CN103540349B - Inferior heavy oil and residual oil hydrotreating combined process for prolonging service life of catalyst - Google Patents
Inferior heavy oil and residual oil hydrotreating combined process for prolonging service life of catalyst Download PDFInfo
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- CN103540349B CN103540349B CN201210241248.8A CN201210241248A CN103540349B CN 103540349 B CN103540349 B CN 103540349B CN 201210241248 A CN201210241248 A CN 201210241248A CN 103540349 B CN103540349 B CN 103540349B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 104
- 238000000034 method Methods 0.000 title claims abstract description 64
- 239000003921 oil Substances 0.000 title claims abstract description 48
- 230000008569 process Effects 0.000 title claims abstract description 28
- 239000000295 fuel oil Substances 0.000 title claims abstract description 19
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 65
- 239000002002 slurry Substances 0.000 claims abstract description 55
- 239000002994 raw material Substances 0.000 claims abstract description 33
- 229910052751 metal Inorganic materials 0.000 claims abstract description 28
- 239000002184 metal Substances 0.000 claims abstract description 28
- 239000007788 liquid Substances 0.000 claims abstract description 16
- 238000000926 separation method Methods 0.000 claims abstract description 11
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 28
- 239000001257 hydrogen Substances 0.000 claims description 28
- 229910052739 hydrogen Inorganic materials 0.000 claims description 28
- 238000006243 chemical reaction Methods 0.000 claims description 27
- 238000012545 processing Methods 0.000 claims description 15
- 239000000463 material Substances 0.000 claims description 13
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 11
- 239000012263 liquid product Substances 0.000 claims description 9
- 238000004517 catalytic hydrocracking Methods 0.000 claims description 8
- 238000006477 desulfuration reaction Methods 0.000 claims description 8
- 230000023556 desulfurization Effects 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims description 8
- 239000011148 porous material Substances 0.000 claims description 8
- 238000007324 demetalation reaction Methods 0.000 claims description 6
- 229910052742 iron Inorganic materials 0.000 claims description 6
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 6
- 239000000047 product Substances 0.000 claims description 6
- 239000000725 suspension Substances 0.000 claims description 5
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 4
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 4
- GEIAQOFPUVMAGM-UHFFFAOYSA-N ZrO Inorganic materials [Zr]=O GEIAQOFPUVMAGM-UHFFFAOYSA-N 0.000 claims description 4
- 230000008676 import Effects 0.000 claims description 4
- 229910044991 metal oxide Inorganic materials 0.000 claims description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 3
- -1 VIB metals Chemical class 0.000 claims description 3
- 239000011575 calcium Substances 0.000 claims description 3
- 229910052791 calcium Inorganic materials 0.000 claims description 3
- 150000004706 metal oxides Chemical class 0.000 claims description 3
- 150000002739 metals Chemical class 0.000 claims description 2
- 239000012535 impurity Substances 0.000 abstract description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 6
- 230000004048 modification Effects 0.000 abstract description 4
- 238000012986 modification Methods 0.000 abstract description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 3
- 229910052717 sulfur Inorganic materials 0.000 abstract description 3
- 239000011593 sulfur Substances 0.000 abstract description 3
- 239000007791 liquid phase Substances 0.000 abstract description 2
- 230000000630 rising effect Effects 0.000 abstract 1
- 239000003795 chemical substances by application Substances 0.000 description 13
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 10
- 238000005516 engineering process Methods 0.000 description 8
- 230000009849 deactivation Effects 0.000 description 7
- 239000012071 phase Substances 0.000 description 6
- 230000008859 change Effects 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 230000001172 regenerating effect Effects 0.000 description 5
- 239000010426 asphalt Substances 0.000 description 4
- 239000002131 composite material Substances 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 230000007774 longterm Effects 0.000 description 4
- 229910052759 nickel Inorganic materials 0.000 description 4
- 230000003245 working effect Effects 0.000 description 4
- 239000004480 active ingredient Substances 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000002010 green coke Substances 0.000 description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 3
- 230000008929 regeneration Effects 0.000 description 3
- 238000011069 regeneration method Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 230000009466 transformation Effects 0.000 description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 2
- 241000772415 Neovison vison Species 0.000 description 2
- 239000005864 Sulphur Substances 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000003321 amplification Effects 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 238000004939 coking Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000010779 crude oil Substances 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 230000002779 inactivation Effects 0.000 description 2
- 229910052809 inorganic oxide Inorganic materials 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 239000011733 molybdenum Substances 0.000 description 2
- 229910000480 nickel oxide Inorganic materials 0.000 description 2
- 238000003199 nucleic acid amplification method Methods 0.000 description 2
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 229910001145 Ferrotungsten Inorganic materials 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- AFTDTIZUABOECB-UHFFFAOYSA-N [Co].[Mo] Chemical compound [Co].[Mo] AFTDTIZUABOECB-UHFFFAOYSA-N 0.000 description 1
- PFRUBEOIWWEFOL-UHFFFAOYSA-N [N].[S] Chemical compound [N].[S] PFRUBEOIWWEFOL-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
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- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- RIVZIMVWRDTIOQ-UHFFFAOYSA-N cobalt iron Chemical compound [Fe].[Co].[Co].[Co] RIVZIMVWRDTIOQ-UHFFFAOYSA-N 0.000 description 1
- WHDPTDWLEKQKKX-UHFFFAOYSA-N cobalt molybdenum Chemical compound [Co].[Co].[Mo] WHDPTDWLEKQKKX-UHFFFAOYSA-N 0.000 description 1
- 238000001246 colloidal dispersion Methods 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
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- 239000012895 dilution Substances 0.000 description 1
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- 238000004821 distillation Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 235000003599 food sweetener Nutrition 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 230000035800 maturation Effects 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 1
- HBVFXTAPOLSOPB-UHFFFAOYSA-N nickel vanadium Chemical compound [V].[Ni] HBVFXTAPOLSOPB-UHFFFAOYSA-N 0.000 description 1
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
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- 239000003765 sweetening agent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
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- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention relates to a poor heavy oil and residual oil hydrotreating combined process, wherein a heavy oil raw material is subjected to hydrogenation pretreatment in a slurry bed, after gas-liquid separation, a liquid-phase product is subjected to hydrogenation modification in a fixed bed, wherein the hydrogenation pretreatment part in the slurry bed comprises a slurry bed hydrogenation reactor and a slurry bed hydrogenation catalyst; the reactors used in the fixed bed hydro-upgrading part mainly comprise the following components in sequence: the method not only improves the hydrogenation and impurity removal capability of the catalyst, but also can prolong the life cycle of the catalyst, can treat residual oil with high metal content, high sulfur, high nitrogen and high asphaltene, and can effectively slow down the rising speed of the pressure drop of the reactor, thereby realizing the long-period operation of the device.
Description
Technical field
The inventive method can be used for field of hydrogenation, is particularly useful for high metal (Ni+V>=200 μ gg
-1), the hydrofining of the heavy distillate of high carbon residue (CCR>=20wt%), high asphalt content, residual oil and oil sands bitumen and hydrotreatment.The inventive method is being guaranteed on higher demetalization, desulfurization, the active basis of denitrogenation and diasphaltene, is extending catalyst work-ing life, improves device long-term operation performance and provide an effective way.
Background technology
At present, along with the aggravation of crude oil in poor quality, heaviness trend, the increase of light-end products demand and the increasingly stringent of environmental regulation, the processing modification technology of residual oil has caused the extensive concern of countries in the world.The deep processing of poor residuum and upgrading, for Appropriate application petroleum resources, improve quality product, improve yield of light oil, have important practical significance.
Residue Hydrotreating Technology is because liquid product yield is high, quality is good, both the increase of market to light-end products demand can be met to maximum, can produce again more clean petroleum products to meet increasingly strict environmental requirement, be the development trend place of residua upgrading technology.Divide from type of reactor, comprise fixed bed, ebullated bed, moving-bed and slurry bed system hydrogenation Four types, fixed bed and moving-bed hydrogenation technique, higher to the requirement of raw material, be not suitable for processing heavy, inferior raw material; Boiling bed hydrogenation technology can process inferior raw material, but operational condition is harsh, and plant investment cost is higher; Slurry bed system hydrogen addition technology then can process various inferior raw material, has that adaptability to raw material is strong, technique is simple, flexible operation, transformation efficiency high, but not yet realize industrialization because the reaction problem such as green coke and engineering amplification.In a word, the core of residual hydrogenation upgrading is reasonably to control depth of conversion, and macromole bituminous matter etc. being easy to coagulation is keeping the stable basis of colloidal dispersion progressively transforms, and avoids green coke to cause catalyst deactivation thus shortens device running period.The successful needs of residual hydrogenation upgrading organically combine the basic chemistry understanding of residual oil, the appropriate design of hydrogenation catalyst and the science amplification of technological process and could realize.On industrial practice, in order to improve catalyzer work-ing life, prolong operating period, investigator proposes multiple solution.
CN1322097C discloses a kind of replaceable reactor and can the method for short-circuit reaction device hydrotreatment of heavy hydrocarbon fraction of adopting.Residual oil is first through a protective belt process, and at protection section, catalyst regeneration or replacing short circuit can be guaranteed in protective belt; And then through hydrodemetallation (HDM) and hydrogenating desulfurization process, the reactor of at least one hydrodemetallation (HDM) section and/or hydrodesulfurizationsection section can short circuit, is beneficial to regeneration and the replacing of catalyzer.By protection and the replacing of catalyzer, guarantee that device can long-term operation, but need higher initial outlay.
CN1349554 discloses a kind of method of the up-flow reactor system hydrotreating heavy feedstocks with stratiform beds.With the heavy feed stock that the residual matter of the upflow fixed bed reactor hydrotreatment metal of the catalyzer of at least two different hydrogenation activities, sulphur and carbon containing is polluted.But the method cycle of operation is short, be generally no more than 1 year.
CN1144860 discloses a kind of method of residual hydrocracking.First reactor in heavy resid hydrogenation reaction system sets up one or more opening for feed, change original catalyzer grating simultaneously, when an anticatalyzer bed pressure drop is the 0.4-0.8 times of apparatus design maximum pressure drop, use next opening for feed successively instead, original opening for feed can enter the mixture of turning oil or turning oil and stock oil simultaneously.This technique effectively can prevent bed pressure drop and extend the work-ing life of residual oil hydrocatalyst, and can increase the processing power of device.
CN00110714.3 discloses a kind of residual oil treatment process.Before heavy resid hydrogenation reaction system, adopt one section of absorption filter agent bed or one section of absorption filter agent bed and one section of adsorption filtration beds to use simultaneously, not only can farthest remove the suspended particle carried in stock oil, but also the Iron sulfuret of the iron naphthenate generation in crude oil and the material of the easy green coke of major part can be removed, at utmost reduce the fouling of residual hydrogenation reactive system reactor, reduce the shutting down number of times caused because of fouling in device running period.
Residual oil density is large, and viscosity is high, and impurity is many, only relies on single processing means to be difficult to obtain desirable product and benefit.Fixed bed hydrogenation process costs is low, simple to operate, technology maturation, but can only the good raw material of handling properties; Slurry bed system hydrogen addition technology then can process various inferior raw material, there is the features such as adaptability to raw material is strong, flexible operation, consider the features of fixed bed and slurry bed system hydrogenation, the present invention plans two kinds of techniques and combines, poor residuum first through slurry bed system hydrogenation as pre-treatment, metal in raw material, sulphur, nitrogen, asphalt content are significantly reduced, and then through fixed bed hydrogenation process, remove impurity wherein further, avoid because raw material viscosity is comparatively large, metallic impurity or asphalt content higher, cause rapid catalyst deactivation, shorten device running period.
Summary of the invention
The object of this invention is to provide a kind of inferior heavy oil, process for hydrogenating residual oil, by adopting unique hydrotreatment flow process, and selecting effective hydrogenation catalyst rightly, reaching and both improving catalyst hydrogenation removing impurities mass-energy power, the extension fixture cycle of operation again.
A kind of inferior heavy oil, residual hydrocracking combination process, it is characterized in that heavy oil and/or residual oil raw material first through slurry bed system weighted BMO spaces, after gas-liquid separation, liquid product is again through fixed bed hydrogenation upgrading, wherein, slurry bed system weighted BMO spaces part comprises a slurry bed system hydrogenator and slurry bed system hydrogenation catalyst, fixed bed hydrogenation upgrading part is reactor used mainly to be comprised sequentially: two upflowing deferrization decalcification reactors, a upflowing demetalization reactor, a fixed bed desulphurization reactor, a fixed bed denitrification reactor, specific as follows: the inlet line of two upflowing deferrization decalcification reactors and outlet line are all equipped with check valve, a pipeline is connected with before outlet line check valve with after another upflowing deferrization decalcification Reactor inlet pipeline check valve, material is made to be able to import from the outlet of a upflowing deferrization decalcification reactor import of another upflowing deferrization decalcification reactor, pipeline is equipped with check valve, the inlet line and outlet line of upflowing demetalization reactor are all equipped with 3-way valve, other two ends in the 3-way valve of upflowing demetalization Reactor inlet pipeline, one end connects the outlet line of streaming demetalization reactor, the other end pipeline connects the 3-way valve on streaming demetalization reactor outlet pipeline, and this 3-way valve also has one end to connect with the source line of fixed bed desulphurization reactor, first raw material is mixed to form suspension slurry with slurry bed system hydrogenation catalyst, then enter slurry bed system hydrogenator and carry out weighted BMO spaces, exported product is through gas-liquid separator, hydrogen-containing gas and liquid product are separated, liquid product is through upflowing deferrization decalcification reactor, reactor is in-built doses hydrogen deferrization decalcification catalyzer, remove a part of iron, slurry bed system catalyzer after calcium and slurry bed system hydrotreatment, its resultant of reaction has two kinds of operation scheme: one is directly enter upflowing demetalization reactor, hydrodemetallation (HDM) (Ni is carried out under catalyst for demetalation exists, V) react, its resultant of reaction is without separation again, directly enter fixed bed desulphurization reactor, hydrodesulfurization reaction is carried out under desulfurization catalyst exists, two is directly enter desulphurization reactor, under desulfurization catalyst exists, carry out hydrodesulfurization reaction, desulphurization reactor resultant of reaction, without separation, directly enters fixed bed denitrification reactor, under denitrification catalyst exists, carry out hydrodenitrification reaction.
In the present invention, the raw material such as residual oil, heavy oil is after slurry bed system hydrotreatment, product is after being separated, liquid product containing slurry bed system Hydrogenation catalyst granule thing enters upflowing deferrization decalcification reactor, after the process of deferrization calcium catalyst, slurry bed system granules of catalyst can effectively be caught, thus extends the life cycle of fixed bed desulfurization catalyst.
Deferrization decalcification plant running process steps can be as follows:
(1) in initial reaction stage, two deferrization decalcification reactors use together, and heavy oil or residual oil raw material are introduced into one of them reactor (representing with A), then enter another reactor (representing with B) and carry out deferrization decalcification reaction.
(2) after reacting for some time, A reactor catalyst is active in the middle and later periods, at this moment can flow to by feed change, and the advanced B reactor of raw material enters A reactor again.
(3) in A reactor, deferrization decalcification catalyzer is in deactivation phases, closes A reactor feed valve, and with regenerating and/or replace with live catalyst the catalyzer of reactor.Now material only enters B reactor.
(4) after A completes and changes agent, the advanced B reactor of material, then enter to change the reactor A of agent.
(5) in B reactor, deferrization decalcification catalyzer is in deactivation phases, closes B reactor feed valve, and with regenerating and/or replace with live catalyst the catalyzer of reactor.Now material only enters A reactor.
(6), after B reactor completes and changes agent, repeating step (1)-step (5) is continued.
For demetalization reactor, in operational process, especially at the active deactivation phases of catalyst for demetalation, material autoreactor out directly enters desulphurization reactor.Simultaneously with regeneration and/or the catalyst for demetalation replacing reactor with live catalyst.After completing catalyzer replacement, material autoreactor out enters demetalization reactor, desulphurization reactor and denitrification reactor more successively.
Method provided by the present invention can process high metal content, high-sulfur, high nitrogen, high bitum residual oil, and effectively can slow down the lift velocity of reactor pressure decrease, thus the long-term operation of implement device.
The logistics direction of up-flow reactor of the present invention flows through beds from bottom to top, and the catalyzer in bed expands slightly.From up-flow reactor bottom feed after mink cell focus or residual oil raw material and hydrogen mixing, make whole beds produce slight expansion, thus slow down the rate of growth of the Pressure Drop of beds, the running period of extension fixture.Same ebullated bed, moving-bed are compared with slurry bed system, and up-flow reactor has invests the features such as low, simple to operate.
Slurry bed system hydrogenation catalyst can form suspension slurry with stock oil, upflowing deferrization decalcification reactor charge hydrogenation deferrization decalcification catalyzer, demetalization reactor charge Hydrodemetalation catalyst, desulphurization reactor filling Hydrobon catalyst, denitrification reactor filling hydrodenitrogenation catalyst.
In the present invention, hydrogenation deferrization decalcification catalyzer, Hydrodemetalation catalyst, Hydrobon catalyst and hydrodenitrogenation catalyst, from left to right, preferably: catalyzer aperture reduces gradually, and granularity reduces gradually, and porosity reduces gradually.
Can load one or more catalyzer respectively in fixed bed hydrogenation upgrading part 4 classification fixed-bed reactor in the present invention, preferably along logistics direction, aperture reduces gradually, and granularity reduces gradually, and porosity reduces gradually.
Slurry bed system hydrogenation catalyst based on the composite catalyst that carbonaceous particle and part molybdenum nickel metal oxide are formed, also can be preferably the mineral substance being rich in the metal active constituents such as nickel, molybdenum, vanadium, iron.Activated-carbon catalyst, for the heavy hydrocarbons in residual oil and the selective adsorption of bituminous matter, has and good presses down burnt ability; Meanwhile, activated-carbon catalyst has very high reactivity for metallic impurity such as the nickel vanadium removed in bituminous matter; Stability Analysis of Structures under active carbon high-temp, acid and alkali-resistance, it is complete that active ingredient is easy to sulfuration, has higher HDS/HDN active than traditional aluminum oxide and silicon oxide catalyst; Surface chemical property can regulate modification, is easy to the precious metal reclaimed wherein.
US4831003 and US5051389 proposes a kind of method of gas phase distillation deposition that adopted by the precursor of molybdenum or nickel isoreactivity metal component and loads to method on gac, and the standby catalyzer of this legal system can be used for the hydrotreatment of heavy oil and dilution stock oil.
US5358634, US5364524, US5374350 select a kind of mean pore size be the gac of 10-40nm as carrier, employing order dipping or co-impregnation load molybdenum cobalt isoreactivity component, this catalyzer has good HDM effect in fixed bed, moving-bed.
US5389241, US5500401 are with 20-40 object gac for carrier, and employing order pickling process prepares the catalyzer for heavy oil HDN process, and the alumina supported catalyst activity that its specific activity is traditional is high.
The metal components such as US5466363 take gac as carrier, nickel-loaded cobalt molybdenum ferrotungsten are for fixed bed or moving-bed hydrotreatment, and the catalyzer part gasification of inactivation, produce synthetic gas and be used for F-T synthesis, a part can be used for making steel in addition.
US5676822 take gac as carrier, adopts the metal such as co-impregnation zinc supported or nickel ferro-cobalt, for removing the impurity such as aromatic hydrocarbons in petroleum naphtha or intermediate oil and sulphur nitrogen.
EP1537912A1 discloses a kind of activated-carbon catalyst preparation method for fixed bed/moving-bed/boiling bed heavy oil hydrogenation.Carrier active carbon is through water vapour modification, and mean pore size, between 20-200nm, forms catalyzer after dip loading iron isoreactivity component, effectively can suppress the generation of coking in reaction process.
The present invention recommends to adopt equi-volume impregnating supported active metals component, prepares the slurry bed system hydrogenation catalyst of high reactivity, anti-coking.The specific surface area particularly adopted is 400 ~ 2000m
2/ g, is preferably 800 ~ 1000m
2the carbonaceous particle of/g is carrier, and active metal oxide charge capacity is preferably 300 ~ 1500 μ g/g, is preferably 500 ~ 1000 μ g/g, and active metal oxide takes from group VIB metal and/or VIII race's metal.
In order to improve the capturing ability of impurity, dust and particle, the hydrogenation deferrization decalcification catalyzer used in the present invention is preferably honeycomb shape, and order number is between 50 ~ 400.General with porous inorganic oxide if aluminum oxide is for carrier, group VIB metal (as W or/and Mo) and/or VIII race's metal (as Co or/and Ni) oxide compound are active ingredient, and the composition of catalyzer is preferably:
1) with Al
2o
3or containing K
2o, MgO, SiO
2, TiO
2, ZrO
2al
2o
3as carrier;
2) pore volume is 0.1 ~ 3.0ml/g, is preferably 0.3 ~ 1.3ml/g;
3) specific surface is 200 ~ 1000m
2/ g, is preferably 400 ~ 800m
2/ g;
4) porosity is 30% ~ 70%, is preferably 50-60%;
5) catalyzer is in corresponding burning amount (as follows), containing 1.0 ~ 10.0%, is preferably the group VIB metal of 5.0 ~ 8.0% (as MoO
3and/or WO
3), and/or 0.5 ~ 3.0%, be preferably VIII race's metal (as CoO and/or NiO) of 1.0 ~ 2.0%.
The Hydrodemetalation catalyst used in the present invention, Hydrobon catalyst and/or hydrodenitrogenation catalyst, preferably with porous inorganic oxide if aluminum oxide is for carrier, group VIB metal (as W or/and Mo) and/or VIII race's metal (as Co or/and Ni) oxide compound are active ingredient, and the composition of catalyzer is preferably:
1) with Al
2o
3or containing K
2o, MgO, SiO
2, TiO
2, ZrO
2al
2o
3as carrier;
2) pore volume is 0.1 ~ 3.0ml/g, is preferably 0.3 ~ 1.3ml/g;
3) specific surface is 20 ~ 400m
2/ g, is preferably 100 ~ 240m
2/ g;
4) catalyzer is in corresponding burning amount (as follows), containing 1.0 ~ 20.0%, is preferably the group VIB metal of 3.0 ~ 16% (as MoO
3and/or WO
3), and/or 0.5 ~ 8.0%, be preferably VIII race's metal (as CoO and/or NiO) of 1.0 ~ 5.5%.
It should be noted that, the catalyzer related in the present invention can adopt ordinary method of the prior art to prepare.
The catalyzer used in the present invention, its carrier can be drip ball forming, spin granulation, extrusion molding, compression molding etc., is best with a ball forming and extrusion molding.Catalyst shape can be honeycombed, spherical, bar shaped (comprising cylindrical, trilobal, quatrefoil etc.), sheet shape.Be best with honeycombed, spherical and Herba Galii Bungei shape.
Heavy oil of the present invention, residual hydrocracking technique, the hydroprocessing technique condition of any applicable this area can be adopted, general processing condition are as follows: hydrogen pressure 5.0MPa ~ 20.0MPa, is preferably 8.0MPa ~ 18.0MPa, it is preferred that 10.0MPa ~ 16.0MPa; Temperature 300 DEG C ~ 450 DEG C, is preferably 360 DEG C ~ 440 DEG C, it is preferred that 360 DEG C ~ 430 DEG C; Volume space velocity 0.2h during liquid
-1~ 3h
-1, be preferably 0.2h
-1~ 2h
-1, it is preferred that 0.2h
-1~ 1h
-1; Hydrogen to oil volume ratio 300 ~ 2000, is preferably 400 ~ 1500, it is preferred that 500 ~ 1000.
Slurry bed system weighted BMO spaces processing condition are as follows: hydrogen pressure 8.0MPa ~ 20.0MPa, is preferably 8.0MPa ~ 18.0MPa, it is preferred that 10.0MPa ~ 16.0MPa; Temperature 350 DEG C ~ 450 DEG C, is preferably 380 DEG C ~ 440 DEG C, it is preferred that 400 ° of C ~ 420 DEG C; Volume space velocity 0.2h during liquid
-1~ 3h
-1, be preferably 0.2h
-1~ 2h
-1, it is preferred that 0.5h
-1~ 1h
-1; Hydrogen to oil volume ratio 300 ~ 2000, is preferably 400 ~ 1500, it is preferred that 500 ~ 1000.In stock oil, slurry bed system hydrogenation catalyst add-on is the 0.5wt% ~ 5wt% of stock oil, and catalyzer can adopt prior art to prepare.
It is benchmark with raw material that transformation efficiency calculates, as raw material be residual oil time, i.e. transformation efficiency=(1-is unconverted residual oil/charging residual oil) × 100%.
Because in the present invention, deferrization decalcification reactor, demetalization reactor have selected up-flow reactor, flow from bottom to top in the logistics direction of up-flow reactor, and in reactor, liquid phase is continuous, and the catalyzer in bed expands slightly.Same ebullated bed, moving-bed are compared with slurry bed system, and up-flow reactor has invests the features such as low, simple to operate.Mink cell focus of the present invention, first residual oil raw material mixes with slurry bed system hydrogenation catalyst, form suspension slurry, after preheating, enter slurry bed system hydrogenator carry out hydrocracking, exported product is through gas-liquid separator, hydrogen-containing gas and liquid product are separated, liquid product is from the bottom feed of the upflowing deferrization decalcification reactor of fixed bed hydrogenation treatment unit, whole beds is made to produce slight expansion, thus slow down the rate of growth of the Pressure Drop of beds, when the technical process adopted can avoid deferrization decalcifying agent and demetalization inactivation, the situation that sweetening agent and denitrfying agent activity also have sizable potentiality effectively not play occurs.Be recommended in deferrization decalcification reactor, demetalization reactor, desulphurization reactor and denitrification reactor simultaneously and select special catalyst, be particularly suitable for processing high-sulfur, high metal content, high bitum residual oil, the long-term operation of implement device.
Accompanying drawing explanation
Fig. 1 is application a kind of inferior heavy oil of the present invention or residual hydrocracking process flow diagram.Below in conjunction with accompanying drawing, the method that the present invention improves is further described, but does not thereby limit the invention.
First inferior heavy oil or residual oil raw material mix with slurry bed system hydrogenation catalyst, form suspension slurry, after preheating, enter slurry bed system hydrogenator carry out hydrocracking, then effluent enters the bottom of up-flow reactor R-1A and/or R-1B of fixed bed hydrogenation treatment unit, deferrization decalcification reaction is carried out with up-flow reactor catalyst exposure, its resultant of reaction has two operation scheme: one is without being separated the bottom directly entering up-flow reactor R-2, carry out hydrodemetallation (HDM) (Ni in the presence of a catalyst, V) react, its resultant of reaction is without separation, directly enter fixed bed desulphurization reactor R-3, carry out hydrodesulfurization reaction in the presence of a catalyst, two is directly enter desulphurization reactor, carries out hydrodesulfurization reaction in the presence of a catalyst.Its desulphurization reactor resultant of reaction, without separation, directly enters fixed bed denitrification reactor R-4.
Deferrization decalcification plant running process steps is as follows:
(1) in initial reaction stage, use together with R-1A with R-1B reactor, heavy oil or residual oil raw material are introduced into R-1A, then enter R-1B and carry out deferrization decalcification reaction.
(2) after reacting for some time, R-1A reactor catalyst is active in the middle and later periods, at this moment can flow to by feed change, and the advanced R-1B reactor of raw material enters R-1A reactor again.
(3) in R-1A reactor, deferrization decalcification catalyzer is in deactivation phases, closes R-1A reactor feed valve, and with regenerating and/or replace with live catalyst the catalyzer of reactor.Now material only enters R-1B reactor.
(4) after R-1A completes and changes agent, the advanced R-1B reactor of material, then enter to change the reactor R-1A of agent.
(5) in R-1B reactor, deferrization decalcification catalyzer is in deactivation phases, closes R-1B reactor feed valve, and with regenerating and/or replace with live catalyst the catalyzer of reactor.Now material only enters R-1A reactor.
(6) repeating step (1)-step (5) is continued.
For demetalization reactor R-2, in operational process, especially in catalyst for demetalation active latter stage, material out can directly enter desulphurization reactor R-3 from deferrization decalcification reactor.And with regenerating and/or replace with live catalyst the catalyst for demetalation of reactor.After completing catalyzer replacement, material out enters demetalization reactor R-2, desulphurization reactor R-3 and denitrification reactor R-4 more successively from deferrization decalcification reactor.
Embodiment
Embodiment all uses the hydroprocessing technique of the inferior heavy oil shown in Fig. 1 or residual oil.
Embodiment 1
Take raw material A as raw material (character is in table 1), under combination process flow process, process 2000h.Slurry bed system weighted BMO spaces processing condition are as follows: hydrogen pressure 18.0MPa; Temperature 430 DEG C; Volume space velocity 0.6h during liquid
-1; Hydrogen to oil volume ratio 1000; Slurry bed system catalyzer is carbonaceous particle and molybdenum oxide composite catalyst, and add-on is 5%, and slurry bed system hydrogenation catalyst prepares according to method in embodiment in CN102049252A 2.The processing condition of fixed bed hydrogenation process are as follows: hydrogen pressure 18.0MPa; Temperature 390 DEG C; Volume space velocity 0.3h during liquid
-1; Hydrogen to oil volume ratio 1000.Each reactor charge catalyzer is followed successively by hydrogenation deferrization decalcification catalyzer, Hydrodemetalation catalyst, Hydrobon catalyst and hydrodenitrogenation catalyst.The honeycomb shape deferrization decalcifying agent BN-01A(80 order that hydrogenation deferrization decalcification catalyzer adopts Jiangxi to answer Tao Kang to produce along Industrial Co., Ltd.); In Hydrodemetalation catalyst, Hydrobon catalyst employing CN101928593A, in embodiment 1, method obtains; Hydrodenitrogenation catalyst, in employing CN101928593A, in embodiment 2, method obtains.Hydrogenation deferrization decalcification catalyzer, hydrodemetallation (HDM) agent, hydrogen desulfurization agent and hydrodenitrification agent, additional proportion is respectively 18%, 20%, 30%, 32%.
Embodiment 2
With raw material B for raw material (character is in table 1), through combination process process 2000h.Slurry bed system weighted BMO spaces processing condition are as follows: hydrogen pressure 12.0MPa; Temperature 390 DEG C; Volume space velocity 0.2h during liquid
-1; Hydrogen to oil volume ratio 800; Slurry bed system hydrogenation catalyst is with embodiment 1, and be carbonaceous particle and nickel oxide composite catalyst, add-on is 0.5%.The processing condition of fixed bed hydrogenation process are as follows: hydrogen pressure 12.0MPa; Temperature 385 DEG C; Volume space velocity 0.25h during liquid
-1; Hydrogen to oil volume ratio 800.Each reactor charge catalyzer is followed successively by hydrogenation deferrization decalcification catalyzer, Hydrodemetalation catalyst, Hydrobon catalyst and hydrodenitrogenation catalyst.Catalyzer and additional proportion are with embodiment 1.
Comparative example 1
Take raw material A as raw material (character is in table 1), same with embodiment 1, merely through fixed bed hydrogenation process 2000h.The processing condition of fixed bed hydrogenation process are as follows: hydrogen pressure 18.0MPa; Temperature 390 DEG C; Volume space velocity 0.3h during liquid
-1; Hydrogen to oil volume ratio 1000.Each reactor charge catalyzer is followed successively by hydrogenation deferrization decalcification catalyzer, Hydrodemetalation catalyst, Hydrobon catalyst and hydrodenitrogenation catalyst.Catalyzer and additional proportion are with embodiment 1.
Comparative example 2
With raw material B for raw material (character is in table 1), same with embodiment 2, merely through slurry bed system weighted BMO spaces technique 2000h.Slurry bed system weighted BMO spaces processing condition are as follows: hydrogen pressure 12.0MPa; Temperature 385 DEG C; Volume space velocity 0.25h during liquid
-1; Hydrogen to oil volume ratio 800; Slurry bed system hydrogenation catalyst is with embodiment 1, and be carbonaceous particle and nickel oxide composite catalyst, add-on is 0.5%.
Feedstock property composition evaluated by table 1
The main physico-chemical property of table 2 used catalyst of the present invention
Table 32000 hours life test-results
Claims (12)
1. an inferior heavy oil, residual hydrocracking combination process, it is characterized in that heavy oil and/or residual oil raw material first through slurry bed system weighted BMO spaces, after gas-liquid separation, liquid product is again through fixed bed hydrogenation upgrading, wherein, slurry bed system weighted BMO spaces part comprises a slurry bed system hydrogenator and slurry bed system hydrogenation catalyst, fixed bed hydrogenation upgrading part is reactor used mainly to be comprised sequentially: two upflowing deferrization decalcification reactors, a upflowing demetalization reactor, a fixed bed desulphurization reactor, a fixed bed denitrification reactor, specific as follows: the inlet line of two upflowing deferrization decalcification reactors and outlet line are all equipped with check valve, a pipeline is connected with before outlet line check valve with after another upflowing deferrization decalcification Reactor inlet pipeline check valve, material is made to be able to import from the outlet of a upflowing deferrization decalcification reactor import of another upflowing deferrization decalcification reactor, pipeline is equipped with check valve, the inlet line and outlet line of upflowing demetalization reactor are all equipped with 3-way valve, other two ends in the 3-way valve of upflowing demetalization Reactor inlet pipeline, one end connects the outlet line of streaming demetalization reactor, the other end pipeline connects the 3-way valve on streaming demetalization reactor outlet pipeline, and this 3-way valve also has one end to connect with the source line of fixed bed desulphurization reactor, first raw material is mixed to form suspension slurry with slurry bed system hydrogenation catalyst, then enter slurry bed system hydrogenator and carry out weighted BMO spaces, product is after gas-liquid separation, liquid product is through upflowing deferrization decalcification reactor, reactor is in-built doses hydrogen deferrization decalcification catalyzer, remove a part of iron, slurry bed system catalyzer after calcium and slurry bed system hydrotreatment, its resultant of reaction has two kinds of operation scheme: one is directly enter upflowing demetalization reactor without separation, hydrodemetallation (HDM) reaction is carried out under catalyst for demetalation exists, its resultant of reaction is without separation, directly enter fixed bed desulphurization reactor, hydrodesulfurization reaction is carried out under desulfurization catalyst exists, two is directly enter desulphurization reactor, under desulfurization catalyst exists, carry out hydrodesulfurization reaction, desulphurization reactor resultant of reaction, without separation, directly enters fixed bed denitrification reactor, under denitrification catalyst exists, carry out hydrodenitrification reaction, slurry bed system weighted BMO spaces processing condition are: hydrogen pressure 8.0MPa ~ 20.0MPa, temperature 350 DEG C ~ 450 DEG C, volume space velocity 0.2h during liquid
-1~ 3h
-1, hydrogen to oil volume ratio 300 ~ 2000, slurry bed system hydrogenation catalyst adopts equi-volume impregnating supported active metals component to obtain, and carrier is specific surface area is 400 ~ 2000m
2the carbonaceous particle of/g, in catalyzer, active metallic content is 300 ~ 1500 μ g/g, catalyst charge accounts for the 0.5wt% ~ 5wt% of stock oil.
2. technique according to claim 1, it is characterized in that hydrogenation deferrization decalcification catalyzer, Hydrodemetalation catalyst, Hydrobon catalyst and hydrodenitrogenation catalyst, catalyzer aperture reduces gradually from left to right, and granularity reduces gradually, and porosity reduces gradually.
3. technique according to claim 1, it is characterized in that fixed bed hydrogenation upgrading part is reactor used and middlely load one or more catalyzer respectively, along logistics direction, aperture reduces gradually, and granularity reduces gradually, and porosity reduces gradually.
4. technique according to claim 1, it is characterized in that in slurry bed system hydrogenation catalyst, active metal oxide takes from group VIB metal and/or VIII race's metal, content is 500 ~ 1000 μ g/g.
5. technique according to claim 1, is characterized in that fixed bed hydrogenation upgrading some processes condition is: hydrogen pressure 5.0MPa ~ 20.0MPa; Temperature 300 DEG C ~ 450 DEG C; Volume space velocity 0.2h during liquid
-1~ 3h
-1; Hydrogen to oil volume ratio 300 ~ 2000.
6. technique according to claim 1 and 2, is characterized in that hydrogenation deferrization decalcification catalyzer is:
1) with Al
2o
3or containing K
2o, MgO, SiO
2, TiO
2, ZrO
2al
2o
3as carrier;
2) pore volume is 0.1 ~ 3.0ml/g;
3) specific surface is 50 ~ 200m
2/ g;
4) porosity is 40% ~ 75%;
5) catalyzer is in corresponding burning amount, containing 1.0 ~ 10.0% group VIB metals and/or 0.5 ~ 3.0% VIII race's metal.
7. technique according to claim 6, it is characterized in that hydrogenation deferrization decalcification catalyzer pore volume is 0.3 ~ 1.3ml/g, specific surface is 80 ~ 150m
2/ g.
8. technique according to claim 6, is characterized in that hydrogenation deferrization decalcification catalyzer contains the MoO of 1.0 ~ 10.0%
3, WO
3in one or both and/or 0.5 ~ 3.0% CoO, NiO in one or both.
9. technique according to claim 1 and 2, is characterized in that Hydrodemetalation catalyst, Hydrobon catalyst, hydrodenitrogenation catalyst consist of:
1) with Al
2o
3or containing K
2o, MgO, SiO
2, TiO
2, ZrO
2al
2o
3as carrier;
2) pore volume is 0.1 ~ 3.0ml/g;
3) specific surface is 20 ~ 400m
2/ g;
4) catalyzer is in corresponding burning amount, the group VIB metal containing 1.0 ~ 20.0% and/or 0.5 ~ 8.0% VIII race's metal.
10. technique according to claim 9, it is characterized in that Hydrodemetalation catalyst, Hydrobon catalyst, hydrodenitrogenation catalyst pore volume are 0.3 ~ 1.3ml/g, specific surface is 100 ~ 240m
2/ g.
11. techniques according to claim 9, is characterized in that Hydrodemetalation catalyst, Hydrobon catalyst, hydrodenitrogenation catalyst contain the MoO of 1.0 ~ 20.0%
3, WO
3in one or both, and/or one or both in CoO, NiO of 0.5 ~ 8.0%.
12. techniques according to claim 9, is characterized in that Hydrodemetalation catalyst, Hydrobon catalyst, hydrodenitrogenation catalyst contain the MoO of 3.0 ~ 16%
3, WO
3in one or both, and/or one or both in CoO, NiO of 1.0 ~ 5.5%.
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| CN111826194B (en) * | 2019-04-19 | 2022-08-09 | 中国石油化工股份有限公司 | Residual oil hydrotreating method |
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| CN114574239A (en) * | 2020-11-30 | 2022-06-03 | 中国石油天然气股份有限公司 | Preparation method of marine fuel oil |
| CN114574240A (en) * | 2020-11-30 | 2022-06-03 | 中国石油天然气股份有限公司 | Method for preparing bunker fuel oil by hydrogenation |
| CN118256279A (en) * | 2022-12-26 | 2024-06-28 | 中国石油天然气股份有限公司 | Deep hydrotreating method for high-iron high-calcium heavy oil |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1335371A (en) * | 2000-07-24 | 2002-02-13 | 中国石油化工股份有限公司 | Heavy hydrocarbon feeding and hydrogenating process |
| CN1484684A (en) * | 2000-12-11 | 2004-03-24 | 法国石油公司 | Method for hydrotreatment of heavy hydrocarbon fraction with switchable reactors and reactors capable of being shorted out |
| CN101928593A (en) * | 2009-06-26 | 2010-12-29 | 中国石油天然气股份有限公司 | Grading combination of heavy oil hydrogenation catalyst |
-
2012
- 2012-07-12 CN CN201210241248.8A patent/CN103540349B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1335371A (en) * | 2000-07-24 | 2002-02-13 | 中国石油化工股份有限公司 | Heavy hydrocarbon feeding and hydrogenating process |
| CN1484684A (en) * | 2000-12-11 | 2004-03-24 | 法国石油公司 | Method for hydrotreatment of heavy hydrocarbon fraction with switchable reactors and reactors capable of being shorted out |
| CN101928593A (en) * | 2009-06-26 | 2010-12-29 | 中国石油天然气股份有限公司 | Grading combination of heavy oil hydrogenation catalyst |
Non-Patent Citations (1)
| Title |
|---|
| "上流式渣油加氢保护剂的开发";胡长禄等;《石油炼制与化工》;20010930;第32卷(第9期);第64-66页 * |
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