CN102041047B - Heavy oil hydrogenation modifying method - Google Patents
Heavy oil hydrogenation modifying method Download PDFInfo
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- CN102041047B CN102041047B CN200910204290.0A CN200910204290A CN102041047B CN 102041047 B CN102041047 B CN 102041047B CN 200910204290 A CN200910204290 A CN 200910204290A CN 102041047 B CN102041047 B CN 102041047B
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Abstract
The invention discloses a heavy oil modifying method which comprises the following steps: mixing a heavy oil raw material with a homogeneous catalyst, and mixing with a supercritical hydrogen supply solvent, wherein the content of the hydrogen supply solvent in the heavy oil raw material is 50 mug/g-5wt%; and in the presence of hydrogen, carrying out heavy oil hydrocracking reaction on the mixture of the heavy oil raw material, the catalyst and the hydrogen supply solvent under certain reaction conditions. In the heavy oil modifying method, suspension bed hydrocracking and supercritical treatment are organically combined, and the respective advantages are given full play to achieve the effect of synergic cooperation, thereby reducing the coking tendency, enhancing the impurity removal capacity and also enhancing the operational stability of the suspension bed hydrocracking.
Description
Technical field
The present invention relates to a kind of heavy oil hydrogenation modifying method, use specifically the suspension bed hydrocracking method of overcritical hydrogen supply dissolvent.
Background technology
At present, because petroleum resources are day by day exhausted, and Economic development constantly increases the demand of oil, and the price of oil goes up rapidly.And, along with the heaviness of crude resources, in the refining process of oil, the productive rate of residual oil is higher, is generally 40%～50%.In addition, more heavy crude is arranged in world's crude oil reserve, it forms the overwhelming majority is residual oil, and is the poor residuum that foreign matter content is very high.The deep processing technology of residual oil has become the emphasis of world refining industry exploitation.
The industrialized method of processing these residual oil or heavy oil comprises at present: method or the combined methods such as catalytic cracking, residual hydrogenation, delayed coking, viscosity breaking, solvent deasphalting.Along with residual oil is more and more inferior, sulphur, nitrogen and metals content impurity are more and more higher, and existing working method has dealt with weak point; On the other hand, the energy inferior such as oil-sand, pitch, synthetic crude also enter into the ranks of refining of petroleum, need suitable method to process the great energy of these reserves, alleviate the demand of social development to produce more light-end products.
The hydrogenation of residual oil suspended bed technology is one of possibility of processing weight, residual oil raw material.The floating bed hydrocracking technology is one of important method of inferior heavy oil lighting, and the major advantage of floating bed hydrocracking technology is to process any inferior raw material, and transformation efficiency is high, and general transformation efficiency can reach more than 90%.But the deficiency of floating bed hydrocracking is that the coke growing amount is larger, the problems such as device obstruction that are easy to react, can't the long period steady running.If operate under the mitigation condition, transformation efficiency is lower, lose the advantage of floating bed hydrocracking technology, and owing to containing more solid matter in Residue of Slurry-bed Hydrocracking, as the coke of the disperse type catalyzer added and generation etc., these solid matters are difficult to effective separation, and tail oil can't further utilize, therefore, the floating bed hydrocracking of low-conversion does not have actually operating value.
CN00123992.9 discloses a kind of normal pressure suspension bed hydrogenation process that adopts liquid multiple-metal catalyst, can be used in the hydrotreatment such as heavy oil, but still have a certain proportion of unconverted tail oil to exist, and unconverted tail oil is difficult to further processing and utilization.And the multimetallic catalyst that has added high dispersive, be difficult to separate, and to follow-up work, brings difficulty.
CN200610026906.6 discloses a kind of method of preparing light oil from supercritical water modified vacuum residuum, in supercritical water, carries out the thermally splitting of vacuum residuum and processes.Although the method is carried out heat cracking reaction in supercritical water, compare and reduced the coking side reaction with common thermal cracking process, for inferior raw material, coking rate is still higher.
Summary of the invention
For the deficiencies in the prior art, the invention provides a kind of heavy oil upgrading process, particularly a kind of suspension bed hydrocracking method that uses overcritical hydrogen supply dissolvent.
Heavy oil upgrading process provided by the invention comprises following content:
Heavy oil feedstock, homogeneous catalyst and overcritical hydrogen supply dissolvent are mixed, and hydrogen supply dissolvent comprises naphthane or perhydronaphthalene, and hydrogen supply dissolvent is 50 μ g/g～5wt% in the add-on of heavy oil feedstock; The gained raw mix, under hydrogen exists, is reacted under the floating bed hydrocracking condition, and the gained reaction effluent carries out the fractionation processing after isolating solid impurity.
Wherein said homogeneous catalyst is the normally used disperse type catalyzer in this area.The active ingredient of catalyzer is one or more in the metallic elements such as Mo, Ni, Co, W, Cr and Fe.Described disperse type catalyzer can, for water miscible inorganic salt such as the nitrate of above-mentioned metal, heteropolyacid salt, ammonium salts, can be both also the organic salts such as the naphthenate of above-mentioned metal, many carbonyl compound.The add-on of catalyzer in heavy oil feedstock counted 50～1000 μ g/g with metal, and preferably 100～800 μ g/g, be preferably 200～500 μ g/g.
Described hydrogen supply dissolvent is 5 μ g/g～5wt% in the add-on of heavy oil feedstock, is preferably 1wt%～3wt%.
Described floating bed hydrocracking condition is: reaction pressure 10～40MPa is preferably 15～25MPa, 350～470 ℃ of temperature of reaction, preferably 420～450 ℃, volume space velocity 0.5～5.0h
-1, 1.0～2.0h preferably
-1, hydrogen to oil volume ratio (under standard pressure) 300～2000, preferably 800～1500.
In the method for heavy oil modification of the present invention, described heavy oil feedstock can be the residual oil of various crude oil, and various oil-sand, pitch or synthetic crude etc., can be also two or more mixture of above-mentioned raw materials.
In heavy oil upgrading process of the present invention, floating bed hydrocracking preferably operates under than the low-conversion condition, and general transformation efficiency is 40%～80%, and most preferably 50%～70%.Lower transformation efficiency can guarantee the running of floating bed hydrocracking Chief Technology Officer cycle stability.
In heavy oil upgrading process of the present invention, described reaction effluent through fractionation plant obtain gas, distillate and>500 ℃ of tail oils, wherein>500 ℃ of tail oils can loop back suspended-bed reactor.
In heavy oil upgrading process of the present invention, overcritical for the supercritical state of hydrogen supply dissolvent or approach the condition of criticality, under this condition hydrogen supply dissolvent can with heavy oil feedstock in the coking precursor fully mixed being incorporated in coking precursor scission reaction hydrogen is provided, prevent its coking, and then reduce coking rate.Raw material in suspension bed technique can be processed, thereby be reached " the eating dry bleeding " to the real meaning of heavy oil.
In heavy oil upgrading process of the present invention, in mixture after supercritical reaction, can adopt the methods such as extraction or fractionation will comprise that the hydrogen supply dissolvent of superfluous hydrogen supply dissolvent or mistake hydrogen is separated, after separation, can use by direct circulation, or recycle after supplementing fresh hydrogen supply dissolvent, or recycle after conventional hydrogenation process.The circulation of hydrogen supply dissolvent can reduce the consumption of fresh hydrogen supply dissolvent.The hydrogen supply dissolvent internal circulating load can be generally 0.1～5 times of fresh hydrogen supply dissolvent volume, can determine by required concrete optimization of reaction effect of experimental process.
In heavy oil upgrading process of the present invention, can also add water, the add-on of water in heavy oil feedstock is 50 μ g/g～5wt%, preferably 0.5wt/g～2wt%.Water can react generating portion hydrogen with coke in reaction system etc. under reaction conditions, under the high pressure-temperature condition, the hydrogen generated can react with the hydrogen supply dissolvent that loses hydrogen, makes to lose the hydrogen supply dissolvent recuperation section hydrogen supply capacity of hydrogen, thereby can reduce the consumption of hydrogen supply dissolvent and improve reaction efficiency.Water and hydrogen supply dissolvent have formed the coordinated effect.
In method of the present invention, in the supercritical state of hydrogen supply dissolvent or approach under critical phase conditions and carry out, fused effect and the reaction effect of coking precursor in hydrogen supply dissolvent and heavy oil have been improved, reduced the coking tendency, strengthened reaction effect simultaneously, improve the ability of imurity-removal, can process heavy oil feedstock more inferior.
Method of the present invention, by floating bed hydrocracking and supercritical solvent combination, postcritical solvent can effectively reduce and alleviate the severity of floating bed hydrocracking, with the technique of independent employing floating bed hydrocracking, compare, in method, the processing condition of floating bed hydrocracking can be relaxed, guaranteed that the floating bed hydrocracking device can the long period steady running, reached the purpose that takes full advantage of raw material.In the supercritical state of hydrogen supply dissolvent or approach under critical phase conditions and carry out, fused effect and the reaction effect of coking precursor in hydrogen supply dissolvent and heavy oil have been improved, reduced the coking tendency, strengthened reaction effect simultaneously, improve the ability of imurity-removal, can process heavy oil feedstock more inferior.Hydrogen supply dissolvent and water are used simultaneously, can reach the coordinated effect, make hydrogen supply dissolvent can partly recover hydrogen supply capacity under response behaviour, reduce the consumption of hydrogen supply dissolvent, improve reaction effect.The introducing of supercritical water, improve heavy oil to colloid, the macromolecular intermiscibility of bituminous matter and hereditary property, reduces the green coke in reaction process.
The accompanying drawing explanation
Fig. 1 is a kind of a kind of signal process flow diagram that uses the suspension bed hydrocracking method of overcritical hydrogen supply dissolvent of the present invention.
Embodiment
Below in conjunction with drawings and Examples, suspension bed hydrocracking method of the present invention is described in detail.
Reactor logistics out through fractionation plant obtain gas, distillate and>500 ℃ of tail oils, wherein tail oil can loop back reactor.
The residual oil raw material character that test is used is listed in table 1.
Heavy oil feedstock adds disperse type catalyzer, and (disperse type catalyzer is this area conventional catalyst, as water-soluble or oil soluble metal catalyzer or solid powder th-1 catalyst etc., and mix with postcritical hydrogen supply dissolvent, catalyst levels is generally 50～1000 μ g/g in metal), hydrogen supply dissolvent comprises naphthane, perhydronaphthalene or water, and hydrogen supply dissolvent accounts for 50 μ g/g of heavy oil feedstock～5%; Condition is conventional floating bed hydrocracking process operation condition, as temperature of reaction: 350～470 ℃, reaction pressure 10～40MPa, volume space velocity 0.1～5.0h
-1, hydrogen to oil volume ratio 300: 1～2000: 1.The transformation efficiency general control of hydrocracking process of suspended bed is 40%～80%, and unconverted tail oil accounts for 20%～60% left and right of raw material.Reacted product enters separator after being separated by filtration out solid impurity, and gas phase is separated with liquid phase, and the solid impurity filtered to isolate etc. can burn or, as the raw material of needle coke, liquid phase enters separation column.Separation column is isolated the hydrogen supply dissolvent of various products and surplus or is lost the hydrogen supply dissolvent of hydrogen.Product after fractionation can be further processed as required.
For further illustrating all main points of the present invention, enumerate following examples.The per-cent related to all is weight percentage.
Embodiment-1
Tahe residual oil is after the processing such as the identical filtration with common process, add 200 μ g/g water-soluble or oil soluble multimetallic catalyst (take containing Ni salt and containing Mo salt be raw material, two kinds of atoms metals were than 1: 3) solution, and mix (naphthane account for residual oil raw material 2%) with postcritical hydrogen supply dissolvent naphthane and carry out floating bed hydrocracking, condition is conventional process operation condition, temperature: 390 ℃, pressure 15MPa, air speed 1.0h
-1, hydrogen-oil ratio 600: 1, the transformation efficiency of floating bed hydrocracking is 62%, floating bed hydrocracking can be at this than long period steady running under low-conversion.
Reacted product enters separator after filtering, and gas phase is separated with liquid phase, and liquid phase enters separation column.Separation column is isolated various products and superfluous hydrogen supply dissolvent.Superfluous hydrogen supply dissolvent can recycle.Reaction result is in Table 2.
Embodiment-2
Take Tahe residual oil as raw material, floating bed hydrocracking step same embodiment-1, it is 405 ℃ that temperature of reaction is controlled, and transformation efficiency is 74%, and floating bed hydrocracking can long period steady running under this transformation efficiency.But postcritical hydrogen supply dissolvent is perhydronaphthalene, account for 2% of heavy oil feedstock, after method of the present invention is processed, reaction result is in Table 2.
Embodiment-3
Press the method that embodiment 2 is identical, when using perhydronaphthalene, also add water, water accounts for 2% of heavy oil feedstock, and reaction result is in Table 2.
Embodiment-4
Press the method that embodiment 1 is identical, when using naphthane, also add water, water accounts for 2% of heavy oil feedstock, and reaction result is in Table 2.
Comparative example-1
The method identical with embodiment 2, supercritical solvent only makes water, and water accounts for 2% of heavy oil feedstock, does not use hydrogen supply dissolvent perhydronaphthalene and naphthane, and reaction result is in Table 2.
Table 1
| Raw material | |
| Density (20 ℃), kg.m -3 | 1008.8 |
| Carbon residue, quality % | 18.4 |
| Viscosity (100 ℃) mm 2.s -1 | 589.8 |
| S, quality % | 2.6 |
| N, quality % | 0.5 |
| Ni，μg.g -1 | 39.7 |
| V，μg.g -1 | 289.8 |
| Colloid, quality % | 25.4 |
| Bituminous matter, quality % | 14.3 |
| Coke yield, quality % | - |
Table 2 generates oil nature
| Embodiment-1 | Embodiment-2 | Embodiment-3 | Embodiment-4 | Comparative example-1 | |
| S, quality % | 1.4 | 1.4 | 1.2 | 1.3 | 1.5 |
| N, quality % | 0.35 | 0.35 | 0.30 | 0.32 | 0.39 |
| Ni，μg.g -1 | 19.5 | 18.9 | 17.1 | 17.4 | 20.7 |
| V，μg.g -1 | 115.5 | 114.7 | 110.5 | 110.8 | 149.4 |
| Colloid, quality % | 16.4 | 10.7 | 8.1 | 8.2 | 17.3 |
| Bituminous matter, quality % | 6.3 | 4.6 | 3.9 | 4.0 | 6.7 |
| Coke yield, quality % | 1.2 | 1.1 | 0.9 | 0.9 | 1.4 |
Claims (9)
1. a heavy oil upgrading process, comprise: heavy oil feedstock, homogeneous catalyst, water and overcritical hydrogen supply dissolvent are mixed, hydrogen supply dissolvent comprises naphthane or perhydronaphthalene, and hydrogen supply dissolvent is 50 μ g/g～5wt% at the content of heavy oil feedstock, and the add-on of water accounts for 50 μ g/g～5wt% of heavy oil feedstock; The gained raw mix, under hydrogen exists, is reacted under the floating bed hydrocracking condition, and the gained reaction effluent carries out the fractionation processing after isolating solid impurity.
2. in accordance with the method for claim 1, it is characterized in that, described hydrogen supply dissolvent is 1wt%～3wt% in the add-on of heavy oil feedstock.
3. in accordance with the method for claim 1, it is characterized in that, the add-on of described water accounts for the 0.5wt%～2wt% of heavy oil feedstock.
4. in accordance with the method for claim 1, it is characterized in that, described floating bed hydrocracking conversion rate control is 40%～80%.
5. in accordance with the method for claim 1, it is characterized in that, described floating bed hydrocracking conversion rate control is 50%～70%.
6. in accordance with the method for claim 1, it is characterized in that, described reaction effluent through fractionation plant obtain gas, distillate and 500 ℃ of tail oils, wherein > 500 ℃ of tail oils loop back reactor.
7. in accordance with the method for claim 1, it is characterized in that, in reaction effluent, adopt extraction or fractionating method will comprise that the hydrogen supply dissolvent of superfluous hydrogen supply dissolvent or mistake hydrogen is separated, after separation, can use by direct circulation, or recycle after supplementing fresh hydrogen supply dissolvent, or recycle after conventional hydrogenation process; The hydrogen supply dissolvent internal circulating load is 0.1～5 times of fresh hydrogen supply dissolvent volume.
8. in accordance with the method for claim 1, it is characterized in that, the active ingredient of described homogeneous catalyst is one or more in Mo, Ni, Co, W, Cr and Fe, and the add-on of catalyzer in heavy oil feedstock counted 50～1000 μ g/g with metal.
9. in accordance with the method for claim 1, it is characterized in that, described floating bed hydrocracking condition is: reaction pressure is 10～40MPa, and temperature of reaction is 380～470.℃, volume space velocity is 0.5～～3.0h
-1, hydrogen to oil volume ratio is 400～2000.
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| CN102876370B (en) * | 2011-07-11 | 2015-02-18 | 中国石油化工股份有限公司 | Hydrocracking method of residual oil |
| CN104232158B (en) | 2014-08-22 | 2016-02-24 | 中国石油大学(北京) | Bituminous matter lightening method |
| CN109628134B (en) * | 2019-02-15 | 2021-01-15 | 华东理工大学 | Method for regulating and controlling heavy oil molecular structure |
| CN113088314A (en) * | 2019-12-23 | 2021-07-09 | 中国科学院青岛生物能源与过程研究所 | Hydrogenation modification method of asphaltene |
| CN111704924B (en) * | 2020-06-22 | 2021-11-16 | 山东京博石油化工有限公司 | Method for inhibiting coke yield increase in delayed coking |
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| CN111748370A (en) * | 2019-03-28 | 2020-10-09 | 中国石油天然气股份有限公司 | Thermal modification method for heavy oil by aid of aid |
| CN111748370B (en) * | 2019-03-28 | 2022-08-05 | 中国石油天然气股份有限公司 | Thermal modification method for heavy oil by aid of aid |
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