner to carry out the embodiment of ebullated bed feeding preheating, adopt empty cartridge reactor, detailed process is: in process furnace with the waste residue oil hydrodenitrogenation catalyst (granularity is 0.8～1.1mm) to be heated to 650 ℃, then with its from the preheating reactor head by gravity transfer to this container; To be preheating to again 250 ℃ residual oil and hydrogen parallel feeding (wherein hydrogen account for the residual oil raw material volume 15%) inject pre-thermal reactor and hot solids material contact heat-exchanging; Wherein the weight ratio of spent catalyst and residual oil raw material is 3.5, and it is 430 ℃ that the logistics of control preheating reactor exit flows out temperature, and working pressure is normal pressure, and the reaction times is 50 minutes.Solid matter does not draw off in reactor, directly carries out the method heating that oxidation is made charcoal in the device.Feed stream after the heating is isolated gas through separator and is boosted to reaction pressure by pump, with enter ebullated bed reactor after high pressure hydrogen mixes and carry out hydrogenation reaction, logistics behind the ebullating bed reactor obtains gas behind water distilling apparatus,＜350 ℃ of distillates and＞350 ℃ of tail oils, use therein boiling-bed catalyst is the loaded catalyst of nickel-loaded and molybdenum, and wherein containing nickel oxide is 3wt%, and containing molybdenum oxide is 8wt%, the catalyzer median size is 0.3mm, and the bulk density of catalyzer is 0.8g/cm
3, specific surface area is 180m
2/ g.
Reaction conditions and the results are shown in Table 2 and table 3.
Table 1 test residual oil raw material character
| Project | Data |
| Density (20 ℃), kg.m -3Carbon residue, % viscosity (100 ℃), mm 2/ s condensation point, ℃ ultimate analysis, wt%C/HS/N metallic element, μ g.g -1Fe/Ni/V four proximate analyses, wt% stable hydrocarbon aromatic hydrocarbon gum asphalt | 1007.8 18.3 576.7 40 86.3/10.7 2.5/0.4 2.9/38.6/287.4 29.0 33.1 24.5 13.4 |
Table 2 reaction conditions
| Numbering | Embodiment 1 | Embodiment 2 |
| Temperature of reaction, ℃ reaction pressure, MPa hydrogen to oil volume ratio reaction velocity, h -1 | 450 16 1000 3.0 | 430 15 500 1.5 |
Table 3 reaction result
| Numbering | Embodiment 1 | Embodiment 2 |
| Reactor product character: desulfurization degree, wt% denitrification percent, 500 ℃ of wt% +Bottoms conversion, wt% | 75 63 71 | 70 54 64 |
Claims (12)
1. the pre-heating mean of a residual oil raw material on bubbling bed comprises the steps:
A) solid matter is heated to 400～800 ℃;
B) solid matter after will heating and be preheated to 200～350 ℃ residual oil raw material and send into pre-thermal reactor makes it carry out abundant contact heat-exchanging, and residual oil raw material is heated to specified temperature;
Wherein said solid matter is heat-carrying inert substance or low activity material, and the weight ratio of solid matter and residual oil raw material is 2～20, and the preheating reactor pressure is 0～0.5MPa, and residual oil raw material outflow temperature is 320～550 ℃ after the heat exchange.
2. according to pre-heating mean claimed in claim 1, it is characterized in that described solid matter is selected from one or more in spent catalyst, sandstone, ore and the mine tailing.
3. according to pre-heating mean claimed in claim 1, it is characterized in that, in described residual oil raw material, mix the hydrogen of 0.1～100v%.
4. according to claim 1 or 3 described pre-heating means, it is characterized in that, the method also comprises step c), with step b) heated stream that obtains isolates gaseous matter, liquid portion is sent into and is carried out hydrogenation reaction in the ebullated bed reactor.
5. according to pre-heating mean claimed in claim 3, it is characterized in that, in described residual oil raw material, mix the hydrogen of 10～60v%.
6. according to pre-heating mean claimed in claim 1, it is characterized in that, described pre-heating mean is taked batch operation or continous way operation.
7. according to pre-heating mean claimed in claim 1, it is characterized in that, the weight ratio of solid matter and residual oil raw material is 5～15, and the residual oil raw material temperature reaches 420～480 ℃ after the heat exchange.
8. according to pre-heating mean claimed in claim 6, it is characterized in that, described batch operation adopts empty cartridge reactor, step b) operating process is, solid matter after the heating is transported in the pre-thermal reactor, residual oil raw material is injected pre-thermal reactor and contact with the hot solids material, carry out heat exchange, the charging after the heat exchange is discharged from the bottom of pre-thermal reactor.
9. according to pre-heating mean claimed in claim 8, it is characterized in that, the solid matter particle granularity that described batch operation adopts is 0.6～1.2mm.
10. according to pre-heating mean claimed in claim 6, it is characterized in that, moving bed process or boiling bed process are adopted in described continous way operation.
11. according to pre-heating mean claimed in claim 10, it is characterized in that, the grain graininess of the solid matter that described operate continuously mode is used is 0.2～0.8mm.
12. according to claim 1,8 or 10 described pre-heating means, it is characterized in that, the mode that described solid matter delivers into reactor is that gravity transfer or gas are carried; The type of heating of the described solid matter that draws off from reactor loops back pre-thermal reactor and uses after adopting the method heating that the device external oxidation makes charcoal.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3481720A (en) * | 1966-04-29 | 1969-12-02 | Sun Oil Co | Process and apparatus for the distillation of solids |
| CN1264415A (en) * | 1997-07-17 | 2000-08-23 | 埃克森研究工程公司 | Integrated residua upgrading and fluid catalytic cracking |
| CN1957065A (en) * | 2004-05-21 | 2007-05-02 | 埃克森美孚化学专利公司 | Process and draft control system for use in cracking a heavy hydrocarbon feedstock in a pyrolysis furnace |
| CN101007961A (en) * | 2005-05-20 | 2007-08-01 | 价值创造公司 | Pyrolysis of residual hydrocarbons |
-
2007
- 2007-10-26 CN CN 200710157793 patent/CN101418223B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3481720A (en) * | 1966-04-29 | 1969-12-02 | Sun Oil Co | Process and apparatus for the distillation of solids |
| CN1264415A (en) * | 1997-07-17 | 2000-08-23 | 埃克森研究工程公司 | Integrated residua upgrading and fluid catalytic cracking |
| CN1957065A (en) * | 2004-05-21 | 2007-05-02 | 埃克森美孚化学专利公司 | Process and draft control system for use in cracking a heavy hydrocarbon feedstock in a pyrolysis furnace |
| CN101007961A (en) * | 2005-05-20 | 2007-08-01 | 价值创造公司 | Pyrolysis of residual hydrocarbons |
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