CN102816599A - Residual oil hydrotreating combined process - Google Patents
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- 238000000034 method Methods 0.000 title claims abstract description 25
- 238000004523 catalytic cracking Methods 0.000 claims abstract description 62
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 52
- 239000003054 catalyst Substances 0.000 claims abstract description 22
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 19
- 239000001257 hydrogen Substances 0.000 claims abstract description 19
- 235000003599 food sweetener Nutrition 0.000 claims description 40
- 239000007789 gas Substances 0.000 claims description 40
- 239000003765 sweetening agent Substances 0.000 claims description 40
- 239000002283 diesel fuel Substances 0.000 claims description 29
- 230000003197 catalytic effect Effects 0.000 claims description 26
- 238000006243 chemical reaction Methods 0.000 claims description 20
- 238000004517 catalytic hydrocracking Methods 0.000 claims description 18
- 239000002002 slurry Substances 0.000 claims description 17
- 239000000463 material Substances 0.000 claims description 16
- 229910052751 metal Inorganic materials 0.000 claims description 14
- 239000002184 metal Substances 0.000 claims description 14
- 239000007795 chemical reaction product Substances 0.000 claims description 12
- 239000003795 chemical substances by application Substances 0.000 claims description 11
- 230000001681 protective effect Effects 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 9
- 238000011049 filling Methods 0.000 claims description 8
- 239000002994 raw material Substances 0.000 claims description 8
- 239000012535 impurity Substances 0.000 claims description 6
- 238000012545 processing Methods 0.000 claims description 6
- 238000002203 pretreatment Methods 0.000 claims description 5
- 238000006477 desulfuration reaction Methods 0.000 claims description 4
- 230000023556 desulfurization Effects 0.000 claims description 4
- 238000004821 distillation Methods 0.000 claims description 4
- -1 setting up Substances 0.000 claims description 4
- 238000007233 catalytic pyrolysis Methods 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- 229910052809 inorganic oxide Inorganic materials 0.000 claims description 2
- 150000002739 metals Chemical class 0.000 claims description 2
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 2
- 229910052698 phosphorus Inorganic materials 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 230000008929 regeneration Effects 0.000 claims description 2
- 238000011069 regeneration method Methods 0.000 claims description 2
- 230000007704 transition Effects 0.000 claims description 2
- 229910052721 tungsten Inorganic materials 0.000 claims description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 11
- 229910052799 carbon Inorganic materials 0.000 abstract description 10
- 230000008021 deposition Effects 0.000 abstract description 5
- 239000003921 oil Substances 0.000 description 106
- 239000000047 product Substances 0.000 description 25
- 230000000052 comparative effect Effects 0.000 description 17
- 238000002156 mixing Methods 0.000 description 7
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 6
- 239000005864 Sulphur Substances 0.000 description 6
- 238000006555 catalytic reaction Methods 0.000 description 6
- 239000010779 crude oil Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 3
- 239000000571 coke Substances 0.000 description 3
- 238000004939 coking Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000000084 colloidal system Substances 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 230000003009 desulfurizing effect Effects 0.000 description 2
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000012190 activator Substances 0.000 description 1
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- 230000007613 environmental effect Effects 0.000 description 1
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- 230000016615 flocculation Effects 0.000 description 1
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- 238000005194 fractionation Methods 0.000 description 1
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- 239000003317 industrial substance Substances 0.000 description 1
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- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
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- 238000007670 refining Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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Abstract
A kind of residual oil hydrotreatment combination process, this method adds a feed inlet before the desulfurizer bed layer of the hydrogenation unit of residual oil, residual oil and hydrogen enter the apparatus to react through the original feed inlet of the hydrogenation unit of residual oil, the hydrogenation residual oil enters the catalytic cracking apparatus to continue reacting, the catalytic cracking recycle oil returns to the hydrogenation unit of residual oil through the feed inlet that is set up additionally and carries on the hydrotreatment; the method can effectively reduce the carbon deposition of the desulfurizer and the catalyst behind the desulfurizer, prolong the operation period of a residual oil hydrotreatment device, improve the yield of light oil with high added value and reduce the usage amount of cold hydrogen.
Description
Technical field
Present method relates to a kind of with residual hydrocracking and catalytic cracking combined technique.
Background technology
Current, oil refining processing industry in the world is being faced with the crude resources severe challenge of heaviness and poor qualityization day by day.2008,3.42 hundred million tons of crude oil in China amount of finish, wherein the heavy crude amount of finish reaches 1.37 hundred million tons, accounts for total amount more than 40%.As everyone knows, residual oil accounts for the crude oil ratio usually 45～75%, and its character significantly is inferior to the lower gas wet goods cut of boiling range, and therefore, the crude oil deep processing is made every effort to maximize the pressure of producing light-end products and industrial chemicals and just dropped on the residual oil naturally.
In the optional technological line of residual oil deep processing, residual hydrogenation and catalytic cracking combined technique are a kind of good technology.Residual oil has improved hydrogen richness after removing impurity such as metal, sulphur, nitrogen through hydrotreatment, can be used as fine RFCC raw material, and residual oil is transformed fully.This technology has obtained increasing application, and in this combination process, catalytic cracking recycle oil is to be circulated to further processing in the catalytic cracking.Because contain polycyclic aromatic hydrocarbons in the heavy cycle oil, thereby light oil yield is low, the green coke amount is big, has increased the revivifier load, has reduced unit capacity and economic benefit.
In addition, in the residual hydrogenation reactor drum, through the hydrotreatment of conversion zones such as protective material bed, metal remover bed; Raw oil residual oil quilt is hydrogenation progressively, and the aromaticity of oil plant is step-down gradually, and dissolved bitumen matter is then flocculated owing to dissolve environmental change gradually; So when touching higher sweetening agent of hydrogenation activity and the catalyzer behind the sweetening agent; It is big that coke forming property becomes, and the accelerator activator inactivation has shortened catalyst life.
US4; 713,221 disclose on conventional residual hydrogenation and catalytic cracking combined basis, and the heavy cycle oil of catalytic cracking (comprising gas oil catalytic cracking and RFCC) is circulated to residual hydrogenation equipment; With carry out hydrogenation after topped crude mixes, hydrogenated residue gets into CCU.The change that this is little can make the benefit of one barrel of crude oil of the every processing in refinery have a net increase of 0.29 dollar.
CN 1119397C discloses a kind of residual hydrocracking---catalytic cracking combination process, is that residual oil and clarified oil get into the residual hydrocracking device together, in the presence of hydrogen and hydrogenation catalyst, carries out hydrogenation reaction; The hydrogenated residue that obtains of reaction gets into CCU, in the presence of cracking catalyst, carries out cracking reaction, and heavy cycle oil is in the CCU circulating inside, react slurry oil obtain clarified oil through separation, be back to hydrogenation unit.
CN 101210200A discloses a kind of residual hydrocracking and catalytic cracking combination process; The thing that steams of residual oil, the heavy catalytic cycle oil that removes solid impurity, optional distillate and optional catalytically cracked oil gets into the residual hydrocracking device together; The hydrogenated residue of gained gets into CCU with optional vacuum gas oil, obtains various products; The catalytic cracking turning oil that removes impurity is circulated to the residual hydrocracking device; Catalytically cracked oil is carried out fractionation by distillation, and be circulated to the residual hydrocracking device.
Bituminous matter in the residual oil is dissolved in colloid, the aromatic hydrocarbons, and along with the carrying out of reaction, the colloid around the bituminous matter, aromatic hydrocarbons are gradually by hydrogenation; The bituminous matter flocculation is separated out, and causes in sweetening agent bed and a large amount of cokings of back segment beds thereof, and aromaticity content is higher in the recycle stock; The introducing of recycle stock can be promoted the dissolving of bituminous matter in residual oil, but with recycle stock and residual oil introducing device together, recycle stock passes through the hydrotreatment of protective material bed and metal remover bed; A large amount of aromatic hydrocarbons are by hydrogenation; Aromaticity reduces significantly, can't give full play to it to bitum dissolving power at sweetening agent bed and back segment beds thereof, and the effect of combination process is had a greatly reduced quality.
Summary of the invention
The combination process that the purpose of this invention is to provide a kind of residual hydrocracking and catalytic cracking.Before the sweetening agent bed of residual hydrocracking device, set up an opening for feed, residual oil hydrogen exist with the hydrotreatment reaction conditions under, contact with residual oil hydrocatalyst and to carry out hydrotreatment and react; Residual oil hydrocatalyst is to comprise three or more of protective material, metal remover, sweetening agent, and different catalysts is divided into different beds fillings.The product separation obtains gas, hydrotreated naphtha, hydrogenated diesel oil and hydrogenated residue.Hydrogenated residue directly or get into CCU together with other optional conventional catalytically cracked stock and further react, reaction product is separated and is obtained dry gas, liquefied gas, catalytic gasoline, catalytic diesel oil, heavy catalytic cycle oil and slurry oil.
In heavy catalytic cycle oil and the slurry oil one or both, through after the pre-treatment, promptly catalytic cracking recycle oil gets into reactor reaction through the opening for feed of before the sweetening agent bed, setting up.Pretreated method can for filter, during distillation, rotation separate etc. one or more, after the pre-treatment, foreign matter content is less than 15ppm.
The combination process of a kind of residual hydrocracking of the present invention comprises residual hydrogenation reactive moieties, catalytic cracking reaction part and catalytic cracking recycle oil reactive moieties;
(1) residual hydrogenation reactive moieties
Residual hydrogenation part of the present invention is the same with traditional residual hydrogenation equipment, and different is before the sweetening agent bed, to have increased an opening for feed.Install employed residual oil and be one or more the mixture in long residuum and the vacuum residuum.The catalyzer grating of residual hydrogenation equipment and filling need not change; Filling simultaneously comprises the catalyzer more than three types or three types of protective material, metal remover, sweetening agent, and sweetening agent is one or more in desulfurization demetalization transition agent, sweetening agent, the highly active desulfurization agent.Different catalysts is divided the bed filling, can be contained in the reactor drum, also can be contained in a plurality of reactor drums.Catalyzer generally is to be carrier with porous inorganic oxide such as aluminum oxide, and the oxide compound of group vib and VIII family metal oxide such as W, Mo, Co, Ni etc. is a reactive metal, optionally adds the catalyzer of auxiliary agents such as P, Si, F.The protective material bed can adopt fixed-bed reactor, also can adopt up-flow reactor, and other beds adopts fixed-bed reactor.
The normal operating condition of residual hydrocracking device is: hydrogen partial pressure 10～22MPa, temperature of reaction is 300 ℃～435 ℃, volume space velocity 0.1～4.5hr
-1, the volume ratio of hydrogen and residual oil is 500～2000, by weight, catalytic cracking recycle oil is 1%～30% of a raw material residual oil.
Residual oil and hydrogen are from the reaction of residual hydrogenation equipment opening for feed access to plant, and catalytic cracking recycle oil gets into reactor drum through the opening for feed of before sweetening agent, setting up, and reaction product can be separated into dry gas, hydrotreated naphtha, hydrogenated diesel oil and hydrogenated residue.
(2) catalytic cracking reaction part
The hydrogenated residue of step (1) gained separately or get into CCU together with other optional conventional catalytically cracked stock and further react, reaction product is separated and is obtained dry gas, liquefied gas, catalytic gasoline, catalytic diesel oil, heavy catalytic cycle oil and slurry oil.Described catalytic cracking can be a catalytic cracking family, like cover such as one in RFCC, catalytic pyrolysis, the voluminous isoparaffin catalytic cracking etc. or several covering devices.
The condition of catalytic cracking is: 470～650 ℃ of temperature of reaction, 0.5～5 second reaction times, the weight ratio 3～10 of catalyzer and raw oil, 650～800 ℃ of regeneration temperatures.
(3) catalytic cracking recycle oil reactive moieties
The catalytic cracking recycle oil reactive moieties can be through one or both the mixture in pretreated heavy catalytic cycle oil and the catalytically cracked oil; Catalytic cracking recycle oil accounts for 1%～30% of raw material residual oil; Must be through metals content impurity in the pretreated recycle stock less than 15ppm, the pretreatment process of recycle stock can be one or more in filtration, distillation, the rotation separation etc.Recycle stock is circulated to the opening for feed access to plant before the residual hydrogenation equipment sweetening agent bed.
Compare with existing method, method provided by the invention can reduce the coking amount of the beds of sweetening agent bed and sweetening agent back, prolongs sweetening agent and back catalyzer duration of service thereof.Recycle stock is without protective material bed, the hydrotreatment of metal remover bed, avoided in the recycle stock polycyclic aromatic hydrocarbons too early by hydrogenation, the bitum dissolving power of progressively separating out in can in sweetening agent and rear catalyst bed thereof, giving full play to residual oil; Simultaneously; Bituminous matter is through preliminary hydrotreatment, and the side chain on the bituminous matter removes because of hydrogenation, can know according to the similar compatibility principle; The solute effect of bituminous matter in recycle stock is better; So the adding of recycle stock can reduce the coking amount of the beds of sweetening agent bed and sweetening agent back, thereby can reduce loss of activity, the running period of extension fixture.
The recycle stock of heavy can more be converted into the lightweight material of high added value through hydrogenation, thereby improves the light weight fluid yield, reduces the externally extracting oil amount.
In addition, can adjust bed temperature, thereby save cold hydrogen consumption through the feeding temperature of adjustment recycle stock.
Description of drawings
The combination process schema of Fig. 1 residual hydrocracking.
Embodiment
Fig. 1 is the schematic flow sheet of the combined technical method of a kind of residual hydrocracking provided by the invention and catalytic cracking; The residual hydrocracking device adopts catalyst grade prescription formula; Every kind of catalyzer is contained in the different reactor drums; Be respectively protective material reactor drum, metal remover reactor drum, reactive desulfurizing agent device and other hydrogen-catalyst reactor, one or more in carbon residue agent, the denitrfying agent are taken off in filling in other hydrogen-catalyst reactor.Before the sweetening agent bed, increase an opening for feed.Different catalysts has been contained in four reactor drums in the synoptic diagram, in reality, also can be contained in one or two or three or five reactor drums.
Get into residual hydrogenation equipment through preheating after mixing from the residual oil of pipeline 01 with from the hydrogen of pipeline 02, contact with hydrogenation catalyst and carry out hydrotreatment and react; The product of residual hydrogenation gets into tripping device through pipeline 06; Obtain dry gas, hydrotreated naphtha, hydrogenated diesel oil, hydrogenated residue; Dry gas, hydrotreated naphtha, hydrogenated diesel oil pass through pipeline 07,08,09 caterpillar respectively, and hydrogenated residue gets into CCU through pipeline 10.Hydrogenated residue contacts with catalytic cracking catalyst in CCU and reacts; Obtain dry gas, liquefied gas, catalytic gasoline, catalytic diesel oil, heavy catalytic cycle oil and slurry oil, dry gas, liquefied gas, catalytically cracked gasoline, catalytic cracking diesel oil are respectively through pipeline 11,12,13,14 caterpillars.Heavy catalytic cycle oil and slurry oil be warp 15,16 caterpillars respectively, through after the pre-treatment, and one or mixture process pipeline 05,04 entering residual hydrogenation equipment sweetening agent bed in the two.Can regulate the temperature of reaction of sweetening agent bed and back beds through the feeding temperature of recycle stock.
One liter of four anti-pilot plant of fixed bed residual hydrogenation that the residual hydrogenation equipment that uses in embodiment and the Comparative Examples is produced as U.S. Xytel company; Device is totally four reactor drums; Load protective material, metal remover, sweetening agent and denitrfying agent respectively; Catalyst property sees that table 1 grade mixing ratio is 5: 40: 30: 25, and catalyzer is that independently develop in the laboratory.In order to carry out experiment, before filling reactive desulfurizing agent device, increased an opening for feed.Using the carbon deposition quantity on the rear catalyst is after catalyzer is drawn off from device, to use ethanol/toluene (50: 50) Suo Shi extracting 50 hours, 200 ℃ dry 5 hours down, use the Flementar elemental analyser to measure then.
Carry out on the small-sized riser reactor pilot plant that FCC tests designs in the laboratory voluntarily in embodiment and the Comparative Examples.
The residual oil that uses in embodiment and the Comparative Examples is Kuwait's long residuum; Catalytically cracked oil and catalytic cracking turning oil are taked fine filtering; Filter back solid impurity content less than 5ppm; Filter the character of back slurry oil, heavy catalytic cycle oil and see table 2, the metal content (Ni+V) in slurry oil and the filtration back turning oil is all less than 15ppm.
Table 1 the present invention uses the main physico-chemical property of catalyzer
Table 2 test raw material oil main character
The main operational condition of table 3
Comparative Examples 1
Catalytic cracking recycle oil adopts and filters the back heavy catalytic cycle oil; After recycle stock and residual oil raw material mix with hydrogen together; Get into the residual hydrogenation pilot plant; Condition according in the table 3 is reacted, and carries out reaction product and is separated into gas, hydrotreated naphtha, hydrogenated diesel oil, hydrogenated residue, and product distributes and running condition is seen table 4; Hydrogenated residue directly or get into catalysis together with other catalytically cracked materials and split device, product is separated into dry gas, liquefied gas, catalytically cracked gasoline, catalytic cracking diesel oil, catalytic cracking turning oil and slurry oil, reaction conditions is seen table 3.
Embodiment 1
Residual oil and hydrogen mixing oil directly get into the residual hydrogenation pilot plant; Catalytic cracking recycle oil advances through the sweetening agent bed and expects a mouthful entering residual hydrogenation reactor drum; React according to the condition in the table 3 equally; Carry out reaction product and be separated into gas, hydrotreated naphtha, hydrogenated diesel oil, hydrogenated residue, product distributes and running condition is seen table 4; Hydrogenated residue directly or get into catalysis together with other catalytically cracked materials and split device, product is separated into dry gas, liquefied gas, catalytically cracked gasoline, catalytic cracking diesel oil, catalytic cracking turning oil and slurry oil.
Through table 4, we can know and compare with Comparative Examples in the hydrogenated products, and the hydrogenated diesel oil yield among the embodiment is high 0.25%, and the sulphur content of hydrogenated residue is low 0.24%; Meanwhile, the carbon distribution on the catalyzer of sweetening agent and back thereof, far below corresponding catalyst in the Comparative Examples, the catalyzer expectation has been Duoed 3 months than Comparative Examples running period.
Table 44000 hour residual hydrogenation product data and catalyst carbon deposition situation
| Embodiment 1 | Comparative Examples 1 | |
| Recycle stock | Heavy catalytic cycle oil | Heavy catalytic cycle oil |
| The residual hydrogenation product distributes, wt% | ||
| C1～C4 | 1.47 | 1.46 |
| Hydrotreated naphtha (C5～180 ℃) | 0.96 | 0.97 |
| Hydrogenated diesel oil (180 ℃～350 ℃) | 7.25 | 7.00 |
| Hydrogenated residue (＞350 ℃) | 87.55 | 87.60 |
| The hydrogenated residue sulphur content, wt% | 0.64 | 0.88 |
| Carbon distribution on the catalyzer | ||
| Sweetening agent H DS1, wt% | 10.9 | 14.4 |
| Sweetening agent HDS2, wt% | 14.7 | 18.5 |
| Denitrfying agent HDN, wt% | 18.1 | 27.6 |
| Estimate running period | 16 | 13 |
| The catalytic cracking product distributes, wt% | ||
| Dry gas | 1.72 | 1.74 |
| Liquefied gas | 10.47 | 10.56 |
| Catalytic gasoline | 44.01 | 44.07 |
| Catalytic diesel oil | 15.43 | 15.38 |
| Catalytic cracking turning oil | 12.78 | 12.70 |
| Slurry oil | 8.02 | 8.12 |
| Coke | 8.68 | 8.71 |
Comparative Examples 2
Catalytic cracking recycle oil adopts the catalytically cracked oil in the table 2; After recycle stock and residual oil raw material mix with hydrogen together; Get into the residual hydrogenation pilot plant, react, carry out reaction product and be separated into gas, hydrotreated naphtha, hydrogenated diesel oil, hydrogenated residue according to the condition in the table 3; Reaction conditions is seen table 3, and product distributes and running condition is seen table 5.Hydrogenated residue directly or get into catalysis together with other catalytically cracked materials and split device, product is separated into dry gas, liquefied gas, catalytically cracked gasoline, catalytic cracking diesel oil, catalytic cracking turning oil and slurry oil.
Embodiment 2
Residual oil and hydrogen mixing oil directly get into the residual hydrogenation pilot plant; Catalytic cracking recycle oil advances through the sweetening agent bed and expects a mouthful entering residual hydrogenation reactor drum; React according to the condition in the table 3 equally, carry out reaction product and be separated into gas, hydrotreated naphtha, hydrogenated diesel oil, hydrogenated residue; Product distributes and running condition is seen table 5.Hydrogenated residue directly or get into catalysis together with other catalytically cracked materials and split device, product is separated into dry gas, liquefied gas, catalytically cracked gasoline, catalytic cracking diesel oil, catalytic cracking turning oil and slurry oil.
Through table 5, we can know and compare with Comparative Examples in the hydrogenated products, and the hydrogenated diesel oil yield among the embodiment is high 0.28%, and the sulphur content of hydrogenated residue is low 0.17%; Meanwhile, the carbon distribution on the catalyzer of sweetening agent and back thereof, far below corresponding catalyst in the Comparative Examples, the catalyzer expectation has been Duoed 2 months than Comparative Examples running period.
Table 54000 hour residual hydrogenation product data and catalyst carbon deposition situation
| Embodiment 2 | Comparative Examples 2 | |
| Recycle stock | Catalytically cracked oil | Catalytically cracked oil |
| The residual hydrogenation product distributes, weight % | ||
| C1～C4 | 1.42 | 1.42 |
| Hydrotreated naphtha (C5～180 ℃) | 0.93 | 0.94 |
| Hydrogenated diesel oil (180 ℃～350 ℃) | 7.39 | 7.11 |
| Hydrogenated residue (＞350 ℃) | 87.57 | 87.62 |
| The hydrogenated residue sulphur content, wt% | 0.72 | 0.89 |
| Carbon distribution on the catalyzer | ||
| Sweetening agent HDS1, weight % | 11.7 | 15.5 |
| Sweetening agent HDS2, weight % | 17.2 | 21.3 |
| Denitrfying agent HDN, weight % | 23.6 | 29.8 |
| Estimate running period | 17 | 15 |
| The catalytic cracking product distributes, wt% | ||
| Dry gas | 1.73 | 1.70 |
| Liquefied gas | 10.49 | 10.57 |
| Catalytic gasoline | 44.01 | 44.05 |
| Catalytic diesel oil | 15.33 | 15.44 |
| Catalytic cracking turning oil | 12.88 | 12.93 |
| Slurry oil | 8.12 | 8.05 |
| Coke | 7.44 | 7.26 |
Comparative Examples 3
The heavy catalytic cycle oil in the catalytic cracking recycle oil employing table 2 and the mixture of catalytically cracked oil, blending ratio is 5: 5; Recycle stock and residual oil raw material get into the residual hydrogenation pilot plant after mixing with hydrogen together, react according to the condition in the table 3, carry out reaction product and are separated into gas, hydrotreated naphtha, hydrogenated diesel oil, hydrogenated residue, and reaction conditions is seen table 3.Product distributes and running condition is seen table 6.Hydrogenated residue directly or get into catalysis together with other catalytically cracked materials and split device, product is separated into dry gas, liquefied gas, catalytically cracked gasoline, catalytic cracking diesel oil, catalytic cracking turning oil and slurry oil.
Embodiment 3
Residual oil and hydrogen mixing oil directly get into the residual hydrogenation pilot plant; Catalytic cracking recycle oil advances through the sweetening agent bed and expects a mouthful entering residual hydrogenation reactor drum; React according to the condition in the table 3 equally, carry out reaction product and be separated into gas, hydrotreated naphtha, hydrogenated diesel oil, hydrogenated residue; Product distributes and running condition is seen table 6.Hydrogenated residue directly or get into catalysis together with other catalytically cracked materials and split device, product is separated into dry gas, liquefied gas, catalytically cracked gasoline, catalytic cracking diesel oil, catalytic cracking turning oil and slurry oil.
Through table 6, we can know and compare with Comparative Examples in the hydrogenated products, and the hydrogenated diesel oil yield among the embodiment is high 0.20%, and the sulphur content of hydrogenated residue is low 0.14%; Meanwhile, the carbon distribution on the catalyzer of sweetening agent and back thereof, far below corresponding catalyst in the Comparative Examples, the catalyzer expectation has been Duoed 2 months than Comparative Examples running period.
4000 hours residual hydrogenation product data of table 6 and catalyst carbon deposition situation
Claims (3)
1. a residual hydrocracking combination process is characterized in that: comprise residual hydrogenation reactive moieties, catalytic cracking reaction part and catalytic cracking recycle oil reactive moieties;
(1) residual hydrogenation reactive moieties
Residual hydrogenation partly is before the sweetening agent bed of traditional residual hydrogenation equipment, to increase an opening for feed; Residual oil is one or more the mixture in long residuum and the vacuum residuum; Catalyzer grating and filling do not change, and filling simultaneously comprises the catalyzer more than three types or three types of protective material, metal remover, sweetening agent, and sweetening agent is one or more in desulfurization demetalization transition agent, sweetening agent, the highly active desulfurization agent; Different catalysts is divided bed filling, is contained in the reactor drum or is contained in a plurality of reactor drums; Catalyzer is to be carrier with the porous inorganic oxide aluminum oxide, and W, Mo, Co optionally add the catalyzer of P, Si or F or/and the oxide compound of Ni is a reactive metal; The protective material bed adopts fixed-bed reactor or adopts up-flow reactor, and other beds adopts fixed-bed reactor;
The operational condition of residual hydrocracking device is: hydrogen partial pressure 10～22MPa, temperature of reaction is 300 ℃～435 ℃, volume space velocity 0.1～4.5hr
-1, the volume ratio of hydrogen and residual oil is 500～2000, by weight, catalytic cracking recycle oil is 1～30% of a raw material residual oil;
Residual oil and hydrogen are from the reaction of residual hydrogenation equipment opening for feed access to plant, and catalytic cracking recycle oil gets into reactor drum through the opening for feed of before sweetening agent, setting up, and reaction product is dry gas, hydrotreated naphtha, hydrogenated diesel oil and hydrogenated residue;
(2) catalytic cracking reaction part
The hydrogenated residue of step (1) gained separately or get into CCU together with other optional conventional catalytically cracked stock and further react, reaction product is dry gas, liquefied gas, catalytic gasoline, catalytic diesel oil, heavy catalytic cycle oil and slurry oil; Described catalytic cracking is the cover of one in RFCC, catalytic pyrolysis, the voluminous isoparaffin catalytic cracking or appoints several covering devices;
The condition of catalytic cracking is: 470～650 ℃ of temperature of reaction, 0.5～5 second reaction times, the weight ratio 3～10 of catalyzer and raw oil, 650～800 ℃ of regeneration temperatures;
(3) catalytic cracking recycle oil reactive moieties
The mixture of one or both in heavy catalytic cycle oil, the catalytically cracked oil through pre-treatment, is circulated to the opening for feed access to plant before the residual hydrogenation equipment sweetening agent bed as recycle stock after making metals content impurity in the oil less than 15ppm.
2. according to the combination process of the described residual hydrocracking of claim 1, it is characterized in that: described residual oil is a kind of or mixture in long residuum and the vacuum residuum.
3. according to the combination process of the described residual hydrocracking of claim 1; It is characterized in that: described catalytic cracking recycle oil is before being circulated to the sweetening agent bed; Earlier through pre-treatment, the method for processing can for filter, during distillation, rotation separate etc. one or more.
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| CN2011101563749A CN102816599A (en) | 2011-06-10 | 2011-06-10 | Residual oil hydrotreating combined process |
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| CN103923698A (en) * | 2013-01-11 | 2014-07-16 | 中国石油化工股份有限公司 | Catalysis conversion method for producing aromatic compounds |
| CN110653008A (en) * | 2018-06-30 | 2020-01-07 | 中国石油化工股份有限公司 | Method for on-line activity recovery of heavy oil hydrotreating catalyst and agent unloading method |
| CN110655948A (en) * | 2018-06-30 | 2020-01-07 | 中国石油化工股份有限公司 | Heavy oil hydrotreating method |
| CN112745952A (en) * | 2019-10-31 | 2021-05-04 | 中国石油化工股份有限公司 | Method and system for processing aromatic-rich distillate oil |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103923698A (en) * | 2013-01-11 | 2014-07-16 | 中国石油化工股份有限公司 | Catalysis conversion method for producing aromatic compounds |
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| CN110653008A (en) * | 2018-06-30 | 2020-01-07 | 中国石油化工股份有限公司 | Method for on-line activity recovery of heavy oil hydrotreating catalyst and agent unloading method |
| CN110655948A (en) * | 2018-06-30 | 2020-01-07 | 中国石油化工股份有限公司 | Heavy oil hydrotreating method |
| CN112745952A (en) * | 2019-10-31 | 2021-05-04 | 中国石油化工股份有限公司 | Method and system for processing aromatic-rich distillate oil |
| CN112745952B (en) * | 2019-10-31 | 2022-07-15 | 中国石油化工股份有限公司 | Method and system for processing aromatic-rich distillate oil |
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