CN103305273B - A kind of catalysis conversion method reducing coke and dry gas yied - Google Patents
A kind of catalysis conversion method reducing coke and dry gas yied Download PDFInfo
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Abstract
A kind of catalysis conversion method reducing coke and dry gas yied, comprise bad heavy feed stock raffinated oil through solvent extraction and extract oil out, wherein raffinate oil and enter the bottom of catalyst cracker, as one of the stock oil of catalytic cracking, extraction oil enters hydrotreating unit and carries out polycyclic aromatic hydrocarbons selective hydrogenation, extraction oil after hydrogenation enters the middle and lower part of catalyst cracker, as the stock oil two of catalytic cracking, the catalytic cracking production that catalytic cracking unit obtains is separated into various product, and catalytic cracking catalyst cyclic regeneration uses.The method forms for the hydrocarbon of bad heavy catalytic raw material, by more reasonably integrated oil refining process technology, improves the utilization ratio of hydrogen, increases total liquid yield, saves petroleum resources; Reduce the productive rate of the by product such as coke, provide a new approach for the oil refining production process realizing reducing carbon emission cleans.
Description
Technical field
The invention belongs to the catalysis conversion method of petroleum hydrocarbon, more particularly, relate to the catalysis conversion method of a kind of bad heavy feed stock solvent extraction, selective hydrogenation process and catalytic cracking integrated technique.
Background technology
Now, lot of challenges that the development of whole world petroleum refining industry faces oil price volatility, weakness of demand, the aggravation of crude oil in poor quality trend, oil quality specification improves, energy-saving and emission-reduction requirement becomes sternly, biofuel develops rapidly etc., minimizing Carbon emission, mitigation of climate change have become petroleum refining industry and to have transformed mode of economic growth, kept the only way of Sustainable development.Catalytic cracking technology is as the most important processing means being produced light-end products in current refinery by mink cell focus, and the coke burning in this process is one of important sources of refinery C discharge, especially for bad heavy feed stock.Therefore in the urgent need to reducing the carbon emission in catalytic cracking process.
Reducing one of method of carbon emission is directly in catalytic cracking process, reduce coke yield.For bad heavy feed stock, because its carbon residue, metal, aromaticity content etc. are higher, the main method reducing coke yield directly improves fcc raw material.
US3775290 discloses and a kind of desalted crude, catalysis heavy cycle oil and wax tailings etc. mixing carries out hydrotreatment, and hydrogenation tail oil carries out the combined technical method of catalytic cracking again.US3852186 discloses the processing method of a kind of hydrogenating desulfurization and catalytic cracking combination.US4780193, EP0351464, CA1302329 disclose a kind of method adopting high pressure, low temperature hydrogenation treatment technology to improve catalytically cracked material quality, the temperature of reaction of this hydrotreater is lower than 390 DEG C, reaction pressure at least at more than 10.0MPa, preferably at more than 12.0MPa.Under the processing condition being conducive to aromatic saturation, improved the cracking performance of catalytic cracking unit raw material by hydrotreatment.CN101684417 discloses a kind of hydrogenation-catalytic cracking combination process of optimization, wax oil raw material reacts in hydrotreatment reaction zone, the hydrogenation wax oil obtained is as catalytically cracked stock, directly catalytic cracking unit is entered without fractionation, catalysis heavy cycle oil loops back hydrotreatment reaction zone, the logistics of high pressure hot separator top gas phase and catalysis gently circulate and enter hydro-upgrading reaction zone with optional gas oil, carry out hydro-upgrading reaction, resultant of reaction obtains hydrotreated naphtha and hydrogenated diesel oil after fractionation.Products scheme is flexible, can produce high-quality low-sulfur gasoline, fine-quality diesel oil and reformer feed simultaneously.
Catalytic cracking and hydroprocessing technique combination another kind of method as US3801495 introduce, utilize method that is Conventional catalytic cracking and hydrotreatment combination process processing heavy feed stock, the heavy distillate that wherein catalytic cracking produces enters hydrotreatment, the steam that catalytic cracking process coke combustion heat release produces is for hydrogen manufacturing, and the hydrogen of generation is used for hydroprocessing technique.
CN100487080 disclose a kind of by first for heavy feed stock hydrogenation again catalytic cracking carry out to produce to greatest extent the chemical industry type oil refining method of propylene, ethene and aromatic hydrocarbons simultaneously.
Be not difficult to find out, for bad heavy catalytic raw material, the method reducing coke yield by improving fcc raw material is by fcc raw material hydrotreatment upgrading.But be directly that hydrogen consumption is too high by the shortcoming of whole fcc raw material hydrotreatment, in addition simultaneously due to general all at least containing paraffinic hydrocarbons in fcc raw material, and paraffinic hydrocarbons can inevitably lose owing to there is acid cracking reaction in hydrogenation process at least partly.
In addition, be the problem not solving raw material stage treatment well by the another one shortcoming of first for the raw material hydrotreatment this combination process of catalytic cracking again.Containing a large amount of hydrogenation of aromatics (or claiming cycloalkanes-aromatic hydrocarbons) in fcc raw material after hydrogenation, and the cracking performance of other paraffinic hydrocarbons contained, naphthenic hydrocarbon is different in this hydrogenation of aromatics and raw material, it very easily transforms, if itself and paraffinic hydrocarbons, naphthenic hydrocarbon carry out catalytic cracking under identical severe operating conditions simultaneously, can cause due to overcracking coke and dry gas yied too high.
Summary of the invention
The object of this invention is to provide a kind of catalysis conversion method reducing coke and dry gas yied, by integrated to solvent extraction, selective hydrogenation process and catalytic cracking process, be mainly used in the catalytic cracking process for bad heavy feed stock, to improve product slates, to reduce coke yield.
The catalysis conversion method of reduction coke provided by the invention and dry gas yied comprises the following steps:
(1) bad heavy feed stock is raffinated oil through solvent extraction and is extracted out oil;
(2) bottom of catalyst cracker is entered from raffinating oil of step (1), as one of the stock oil of catalytic cracking;
(3) enter hydrotreating unit from the extraction oil of step (1) and carry out polycyclic aromatic hydrocarbons selective hydrogenation;
(4) from the oil of the extraction after hydrogenation of step (3), the middle and lower part of step (2) described catalyst cracker is entered, as the stock oil two of catalytic cracking;
(5) catalytic cracking production that catalytic cracking unit obtains is separated into various product, and catalytic cracking catalyst cyclic regeneration uses.
Catalysis conversion method provided by the invention is so concrete enforcement:
1, solvent extraction unit
Bad heavy feed stock and solvent enter extraction tower, and extraction obtains all solvent-laden raffinate and Extract, and raffinate and Extract are raffinated oil respectively through recycling design and extracted oil out, reclaim the solvent cycle obtained and use.Described solvent is selected from furfural, lightweight oil, methyl-sulphoxide, tetramethylene sulfone, N-Methyl pyrrolidone, dimethyl formamide, monoethanolamine, ethylene glycol, 1, one or more in 2-propylene glycol, the mixture of preferred furfural or furfural and lightweight oil, furfural accounts for the 5-80 % by weight of described mixture, water-content wherein in furfural is 0-10 % by weight, be dry furfural when water-content is 0, as water-content > 0 and be wet furfural when being less than 10 % by weight; Lightweight oil is selected from one or more in virgin naphtha, hydrotreated naphtha, catalytic gasoline, coker gasoline, pressure gasoline, and its boiling spread (boiling range) is 70-210 DEG C of preferred 90-130 DEG C, aromaticity content≤5 % by weight.Extraction temperature is 20-120 DEG C, and the weight ratio of solvent and bad heavy feed stock is 0.2-5.
The bad heavy feed stock that the inventive method is suitable for can be petroleum fractions of different boiling ranges and composition thereof.Specifically, be selected from one or more in decompressed wax oil, normal pressure wax oil, long residuum, vacuum residuum, wax tailings, deasphalted oil, its density (20 DEG C) is greater than 910 kgs/m
3, unsaturation hydrocarbon content is greater than 30 heavy %.
Preferred solvent extraction flow process is as follows:
Bad heavy feed stock enters solvent pairs extraction tower, and furfural enters solvent pairs tower top as the first solvent, and lightweight oil enters extraction tower bottom as the second solvent, and solvent-laden water enters dehydration tower recycling design, and solvent cycle uses.The raffinate that solvent pairs extraction tower tower top distillates enters raffinate stripping tower, and recovered solvent enters solvent tank, comprises the first solvent, water and the second solvent that are divided into three layers in solvent tank.Raffinating oil of gained at the bottom of raffinate stripping tower tower enters catalytic cracking unit by feed nozzle of raffinating oil.The Extract distillated at the bottom of solvent pairs extraction tower tower enters flashing tower, flashing tower tower top distillates solvent and enters solvent tank, the Extract distillated at the bottom of flashing tower tower enters extract stripper, stripper overhead distillates solvent and enters solvent tank, and the extraction oil (heavy crude aromatic hydrocarbons) obtained bottom stripping tower enters hydrotreating unit, and to carry out polycyclic aromatic hydrocarbons selective hydrogenation saturated.Wherein extract the main petroleum aromatics being greater than 90% containing purity in oil out.
The operational condition of solvent pairs extraction tower is: tower top temperature 60-100 DEG C, and tower middle portion temperature is 50-75 DEG C, column bottom temperature 20-70 DEG C.The weight ratio of furfural, lightweight oil and bad heavy feed stock is 0.5-2.5: 0.2-1.0: 1 preferred 0.5-1.0: 0.3-0.6: 1.
2, hydrotreating unit
From extraction oil and other optional secondary processing wax oils mixing of solvent extraction unit, then heat and mix with hydrogen, enter the hydrotreatment reaction zone of filling hydrogenation catalyst, carry out polycyclic aromatic hydrocarbons selective hydrogenation saturated, reaction generates oil and enters hot high partial pressures separator, the gaseous stream that high pressure hot separator top reserves is the lighter hydrocarbons that hydrogen-rich gas and hydrotreatment reaction generate, and the logistics of high pressure hot separator bottom liquid phases isolates through thermal low-pressure separators the hydrogenation extraction oil obtained after dissolved gases further, directly extract oil burner nozzle out by hydrogenation without fractionation and enter catalytic cracking unit.
Other secondary processing wax oils described are selected from wax tailings or/and deasphalted oil." other optional secondary processing wax oils " represent that other secondary processing wax oils described are selection components of hydrotreated feed, and the extraction oil from solvent extraction unit is then the necessary component of hydrotreated feed.In other words, the raw material of hydrotreatment can be independent extraction oil, also can be the mixture of the wax oil extracting oil and other secondary processing described out.
The reactive system of described hydrotreater is generally fixed-bed reactor, and hydrotreatment reaction conditions is: reaction pressure 8.0-16.0MPa, preferred 11.0MPa-15.0MPa; Temperature of reaction 300-430 DEG C, preferred 310-380 DEG C; Volume space velocity 0.2-5.0h
-1, preferred 0.4-3.0h
-1; Hydrogen to oil volume ratio 300-1000Nm
3/ m
3.
Catalyst loading pattern in described hydrotreatment fixed-bed reactor loads hydrogenation protecting agent, hydrodemetallation (HDM) sweetening agent and hydrotreating catalyst successively.With integer catalyzer volume for benchmark, the admission space percentage ratio of hydrogenation protecting agent, optional hydrodemetallation (HDM) sweetening agent, hydrotreating catalyst is respectively 2-20 volume %, 0-20 volume %, 60-98 volume %.
Described hydrogenation protecting agent comprises the alumina supporter of the heavy % nickel oxide of 0.5-5.0, the heavy % molybdenum oxide of 2.0-10.0 and surplus.
Described hydrodemetallation (HDM) sweetening agent comprises the alumina supporter of the heavy % cobalt oxide of 2.0-7.0, the heavy % molybdenum oxide of 10.0-30.0 and surplus.
Described hydrotreating catalyst be load at unformed aluminum oxide or/and the group vib in silica-alumina supports is or/and VIII non-precious metal catalyst, wherein said group vib base metal be molybdenum or/and tungsten, VIII base metal is one or more in nickel, cobalt, iron.
3, catalytic cracking unit
Catalytic cracking unit reactor used can be the reducing riser reactor of the double-reaction area including the first and second reaction zones, and the detailed description of this reducing riser reactor is shown in ZL99105903.4; Also can be the compound reactor be made up of riser tube and fluidized-bed, the compound reactor be made up of riser tube and downstriker transfer limes, the compound reactor be made up of two or more riser tube, the compound reactor be made up of two or more fluidized-bed, the compound reactor that is made up of two or more moving-bed.First reactor of compound reactor is called the first reaction zone in the methods of the invention, and the second reactor is called second reaction zone.The preferred reactor of the inventive method is reducing riser reactor.
No matter be reducing riser reactor or compound reactor, feed nozzle of raffinating oil is set in the first reaction zone, raffinate oil from this nozzle and enter the first reaction zone reaction; Arrange hydrogenation in second reaction zone and extract oily feed nozzle out, hydrogenation is extracted oil out and is entered second reaction zone reaction from this nozzle.
When adopting compound reactor to be reactor, in compound reactor, the first reaction zone processing condition are: temperature of reaction is 450-650 DEG C of preferred 470-530 DEG C, pressure (absolute pressure) 0.15-0.4MPa, preferred 0.2-3 second residence time 0.2-6 second, catalytic cracking catalyst and the weight ratio (agent-oil ratio) of raffinating oil are 5-30, water vapor and the weight ratio (water-oil ratio) of raffinating oil are 0.05-0.6.In compound reactor, the processing condition of second reaction zone are: temperature of reaction 10-100 DEG C, preferred 15-80 DEG C lower than the first reaction zone temperature; In pressure (absolute pressure) 0.15-0.4MPa, weight hourly space velocity 0.5-60h-1, this reaction zone, catalytic cracking catalyst and hydrogenation extract the weight ratio (agent-oil ratio) of oil out is 5-50, and the weight ratio (water-oil ratio) that water vapor and hydrogenation extract oil out is 0.05-0.6.
When adopting the reducing riser reactor containing the first and second reaction zones to be reactor, the processing condition of reducing riser reactor are: pressure (absolute pressure) 0.15-0.4MPa of reactor.In first reaction zone: temperature of reaction is 450-650 DEG C of preferred 470-530 DEG C, preferred 0.2-3 second residence time 0.2-6 second, catalytic cracking catalyst and the weight ratio of the weight ratio (agent-oil ratio) of raffinating oil are 5-30, water vapor and the weight ratio (water-oil ratio) of raffinating oil is 0.05-0.6.In second reaction zone: temperature of reaction 10-100 DEG C, preferred 15-80 DEG C lower than the first reaction zone temperature; Weight hourly space velocity 0.5-60h-1, in this reaction zone, catalytic cracking catalyst and hydrogenation extract the weight ratio (agent-oil ratio) of oil out is 5-50, and the weight ratio (water-oil ratio) that water vapor and hydrogenation extract oil out is 0.05-0.6.
No matter adopt compound reactor or reducing riser reactor, second reaction zone temperature will lower than the first reaction zone temperature.Need further injected media at the combining site of second reaction zone and the first reaction zone, medium is the reclaimable catalyst of low temperature or regenerated catalyst mainly, the regenerated catalyst of preferred low temperature.
Catalytic cracking unit catalytic cracking catalyst used comprises zeolite, inorganic oxide and optional clay, and the content of each component is respectively: the heavy % of zeolite 10-50 heavy %, inorganic oxide 5-90 heavy %, clay 0-70.Zeolite, as active ingredient, is selected from large pore zeolite and/or mesopore zeolite, one or more in wherein large pore zeolite is selected from Rare Earth Y (REY), rare earth hydrogen Y (REY), different methods obtain super steady Y, high silicon Y; Mesopore zeolite is selected from ZSM series zeolite and/or ZRP zeolite, also can carry out modification to transition metals such as the non-metallic elements such as above-mentioned mesopore zeolite phosphorus and/or iron, cobalt, nickel.About the more detailed description of ZRP zeolite is see US5232675; ZSM series zeolite is selected from one or more the mixture among the zeolite of ZSM-5, ZSM-11, ZSM-12, ZSM-23, ZSM-35, ZSM-38, ZSM-48 and other similar structures, about the more detailed description of ZSM-5 is see US3702886.Inorganic oxide, as caking agent, is selected from silicon-dioxide (SiO
2) and/or alchlor (Al
2o
3).Clay, as matrix (carrier), is selected from kaolin and/or halloysite.
The invention has the advantages that:
1, improve different oil Refining Technologies utilization benefit, strengthening oil Refining Technologies is more reasonably integrated, cleans provide a new approach for realizing reducing the oil refining production process of carbon emission.
2, improve the hydrogen utilization ratio in raw material, improve again the utilization ratio of the hydrogen of hydrotreatment simultaneously, thus can petroleum resources be saved.
3, the hydrocarbon for different bad heavy catalytic raw materials forms, the real processing route realizing " cutting the garment according to the figure " formula, thus the processing benefit of hydrocarbon resource is maximized.
Accompanying drawing explanation
Accompanying drawing is the catalysis conversion method schematic flow sheet of reduction coke provided by the invention and dry gas yied.In accompanying drawing, each numbering is described as follows:
1,3,6,7,9,10,12,13,14,15,17,19,20,21,22,26,30,31,33,34,35,36,38,39,42,44 all pipeline is represented; 2 is solvent pairs extraction tower; 5 is raffinate stripping tower; 8 is flashing tower; 11 is extract stripper; 16 is fixed bed hydrogenation device; 18 is separation system; 23 extract oily feed nozzle out for hydrogenation; 24 is feed nozzle of raffinating oil; 25 is variable diameters riser reactor; 27 is settling vessel; 28 is cyclonic separator; 29 is stripping stage; 32 is revivifier; 37 is solvent tank; 40 is the first reaction zone of variable diameters riser reactor 25; 41 is the second reaction zone of variable diameters riser reactor 25; 43 is catalyst cooler.
Embodiment
Below in conjunction with accompanying drawing, preferred forms provided by the present invention is further described.
Fig. 1 is solvent extraction, hydrotreatment and catalytic cracking integrated process flow schematic diagram, and shape, the size of equipment and pipeline not by the restriction of accompanying drawing, but are determined as the case may be.
Solvent extraction unit: bad heavy feed stock enters solvent pairs extraction tower 2 through pipeline 1, enter the top of solvent pairs extraction tower 2 through pipeline 39 from the moisture furfural of solvent tank 37, enter the bottom of solvent pairs extraction tower 2 through pipeline 38 from the lightweight oil of solvent tank 37, bad heavy feed stock carries out solvent pairs extracting in tower.The raffinate distillated from solvent pairs extraction tower 2 top enters raffinate stripping tower 5 through pipeline 3, and the solvent distillated from raffinate stripping tower 5 top enters solvent tank 37 through pipeline 6, and bottom raffinate stripping tower 5, gained is raffinated oil and entered catalytic cracking unit through pipeline 7.The Extract distillated bottom solvent pairs extraction tower 2 enters flashing tower 8 through pipeline 4, the solvent distillated from flashing tower 8 top enters solvent tank 37 through pipeline 9, Extract bottom flashing tower 8 enters extract stripper 11 through pipeline 10, the solvent distillated from extract stripper 11 top enters solvent tank 37 through pipeline 12, and the Extract distillated bottom extract stripper 11 enters hydrotreating unit through pipeline 13.
Hydrotreating unit: from extraction oil and the recycle hydrogen from pipeline 15 of pipeline 13 solvent extraction unit, optionally from the new hydrogen of pipeline 44, optionally from after other secondary processing wax oils (as wax tailings or/and deasphalted oil) mixing of pipe 14, enter fixed bed hydrogenation device 16 to contact with hydrogenation catalyst and carry out polycyclic aromatic hydrocarbons saturated reaction, the reaction generation oil obtained enters separation system 18 through pipeline 17 and is separated, the gaseous stream at separation system 18 top is extracted out through pipeline 19, and bottom liquid phases logistics and hydrogenation extraction oil deliver to catalytic cracking unit through pipeline 20 extraction.
Catalytic cracking unit: pre-lift steam enters from the pre lift zone bottom variable diameters riser reactor 25 through pipeline 26, the regenerated catalyst of heat enters riser tube pre lift zone through regenerator sloped tube 36 and is promoted by pre-lift steam.After pipeline 7 mixes by a certain percentage with the atomizing steam from pipeline 22, enter the first reaction zone 40 of variable diameters riser reactor 25 from feed nozzle 24 of raffinating oil from raffinating oil of solvent extraction unit, mix with thermocatalyst after react, up.Hydrogenation from hydrotreating unit is extracted oil out and extract from hydrogenation the second reaction zone 41 that oily feed nozzle 23 enters variable diameters riser reactor 25 out after pipeline 20 is mixed by a certain percentage with the atomizing steam from pipeline 21, the regenerated catalyst of heat also enters second reaction zone 41 through inclined tube 42 after catalyst cooler 43 cools, and contacts further, reacts, up with catalyzer.Reacted oil agent mixture enters settling vessel 27, cyclonic separator 28 in gas solid separation system fast, and reaction product is gone separation system to be separated through pipeline 31 and obtained various catalyst article.After reaction, the reclaimable catalyst of band charcoal enters stripper 29, through entering revivifier 32 from after the water vapor stripping of pipeline 30 by inclined tube 33 to be generated, reclaimable catalyst is coke burning regeneration in the air from pipeline 35, flue gas goes out revivifier through pipeline 34, and the regenerated catalyst of heat returns riser tube bottom cycle through regenerator sloped tube 36,42 and uses.
The following examples will be further described the present invention, but not thereby limiting the invention.The raw material used in embodiment, comparative example is the decompressed wax oil mixing refining vacuum residuum; its character lists in table 1; in the fixed-bed reactor of hydrotreating unit, the hydrogenation catalyst commercial grades of filling is respectively RG-10A/RG-10B/RMS-1/RN-32V (hydrogenation protecting agent A/ hydrogenation protecting agent B/ hydrodemetallation (HDM) sweetening agent/hydrotreating catalyst); admission space ratio is 4: 4: 15: 77, is produced by Sinopec catalyzer branch office.The catalyzer commercial grades of catalytic unit is MLC-500, is produced by Sinopec catalyzer branch office.
Embodiment
The present embodiment illustrates and adopts method provided by the invention, the products distribution of raw material after medium-sized solvent extraction, hydrotreatment and catalytic cracking unit process and the situation of product property.
First enter the solvent pairs extraction tower of solvent extraction unit from middle part after bad heavy feed stock preheating, the first solvent furfural (containing 6 % by weight moisture) that wets enters from tower top, second solvent virgin naphtha (boiling range 90-120 DEG C) enters at the bottom of tower, the ratio of the weight of wet furfural, virgin naphtha, bad heavy feed stock is 2: 0.8: 1, extracting tower top temperature is 90 DEG C, tower middle portion temperature 65 DEG C, column bottom temperature 42 DEG C.Raffinate is substantially identical with the operational condition of the stripping tower of Extract, enters tower temperature 215 DEG C, and tower top temperature is 120 DEG C, column bottom temperature 220 DEG C, and vapor flow of stripper is into tower amount 5 % by weight.The operational condition of Extract flashing tower is: enter tower temperature 185 DEG C, and tower top temperature is 140 DEG C, column bottom temperature 200 DEG C.Solvent tank service temperature is 35 DEG C.
The reducing riser reactor of catalytic unit, raffinates oil into the first reaction zone of riser reactor; Hydrogenation extracts the second reaction zone that oil enters riser reactor out, and the temperature through cooled regenerated catalyst entering second reaction zone controls at 655 DEG C.The prevailing operating conditions of catalytic unit lists in table 2.
The operational condition of hydrotreating unit also lists in table 2.
The product slates of embodiment lists in table 3.
Comparative example 1
Medium-sized tester is identical with embodiment with catalyzer.Just bad heavy catalytic raw material is without Aromatics Extractive Project unit, but all directly on medium-sized hydrotreater, carry out hydrotreatment, the first reaction zone that the hydrotreatment oil obtained after hydrotreatment enters medium-sized catalytic cracking reducing riser reactor from the feed nozzle of raffinating oil embodiment is subsequently reacted, and the hydrogenation of reducing riser reactor second reaction zone extracts oily feed nozzle stopping charging out in this comparative example, do not introduce cooled regenerated catalyst in second reaction zone simultaneously yet.Operational condition in this comparative example and products distribution list in table 2 and table 3 respectively, and gasoline composition lists in table 3.
Comparative example 2
Medium-sized tester is identical with embodiment with catalyzer.Bad heavy catalytic raw material is first through Aromatics Extractive Project unit, and the same embodiment of extraction procedure condition, extraction oil also enters on medium-sized hydrotreater and carries out hydrotreatment.But with embodiment difference be, hydrogenation that hydrogenation obtains is extracted out oil and is not the first and second reaction zones simultaneously being entered reducing riser reactor by the feed nozzle separated separately respectively from raffinating oil of aromatic hydrocarbons processing unit, but enters the first reaction zone reaction, up from the feed nozzle of raffinating oil of reducing riser reactor first reaction zone together after mixing.In this comparative example, the hydrogenation of reducing riser reactor second reaction zone extracts oily feed nozzle stopping charging out, does not also introduce cooled regenerated catalyst in second reaction zone simultaneously.Operational condition in this comparative example and products distribution list in table 2 and table 3 respectively, and gasoline composition lists in table 3.
As can be seen from Table 3, relative to comparative example 1, the hydrogen consumption of the present invention's processing is 0.34 heavy %, reduce 69.09 heavy %, and the products distribution of catalytic cracking be improved significantly, as dry gas and coke yield obviously reduce, wherein coke yield reduces 1.1 units, and fall is 11.58%; Dry gas yied reduces 0.58 unit, and fall is 19.33%, and total catalytic unit liquid product yield (being called for short total liquid yield, is liquefied gas, catalytic gasoline and solar oil three yield sum) adds 1.33 units.
As can be seen from Table 3, compare with comparative example 2, charging is separated for different hydrocarbon constitutive materials owing to have employed, optimize respective cracking behavior, so the products distribution of catalytic cracking of the present invention is improved significantly, wherein coke yield reduces 1.26 units than comparative example 2, and fall is 13.04%; Dry gas yied reduces 0.73 unit, and fall is 23.17%, and total liquid yield adds 1.79 units.
Table 1
| Material name | Bad mink cell focus |
| Density (20 DEG C), kg/m 3 | 932.7 |
| Carbon residue, heavy % | 5.6 |
| Carbon, heavy % | 86.69 |
| Hydrogen, heavy % | 12.11 |
| Boiling range, DEG C | |
| Initial boiling point | 252 |
| 10％ | 433 |
| 50％ | 552 |
| Hydrocarbon system forms, heavy % | |
| Stable hydrocarbon | 46 |
| Aromatic hydrocarbons | 44.6 |
| Colloid+bituminous matter | 9.4 |
Table 2
| Embodiment | Comparative example 1 | Comparative example 2 | |
| Catalytic unit | |||
| Temperature of reaction, DEG C | |||
| First reaction zone | 515 | 515 | 515 |
| Second reaction zone | 490 | 505 | 505 |
| The residence time, second | 5.4 | ||
| Raffinate oil | 5.4 | 5.4 | |
| Hydrogenation extracts oil out | 2.2 | 5.4 | |
| Agent-oil ratio | 6.0 | 6.0 | |
| Catalyzer/raffinate oil | 11.0 | ||
| Catalyzer/hydrogenation extracts oil out | 15.0 | ||
| Water-oil ratio | 0.08 | 0.08 | |
| Water vapor/raffinate oil | 0.08 | ||
| Water vapor/hydrogenation extracts oil out | 0.08 | ||
| Hydrogenation unit | |||
| Hydrogen dividing potential drop, MPa | 12.0 | 8.0 | 12.0 |
| Temperature of reaction, DEG C | 360 | 370 | 360 |
| Cumulative volume air speed, h -1 | 1.0 | 1.5 | 1.0 |
| Hydrogen to oil volume ratio, Nm 3/m 3 | 650 | 500 | 650 |
Table 3
| Embodiment | Comparative example 1 | Comparative example 2 | |
| Product slates, heavy % | |||
| Hydrogen sulfide | 1.27 | 1.60 | 1.27 |
| Ammonia | 0.06 | 0.12 | 0.06 |
| Dry gas | 2.42 | 3.00 | 3.15 |
| Liquefied gas | 15.45 | 16.7 | 16.2 |
| Gasoline | 43.4 | 41.48 | 41.3 |
| Wherein petroleum naphtha | 0.45 | 0.77 | 0.45 |
| Catalytic gasoline | 42.95 | 40.71 | 40.85 |
| Solar oil | 25.24 | 24.9 | 24.8 |
| Heavy oil | 4.10 | 3.80 | 3.90 |
| Coke | 8.40 | 9.50 | 9.66 |
| Add up to | 100.34 | 101.1 | 100.34 |
| Chemistry consumption hydrogen, heavy % | 0.34 | 1.10 | 0.34 |
| Catalysis total liquid yield, heavy % | 83.64 | 82.31 | 81.85 |
Claims (19)
1. reduce a catalysis conversion method for coke and dry gas yied, it is characterized in that the method comprises the following steps:
(1) bad heavy feed stock is raffinated oil through solvent extraction and is extracted out oil, and described bad heavy feed stock is selected from one or more in decompressed wax oil, normal pressure wax oil, long residuum, vacuum residuum, wax tailings, deasphalted oil, and its density is greater than 910 kgs/m
3, unsaturation hydrocarbon content is greater than 30 heavy %;
(2) bottom of catalyst cracker is entered from raffinating oil of step (1), as one of the stock oil of catalytic cracking;
(3) enter hydrotreating unit from the extraction oil of step (1) and carry out polycyclic aromatic hydrocarbons selective hydrogenation, catalyst loading pattern in hydrotreatment fixed-bed reactor loads hydrogenation protecting agent, optional hydrodemetallation (HDM) sweetening agent and hydrotreating catalyst successively, with integer catalyzer volume for benchmark, the admission space percentage ratio of hydrogenation protecting agent, optional hydrodemetallation (HDM) sweetening agent, hydrotreating catalyst is respectively 2-20 volume %, 0-20 volume %, 60-98 volume %;
(4) from the oil of the extraction after hydrogenation of step (3), the middle and lower part of step (2) described catalyst cracker is entered, as the stock oil two of catalytic cracking;
(5) catalytic cracking production that catalytic cracking unit obtains is separated into various product, and catalytic cracking catalyst cyclic regeneration uses.
2. method according to claim 1, is characterized in that one or more that described solvent is selected from furfural, lightweight oil, methyl-sulphoxide, tetramethylene sulfone, N-Methyl pyrrolidone, dimethyl formamide, monoethanolamine, ethylene glycol, 1,2-PD.
3. method according to claim 1, is characterized in that described solvent is furfural.
4. method according to claim 1, it is characterized in that described solvent is the mixture of furfural and lightweight oil, furfural accounts for the 5-80 % by weight of described mixture.
5., according to method described one of in claim 2,3 or 4, it is characterized in that the water-content in described furfural is 0-10 % by weight.
6. the method according to claim 2 or 4, it is characterized in that one or more that described lightweight oil is selected from virgin naphtha, hydrotreated naphtha, catalytic gasoline, coker gasoline, pressure gasoline, its boiling spread is 70-210 DEG C, aromaticity content≤5 % by weight.
7. method according to claim 2, is characterized in that described extraction temperature is 20-120 DEG C, and the weight ratio of solvent and bad heavy feed stock is 0.2-5.
8. method according to claim 1, it is characterized in that the extraction oil from solvent extraction unit and other optional secondary processing wax oils mixing, then heat and mix with hydrogen, enter the hydrotreatment reaction zone of filling hydrogenation catalyst, carry out polycyclic aromatic hydrocarbons selective hydrogenation saturated, reaction generates oil and enters hot high partial pressures separator, the gaseous stream that high pressure hot separator top reserves is the lighter hydrocarbons that hydrogen-rich gas and hydrotreatment reaction generate, and the logistics of high pressure hot separator bottom liquid phases isolates through thermal low-pressure separators the hydrogenation extraction oil obtained after dissolved gases further, directly extract oil burner nozzle out by hydrogenation without fractionation and enter catalytic cracking unit.
9. method according to claim 8, is characterized in that other secondary processing wax oils described are selected from wax tailings or/and deasphalted oil.
10. method according to claim 8, it is characterized in that hydrotreating reactor is fixed bed, hydrotreatment reaction conditions is: reaction pressure 8.0-16.0MPa, temperature of reaction 300-430 DEG C, volume space velocity 0.2-5.0h
-1, hydrogen to oil volume ratio 300-1000Nm
3/ m
3.
11. methods according to claim 10, it is characterized in that hydrotreatment reaction pressure is 11.0MPa-15.0MPa, temperature of reaction is 310-380 DEG C, and volume space velocity is 0.4-3.0h
-1.
12. methods according to claim 1, is characterized in that described hydrogenation protecting agent comprises the alumina supporter of the heavy % nickel oxide of 0.5-5.0, the heavy % molybdenum oxide of 2.0-10.0 and surplus; Described hydrodemetallation (HDM) sweetening agent comprises the alumina supporter of the heavy % cobalt oxide of 2.0-7.0, the heavy % molybdenum oxide of 10.0-30.0 and surplus; Described hydrotreating catalyst be load at unformed aluminum oxide or/and the group vib in silica-alumina supports is or/and VIII non-precious metal catalyst, wherein said group vib base metal be molybdenum or/and tungsten, VIII base metal is one or more in nickel, cobalt, iron.
13. methods according to claim 1, it is characterized in that described catalyst cracker is selected from the reducing riser reactor comprising two reaction zones, the compound reactor be made up of riser tube and fluidized-bed, the compound reactor be made up of riser tube and downstriker transfer limes, the compound reactor be made up of two or more riser tube, the compound reactor be made up of plural fluidized-bed, or the compound reactor to be made up of plural moving-bed, wherein the first reactor of compound reactor is called the first reaction zone, second reactor is called second reaction zone.
14. methods according to claim 13, is characterized in that described catalyst cracker is the reducing riser reactor comprising two reaction zones.
15. methods according to claim 13 or 14, is characterized in that described catalyst cracker first reaction zone arranges feed nozzle of raffinating oil, and raffinate oil from this nozzle and enter the first reaction zone reaction; Arrange hydrogenation in second reaction zone and extract oily feed nozzle out, hydrogenation is extracted oil out and is entered second reaction zone reaction from this nozzle.
16. methods according to claim 13, it is characterized in that the first reaction zone processing condition are: temperature of reaction is 450-650 DEG C, pressure 0.15-0.4MPa, residence time 0.2-6 second, catalytic cracking catalyst and the weight ratio of raffinating oil are 5-30, and water vapor and the weight ratio of raffinating oil are 0.05-0.6; The processing condition of second reaction zone are: temperature of reaction than the low 10-100 DEG C of the first reaction zone temperature, pressure 0.15-0.4MPa, weight hourly space velocity 0.5-60h
-1, the weight ratio that catalytic cracking catalyst and hydrogenation extract oil out is 5-50, and the weight ratio that water vapor and hydrogenation extract oil out is 0.05-0.6.
17. methods according to claim 16, is characterized in that the first reaction zone processing condition are: temperature of reaction is 470-530 DEG C, residence time 0.2-3 second; The processing condition of second reaction zone are: temperature of reaction is than the low 15-80 DEG C of the first reaction zone temperature.
18. methods according to claim 16 or 17, it is characterized in that described catalytic cracking catalyst comprises zeolite, inorganic oxide and optional clay, the content of each component is respectively: the heavy % of zeolite 10-50 heavy %, inorganic oxide 5-90 heavy %, clay 0-70.
19. methods according to claim 18, is characterized in that described zeolite is selected from large pore zeolite and/or mesopore zeolite.
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| CN106467759B (en) * | 2015-08-21 | 2018-05-25 | 中国石油化工股份有限公司 | A kind of heavy oil pretreatment and the combined method of catalytic cracking |
| CN106590740B (en) * | 2015-10-15 | 2018-11-02 | 中国石油化工股份有限公司 | A kind of inferior raw material oil treatment process |
| CN114106869A (en) * | 2020-09-01 | 2022-03-01 | 中国石油化工股份有限公司 | Method for separating aromatic hydrocarbon and alkane in diesel oil fraction and method for processing high aromatic hydrocarbon diesel oil fraction |
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| CN1064390C (en) * | 1996-09-06 | 2001-04-11 | 中国石油化工总公司 | Double-solvant extraction for inferior paraffin base oil |
| CN102021030A (en) * | 2009-09-17 | 2011-04-20 | 中国石油化工股份有限公司 | Catalytic conversion method |
| CN102373084A (en) * | 2010-08-19 | 2012-03-14 | 中国石油化工股份有限公司 | Method producing light fuel oil and propylene from poor residual oil |
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| CN1064390C (en) * | 1996-09-06 | 2001-04-11 | 中国石油化工总公司 | Double-solvant extraction for inferior paraffin base oil |
| CN102021030A (en) * | 2009-09-17 | 2011-04-20 | 中国石油化工股份有限公司 | Catalytic conversion method |
| CN102373084A (en) * | 2010-08-19 | 2012-03-14 | 中国石油化工股份有限公司 | Method producing light fuel oil and propylene from poor residual oil |
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