CN104650972B - Reduce the method for hydrogen cracking of light fraction product sulfur content - Google Patents
Reduce the method for hydrogen cracking of light fraction product sulfur content Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 84
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 64
- 239000001257 hydrogen Substances 0.000 title claims abstract description 64
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 64
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims abstract description 21
- 229910052717 sulfur Inorganic materials 0.000 title claims abstract description 20
- 239000011593 sulfur Substances 0.000 title claims abstract description 20
- 238000005336 cracking Methods 0.000 title claims abstract description 14
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 88
- 238000006243 chemical reaction Methods 0.000 claims abstract description 73
- 150000001336 alkenes Chemical class 0.000 claims abstract description 20
- 238000004517 catalytic hydrocracking Methods 0.000 claims description 91
- 239000003054 catalyst Substances 0.000 claims description 84
- 239000007789 gas Substances 0.000 claims description 66
- 239000012071 phase Substances 0.000 claims description 56
- 238000007670 refining Methods 0.000 claims description 30
- 239000007788 liquid Substances 0.000 claims description 21
- 239000000047 product Substances 0.000 claims description 21
- 239000007791 liquid phase Substances 0.000 claims description 20
- 239000000463 material Substances 0.000 claims description 16
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- 229920006395 saturated elastomer Polymers 0.000 claims description 13
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 claims description 12
- 239000002994 raw material Substances 0.000 claims description 11
- 238000000605 extraction Methods 0.000 claims description 8
- 238000011049 filling Methods 0.000 claims description 8
- 239000007795 chemical reaction product Substances 0.000 claims description 6
- 239000002283 diesel fuel Substances 0.000 claims description 6
- 238000000746 purification Methods 0.000 claims description 6
- 239000003245 coal Substances 0.000 claims description 5
- 238000002309 gasification Methods 0.000 claims description 5
- 239000011229 interlayer Substances 0.000 claims description 5
- 238000000926 separation method Methods 0.000 claims description 5
- 125000003118 aryl group Chemical group 0.000 claims description 4
- 239000007792 gaseous phase Substances 0.000 claims description 3
- 238000005192 partition Methods 0.000 claims description 3
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- 230000003197 catalytic effect Effects 0.000 claims description 2
- 239000011280 coal tar Substances 0.000 claims description 2
- 239000003921 oil Substances 0.000 description 45
- 238000005516 engineering process Methods 0.000 description 15
- 239000002808 molecular sieve Substances 0.000 description 9
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 9
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 8
- 238000012805 post-processing Methods 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 4
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 4
- 229910052759 nickel Inorganic materials 0.000 description 4
- 238000011160 research Methods 0.000 description 4
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- 238000001816 cooling Methods 0.000 description 3
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- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229910052721 tungsten Inorganic materials 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
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- 238000005191 phase separation Methods 0.000 description 2
- 240000005702 Galium aparine Species 0.000 description 1
- 235000014820 Galium aparine Nutrition 0.000 description 1
- 241000612118 Samolus valerandi Species 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 241000219793 Trifolium Species 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000011959 amorphous silica alumina Substances 0.000 description 1
- 229910021417 amorphous silicon Inorganic materials 0.000 description 1
- -1 arene compound Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 235000005770 birds nest Nutrition 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 238000001833 catalytic reforming Methods 0.000 description 1
- 230000001413 cellular effect Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000004508 fractional distillation Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- ZZUFCTLCJUWOSV-UHFFFAOYSA-N furosemide Chemical compound C1=C(Cl)C(S(=O)(=O)N)=CC(C(O)=O)=C1NCC1=CC=CO1 ZZUFCTLCJUWOSV-UHFFFAOYSA-N 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 239000012263 liquid product Substances 0.000 description 1
- 230000002101 lytic effect Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G67/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/04—Diesel oil
Landscapes
- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The present invention relates to a kind of method for hydrogen cracking reducing light fraction product sulfur content.Be mainly characterized by back end hydrogenation refine carry out under conditions of temperature relative reduction and hydrogen to oil volume ratio are less olefins hydrogenation reaction and hydro-sweetening reaction.Compared with prior art, the inventive method can effectively reduce the sulfur content in light fraction product.
Description
Technical field
The processing method that the invention belongs to oil Refining Technologies, particularly relates to method for hydrogen cracking, reduces the method being hydrocracked light ends oil mercaptans content.
Background technology
Environmental regulation increasingly stringent in global range, it is desirable to each refiner produces the light clean fuel of clean environment firendly.In oil Refining Technologies, hydrogen addition technology is one of most effective means producing cleaning products from inferior raw material, and therefore hydrogenation plant has become as the standard configuration of oil plant, and the hydrogenation plant in oil refining enterprise is on the increase, and the proportion accounting for crude runs is gradually increased.
Hydrocracking technology is the one in hydrogen addition technology, is the most important means that heavy inferior distillate is converted into cleaning products.Hydrocracking technology is typically with the close distillate of vacuum distillate or other boiling range as raw material, being reacted by hydrodesulfurization, hydrodenitrogeneration, hydrogenation deoxidation, olefins hydrogenation, aromatic hydrogenation is saturated, be hydrocracked etc. and produce high-quality naphtha, boat coal and diesel oil, hydrocracking tail oil is also steam cracking ethylene raw and the isomerization dewaxing Lube basic oil material feedstocks of high-quality simultaneously.Along with crude oil heaviness day by day and in poor quality, and requiring to generate high-quality light-end products, hydrocracking technology has obtained more being widely applied as far as possible.
Hydrocracking process technology can be generally divided into single-stage hydrocracking technique, single hop serial hydrocracking technique and two-stage reforming technique etc. by work flow, and these technologies all use the hydrocracking catalyst with lytic activity.Due in hydrocracking process, intermediate product alkene can be generated when macromolecular cleavage becomes little molecule, if these alkene can not obtain being hydrogenated with saturated in time, and have the existence of hydrogen sulfide will generate mercaptan in reaction or follow-up fractional distillation process, this main cause that namely sulfur content (predominantly mercaptan) of light ends is higher in isocrackate.In order to solve this problem, the method commonly used most is at the bottom of hydrocracking catalyst filling hydrogenation post-processing catalyst (catalyst for refining after also referred to as), hydrogenation post-processing catalyst can be same catalyst with pretreating catalyst by hydrocracking, it is also possible to develops special catalyst.For existing single hop serial hydrocracking technology, temperature is operated relatively low during the initial stage, generate alkene when by post-processing catalyst can the overwhelming majority or complete hydrogenation saturated, but when mid-term or latter stage, along with the raising of reaction temperature can be caused some olefin can not obtain being hydrogenated with saturated by thermodynamic (al) restriction；And for single-stage hydrocracking technique, owing to catalyst not containing molecular sieve (or containing a small amount of molecular sieve), hydrogenation cracking activity is relatively low, the operation temperature in initial stage and latter stage is the highest, also implying that being hydrocracked the alkene of generation can not be hydrogenated with saturated probability in time and be greatly increased, the light fraction product sulfur levels being i.e. hydrocracked is of a relatively high.
Single-section two-catalyst hydrocracking method disclosed in CN100526431C, one-stage serial hydrocracking method disclosed in CN101148614B, CN101460596, US20030085154, hydrocracking process disclosed in these mainly reduces light distillate sulfur content at the bottom of hydrocracking catalyst filling hydrogenation post-processing catalyst, their difference is whether hydrogenation post-processing catalyst is special-purpose catalyst, or is not related to whether load hydrogenation post-processing catalyst.Disclosed in CN101333459, a kind of hydrogenating conversion process is suitable for processing long distillate feedstock oil, can pass through lighter combined hydrogenation refining reaction district by being hydrocracked product stream, thus reduce light component sulfur content, but have bigger restriction to feedstock oil.CN1266256C is disclosed improves method for hydrogen cracking, use and load hydrotreating catalyst on the top of high pressure hot separator, utilize the steam stripped method of hot hydrogen by light ends oil by saturated a part of arene compound during beds, shortcoming is that only the light ends obtained in high pressure hot separator have been carried out hydrogenation saturated, and there is also the situation that hydrogen to oil volume ratio is excessive, it is unfavorable for being smoothed out of hydrogenation reaction.
It addition, the rate of gasification in hydrocracking reactor is higher, particularly in cracker lower catalyst bed layer, the light component of a lot of crackings can not derive reactor in time, carry out secondary or repeatedly cracking generate C1～C4Product, reduces and is hydrocracked liquid receipts.And increasing and the increase of repeatedly cracking reaction along with the light component of gas phase, in hydrocracking reactor, beds carbon deposit from top to bottom is also gradually increased.
Summary of the invention
For the deficiencies in the prior art, the present invention provides a kind of hydrocracking process reducing light fraction product sulfur content, can effectively reduce the content of mercaptan in light ends oil.
The present invention reduces the method for hydrogen cracking of light fraction product sulfur content and includes following content:
A the hydrogenation reactor of () hydrocracking process flow process loads the hydrocracking catalyst of routine, and optionally load protective agent, pretreating catalyst by hydrocracking；
B () arranges back end hydrogenation finishing reactor, load back end hydrogenation catalyst for refining；Will originally be seated in the back end hydrogenation catalyst for refining bottom hydrocracking reactor to change into being seated in back end hydrogenation finishing reactor；
C () first feedstock oil and hydrogen are mixed and heated after, carrying out hydrocracking reaction under hydrogenation process conditions, then hydrocracking reaction effluent enters high pressure hot separator isolated gas phase and liquid phase；
D the gas phase of () high pressure hot separator isolated enters cyclone separator after heat exchange is lowered the temperature, obtain gas phase and liquid phase after separation, and wherein the isolated gas phase of cyclone separator is at least partially into the recycling of cold anticyclone isolated hydrogen-rich gas；
E oil phase and the hydrogeneous material of high temperature that the liquid phase of () cyclone separator isolated, cold high pressure separator obtain are mixed in low pressure back end hydrogenation finishing reactor, and back end hydrogenation purification stream separates in low pressure and wherein obtains low-pressure gas and liquid；
F liquid that the liquid phase of () high pressure hot separator isolated and back end hydrogenation finishing reactor logistics entrance low pressure separator obtain obtains various light-end products and tail oil after being mixed and fed into fractionating system.
In the inventive method step (a); the protective effect before feedstock oil contacts is played in described GPF (General Protection False agent with hydrogenation major catalyst; retaining and accommodate mechanical admixture, by inorganic matter hydrogenation and removings such as metal such as Fe, Ca, Ni, by alkene etc., easily condensation component or easy polymeric component hydrogenation are saturated.Containing a small amount of active metal component in protective agent; it is shaped as the abnormal shapes such as porous ball, tooth ball, bird-nest type, Raschig ring, clover, bunge bedstraw herb, trilobed wheel, four impellers, butterfly-type and cellular pellet; particle diameter 2mm ~ 20mm; typically at least include two kinds; and granularity is gradually reduced from top to bottom, hydrogenation activity is gradually increased.Can prepare by the existing method in this area, it is possible to use commodity protective agent.Whether protective agent uses or consumption is according to the quality condition of raw material, determines by this area Conventional wisdom.As in raw material during content of impurities height, protective agent consumption is more.
In the inventive method step (a), described pretreating catalyst by hydrocracking, mainly by saturated to impurity removal, alkene and the aromatic hydrogenations such as the sulphur in feedstock oil, nitrogen, oxygen.The especially amount of nitrides in the material after weighted BMO spaces reaches the feed needs of hydrocracking catalyst.Hydrogenation active component is one or more in W, Mo, Ni and Co.Can prepare by the existing method in this area, it is possible to use commodity pretreating catalyst by hydrocracking.For single-stage hydrocracking technique, pretreating catalyst by hydrocracking can not be used, and directly use Catalyst For Single-stage Hydrocracking.When using protective agent and pretreating catalyst by hydrocracking, reaction mass presses flow direction by protective agent, pretreating catalyst by hydrocracking and hydrocracking catalyst.
In the inventive method step (a), described hydrocracking catalyst, this catalyst can be molecular sieve type catalyst, its molecular sieve type mainly includes that Y type molecular sieve, Beta type molecular sieve, ZSM Series Molecules sieve, MCM Series Molecules sieve or complex type molecular sieve etc. are widely used in one or more in the molecular sieve of hydrogen addition technology, it is also possible to be amorphous silicon aluminium type catalyst.Hydrogenation active component is one or more in W, Mo, Ni and Co.Can prepare by the existing method in this area, it is possible to use commodity hydrocracking catalyst.
In the inventive method step (b), described back end hydrogenation catalyst for refining, mainly will be hydrocracked the olefins hydrogenation in product, the reactions such as part aromatic hydrogenation is saturated, the hydrodesulfurization of mercaptan.Back end hydrogenation catalyst for refining can be identical with pretreating catalyst by hydrocracking, it is possible to use Hydrogenation is strong, acid alap special-purpose catalyst.Can prepare by the existing method in this area, it is possible to use commodity pretreating catalyst by hydrocracking or post-processing catalyst.Not using back end hydrogenation catalyst for refining in hydrocracking reactor, hydrocracking catalyst can be loaded in the vacant space of this part, improves disposal ability.
In the inventive method step (b), described low-temp reaction device refers to the reactor operated at relatively low temperature.
In the inventive method step (b), if the space bottom the hydrocracking reactor that described clearance spaces is vacated after not loading back end hydrogenation catalyst for refining in referring to reactor, hydrocracking catalyst can be loaded, so can reduce the air speed of hydrocracking catalyst, it is also possible to the inert medias such as filling porcelain ball.
In the inventive method step (c), described feedstock oil is straight-run gas oil, decompressed wax oil, the wax oil after hydrotreating, diesel oil, catalytic cycle oil, coal tar, one in liquefied coal coil etc. and/or several.
In the inventive method step (c), the described pretreatment reaction district that is hydrocracked comprises protective agent and pretreating catalyst by hydrocracking.The process conditions usually reaction pressure being hydrocracked pretreatment reaction district is 4.0MPa ~ 20.0MPa, and hydrogen to oil volume ratio is 300:1 ~ 2500:1, and volume space velocity is 0.1h-1~4.0h-1, average reaction temperature is 200 DEG C ~ 450 DEG C.
In the inventive method step (c), described hydrocracking reaction district is built-in fills out hydrocracking catalyst.The process conditions in hydrocracking reaction district usually reaction pressure is 4.0MPa ~ 20.0MPa, and hydrogen to oil volume ratio is 300:1 ~ 2500:1, and volume space velocity is 0.2h-1~6.0h-1, average reaction temperature is 280 DEG C ~ 445 DEG C.
In the inventive method step (d), the operation temperature of described high pressure hot separator is 180～360 DEG C.
In the inventive method step (d), in described hydrogen-rich gas, hydrogen content is more than 50v%, and technology for hydrogen purification can be selected to be improved further by the content of hydrogen.
In the inventive method step (d), in described hydrogen-rich gas, hydrogen sulfide content is more than 0.4V%, it may be considered that arrange desulphurization of recycle hydrogen facility.
In the inventive method step (d), described cyclone hydraulic separators is gas-liquid separation, and after temperature being reduced, in gas phase, the liquid of condensation is separated.
In the inventive method step (d), in described hydrogen-rich gas, hydrogen content is more than 50v%, and technology for hydrogen purification can be selected to be improved further by the content of hydrogen.
In the inventive method step (e), described low pressure back end hydrogenation finishing reactor is the reactor of filling back end hydrogenation catalyst for refining, and operation pressure is 1 ~ 6MPa, preferably 1 ~ 4MPa.
In the inventive method step (e), in described hydrogen-rich gas, hydrogen content is more than 50v%, and technology for hydrogen purification can be selected to be improved further by the content of hydrogen.
In the inventive method step (f), described various light-end products include liquefied gas, light naphthar, heavy naphtha, boat coal and diesel oil etc..
In the inventive method step (f), described tail oil can go out system as product, it is also possible to some or all of recycling.
In the inventive method, first hydrocracking reaction effluent lowers the temperature through heat exchanger in the gas phase of hot high score isolated, after temperature reduces, light distillate in gas phase is at least partly changed into liquid phase by liquid phase separation out, the naphtha cut that above-mentioned liquid phase material hydrogeneous with the high temperature meeting hydrogen to oil volume ratio requirement and cold high score obtain mixes and carries out back end hydrogenation refining reaction, the temperature of back end hydrogenation refining reaction is 60～280 DEG C, preferably temperature is 100～260 DEG C, the hydrogen to oil volume ratio of back end hydrogenation refining reaction is 30:1～500:1, preferably 50:1～300:1.
In the application, hot high score refers to high pressure hot separator, operation pressure identical with the pressure of reaction system (ignoring the pressure loss of Flow of Goods and Materials), and operation temperature is that hydrocracking reactor outlet temperature is to 180 DEG C.Cold high score refers to cold high pressure separator, operation pressure identical with the pressure of reaction system (ignoring the pressure loss of Flow of Goods and Materials), and operation temperature is 30～80 DEG C.Temperature after hot high score isolated gas phase heat exchange cooling is 150～250 DEG C.After temperature reduction, the light distillate in gas phase uses cyclone separator by liquid phase separation out after being changed into liquid phase.
In the application, the hydrogeneous material of high temperature comes from one or more in the gas phase drawn in hydrocracking reaction effluent, high pressure hot separator gas phase, hydrocracking reactor.After the consumption of the hydrogeneous material of high temperature, hydrofining reaction reaches required temperature and hydrogen-oil ratio is as the criterion.Concrete consumption, according to the condition needed for the character of each material, back end hydrogenation refining reaction, required product property etc., is determined by this area Conventional wisdom by those skilled in the art.
In the application, the gas phase drawn in hydrocracking reactor, refer in hydrocracking reactor at least provided with two beds, gas phase is set between at least one adjacent catalyst bed and draws pipeline, partial gas phase is drawn hydrocracking reactor.2～8 beds are typically set in hydrocracking reactor, according to current unit scale, 4 beds are typically set.Generally, at reaction conditions after raw material reaction rate of gasification (rate of gasification refers at reaction conditions, the raw material being converted into gas phase accounts for the ratio of raw material gross mass, not hydrogen) more than 30%(mass) the catalyst bed interlayer of preferably greater than 50% arranges gas phase and draws pipeline and draw gaseous stream.Gas phase is drawn pipeline and is preferably provided at catalyst bed interlayer gas-liquid partition tray or the lower section of cold hydrogen box, and gas phase is drawn pipeline and is provided with flow control valve.During normal operating, a gas-phase space can be formed at the bottom of gas-liquid partition tray or cold hydrogen box, and gas phase is drawn pipeline opening in reactor and is arranged in this gas-phase space, and liquid phase material does not the most enter gas phase and draws pipeline.Preferably draw pipeline opening part in gas phase and baffle plate is set, prevent liquid phase from entering gas phase further and draw pipeline.The gaseous phase materials flow drawing pipeline extraction of gas phase is the 10%～80% of circulating hydrogen flow by volume, preferably 30%～60%.
In the inventive method, the volume space velocity (to be hydrocracked liquid charging stock calculating) that back end hydrogenation refines is 1～30h-1, preferably 5～20h-1.Back end hydrogenation refines the conventional hydro that catalyst is this area of use and processes catalyst, typically with aluminum oxide as carrier, with elements such as W, Mo, Ni, Co as active component.
In the inventive method, back end hydrogenation refining reaction is carried out in the reactor being separately provided.
In hydrocracking reaction effluent, containing a small amount of alkene, and alkene reacts, with hydrogen sulfide, the mercaptan generated.In the prior art, the method directly loading appropriate back end hydrogenation catalyst for refining bottom hydrocracking reactor is used.But this mode effect is unsatisfactory, the situation that in product, mercaptans content exceeds standard often occurs, even more serious during the later stage the most aborning.Found by research, in being hydrocracked effluent, generally contain alkene and reacted, with hydrogen sulfide, the mercaptan generated, and contain alkene simultaneously, and the dynamics of olefins hydrogenation and the reaction of mercaptan hydrodesulfurization two types is different with thermodynamic behaviour, optimum reaction environment is different, and therefore prior art uses fixing back end hydrogenation purification condition, it is impossible to ensure that product mercaptans content is stablized qualified.The application passes through fast reaction under the refined relatively lower temp of back end hydrogenation and less hydrogen to oil volume ratio, make major part olefins hydrogenation, major part mercaptan hydrodesulfurization, at relatively low temperature, avoid the impact that thermodynamical equilibrium limits, the a small amount of alkene of residue and mercaptan thoroughly can be removed, on the one hand improve reaction efficiency, improve combined reaction effect, on the other hand ensure that constant product quality, and take full advantage of reaction heat without the extra thermal source increased required for back end hydrogenation refining reaction.
Additionally, the gas phase drawn in hydrocracking reactor has the advantage that for the hydrogeneous material of high temperature, (1) hydrocracking catalyst bed is directly led out due to the light component of gas phase that part is the most cracked, decrease secondary or the repeatedly cracking reaction of light component, the liquid product yield being hydrocracked can be improved；(2) secondary of light component or repeatedly cracking reaction minimizing in hydrocracking reactor lower catalyst bed layer, can reduce the carbon deposit of beds, the service cycle of extension fixture.
Accompanying drawing explanation
Fig. 1 is the principle flow chart that the present invention reduces light fraction sulfur content hydrocracking process.
nullWherein: 1-feedstock oil，2-raw oil pump，Feedstock oil after 3-supercharging，4-hydrocracking reaction district，5-hydrocracking reaction effluent，6-high pressure hot separator，7-high pressure hot separator gas phase，8-heat exchanger，9-cyclone separator，10-cyclone separator liquid phase，11-cyclone separator gas phase，12-major part high temperature cyclone separator gas phase，13-1-fraction high temperature cyclone separator gas phase，13-2-fraction is hydrocracked effluent，13-3-fraction high pressure hot separator gas phase，14-air cooling，The cold high score of 15-，16-cold high score high pressure hydrogen-rich gas，17-circulating hydrogen compressor，The new hydrogen of 18-，19-and new hydrogen mixing Posterior circle hydrogen，20-heat exchange Posterior circle hydrogen，21-cold high score liquid phase，22-back end hydrogenation refining reaction district，23-back end hydrogenation is refined generates logistics，24-high pressure hot separator liquid phase，25-fractionating system，26-light naphthar，27-heavy naphtha，28-navigates coal，29-diesel oil，30-tail oil，31-recycle oil.
Detailed description of the invention
nullIn the method for the present invention, the embodiment relative to Fig. 1 is specific as follows: the feedstock oil of hydrocracking unit mix with hydrogen after by filling pretreating catalyst by hydrocracking be hydrocracked pretreatment reaction district，Next proceed through the hydrocracking reaction district of filling hydrocracking catalyst，It is hydrocracked generation logistics to be directly entered high pressure hot separator and carry out gas-liquid separation，Gas phase enters cyclone separator after heat exchanger is lowered the temperature，The major part of isolated after air cooling in cold high score isolated hydrogen-rich gas and cold burden liquid，Hydrogen-rich gas is after desulfurization or direct reuse，The cold burden liquid of the liquid phase of cyclone separator and fraction gas phase and high score is mixed into back end hydrogenation finishing reactor after being all depressured，At lower temperature、The olefins hydrogenation under the conditions of less hydrogen to oil volume ratio and lower pressure, hydrocracking reaction process generated，By mercaptan hydrodesulfurization therein，Go successively to cold high pressure separator is carried out gas-liquid separation through being hydrogenated with saturated and hydro-sweetening logistics，Product liquid continues through the various light-end products of fractionating system isolated with hot high score liquid phase after mixing，Thus realize considerably reducing the mercaptans content in light distillate.
The concrete condition of the present invention is further illustrated below by embodiment.Protective agent FZC-100, FZC-102B and FZC103 is the hydrogenation protecting agent of China Petroleum and Chemical Corporation Fushun Petrochemical Research Institute's development and production, catalyst FF-46 is the hydrogenation pretreatment catalyst of China Petroleum and Chemical Corporation Fushun Petrochemical Research Institute's development and production, also serve as the back end hydrogenation catalyst for refining of embodiment, catalyst FC-50, FC-32 and ZHC-02 is the hydrocracking catalyst of China Petroleum and Chemical Corporation Fushun Petrochemical Research Institute's development and production, containing Y type molecular sieve in FC-50 and FC-32 catalyst, ZHC-02 catalyst is with amorphous silica-alumina as acid carrier.Embodiment 4～6 be hydrogenation after refine the result under lower pressure.Hydrocracking reactor arranges 4 beds (being referred to as the 1st bed, the 2nd bed, the 3rd bed and the 4th bed from top to bottom successively), and the catalyst amount of each beds is identical.
Table 1 feedstock oil main character
| Feedstock oil | Iran VGO | Saudi Arabia VGO |
| Density (20 DEG C)/g cm-3 | 0.912 | 0.923 |
| Boiling range/DEG C | 350~550 | 320~570 |
| Sulfur content, wt% | 1.33 | 2.85 |
| Nitrogen content/μ g g-1 | 1577 | 803 |
Table 2 embodiment process conditions and result of the test
| Process conditions | Embodiment 1 | Reference Example 1 | Embodiment 2 | Embodiment 3 |
| Feedstock oil | Iran VGO | Iran VGO | Iran VGO | Saudi Arabia VGO |
| Pretreatment section operating condition | ||||
| Pressure/MPa | 15.0 | 15.0 | 12.0 | 17.0 |
| Catalyst | FF-46 | FF-46 | FF-46 | FZC-100/FZC-102B/FZC-103/FF-46 |
| Cumulative volume air speed/h-1 | 1.0 | 1.0 | 0.8 | 8.0 |
| Hydrogen to oil volume ratio | 700 | 700 | 1000 | 1200 |
| Average reaction temperature/DEG C | 370 | 370 | 375 | 380 |
| Generate oil nitrogen content/μ g g-1 | 4.5 | 4.5 | 7.5 | 15.0 |
| Cracking zone operating condition | ||||
| Pressure/MPa | 15.0 | 15.0 | 12.0 | 17.0 |
| Catalyst | FC-32 | FC-32 | FC-50 | ZHC-02 |
| Volume space velocity/h-1 | 1.5 | 1.5 | 1.2 | 1.0 |
| Hydrogen to oil volume ratio | 1000 | 1000 | 1200 | 800 |
| Average reaction temperature/DEG C | 375 | 375 | 370 | 405 |
| Back end hydrogenation refining stage operating condition | ||||
| Catalyst | FF-46 | FF-46 | FF-46 | FF-46 |
| Pressure/MPa | 3.0 | 15.0 | 1.5 | 2.0 |
| Volume space velocity/h-1 | 15.0 | 15.0 | 10.0 | 20.0 |
| Hydrogen to oil volume ratio | 400 | 1000 | 200 | 60 |
| Reaction temperature/DEG C | 270 | 385 | 210 | 190 |
| Feed stock conversion, quality % | ~75 | ~75 | ~65 | ~70 |
| Product yield and product quality | ||||
| Light naphthar yield, % | 4.7 | 4.7 | 3.3 | 4.0 |
| Light naphthar sulfur content, μ g/g | <0.5 | 25 | <0.5 | <0.5 |
| Heavy naphtha yield, % | 20.8 | 20.8 | 8.9 | 8.4 |
| Heavy naphtha sulfur content, μ g/g | <0.5 | 1.0 | <0.5 | <0.5 |
| Boat yield of coal, % | 28.4 | 28.4 | 31.5 | 32.9 |
| Boat coal sulfur content, μ g/g | <0.5 | 2.0 | <0.5 | <0.5 |
| Diesel yield, % | 17.5 | 17.5 | 19.6 | 22.2 |
| Diesel oil sulfur content, μ g/g | 1.0 | 1.0 | 1.0 | 1.0 |
| Tail oil yield, % | 24.8 | 24.8 | 35.7 | 29.8 |
| Tail oil sulfur content, μ g/g | 2.4 | 2.4 | 2.0 | 1.8 |
Embodiment 1-1,2-1,3-1, draw high temperature hydrogen from hydrocracking reactor and introduce back end hydrogenation finishing reactor mutually, fully enter cold high score from the isolated gas phase of cyclone separator.
By flow process and the condition of embodiment 1, drawing the hydrogeneous gas phase of high temperature in the 2nd bed bottom and refine for back end hydrogenation, extraction is the 20% of circulation hydrogen amount (volume), forms embodiment 1-1, then C5 +Liquid receives (quality) increases by 1.42 percentage points than embodiment 1.
By flow process and the condition of embodiment 2, drawing the hydrogeneous gas phase of high temperature in the 3rd bed bottom and refine for back end hydrogenation, extraction is the 50% of circulation hydrogen amount (volume), forms embodiment 2-1, then C5 +Liquid receives (quality) increases by 2.68 percentage points than embodiment 2.
By flow process and the condition of embodiment 3, drawing the hydrogeneous gas phase of high temperature in the 3rd bed bottom and refine for back end hydrogenation, extraction is the 70% of circulation hydrogen amount (volume), forms embodiment 3-1, then C5 +Liquid receives (quality) increases by 3.17 percentage points than embodiment 3.
Be can be seen that by embodiment, use the inventive method, the heat exchanger space at Appropriate application hydrocracking reactor rear portion, the alkene generated by hydrocracking reaction under alternating temperature operating condition is saturated and by mercaptan hydrodesulfurization, such that it is able to the sulfur content of the light-end products such as light naphthar, heavy naphtha is greatly lowered.Being hydrocracked light naphthar and be generally used for ethylene raw, heavy naphtha is generally used for catalytic reforming raw material, and these two kinds of raw materials generally individually require that sulfur content can stably meet product quality requirement at 0.5 below μ g/g, the product that the application scheme obtains.
Claims (18)
1. reduce a method for hydrogen cracking for light fraction product sulfur content, including following content:
A the hydrogenation reactor of () hydrocracking process flow process loads hydrocracking catalyst, and optionally load protective agent, pretreating catalyst by hydrocracking；
B () arranges back end hydrogenation finishing reactor, load back end hydrogenation catalyst for refining；
C () first feedstock oil and hydrogen are mixed and heated after, carrying out hydrocracking reaction under hydrogenation process conditions, then hydrocracking reaction effluent enters high pressure hot separator isolated gas phase and liquid phase；
D the gas phase of () high pressure hot separator isolated enters cyclone separator after heat exchange is lowered the temperature, obtain gas phase and liquid phase after separation, and wherein the isolated gas phase of cyclone separator is at least partially into the recycling of cold anticyclone isolated hydrogen-rich gas；
E oil phase and the hydrogeneous material of high temperature that the liquid phase of () cyclone separator isolated, cold high pressure separator obtain are mixed in low pressure back end hydrogenation finishing reactor, and back end hydrogenation purification stream obtains low-pressure gas and liquid in low pressure separator；
F liquid that the liquid phase of () high pressure hot separator isolated and back end hydrogenation finishing reactor logistics entrance low pressure separator obtain obtains various light-end products and tail oil after being mixed and fed into fractionating system.
Method the most according to claim 1, it is characterised in that: in step (a), when using protective agent and pretreating catalyst by hydrocracking, reaction mass presses flow direction by protective agent, pretreating catalyst by hydrocracking and hydrocracking catalyst.
Method the most according to claim 1, it is characterised in that: in step (b), described back end hydrogenation catalyst for refining, mainly will be hydrocracked the olefins hydrogenation in product, part aromatic hydrogenation is saturated, the hydrodesulfurization reaction of mercaptan.
Method the most according to claim 1, it is characterised in that: in step (c), feedstock oil is the one in the wax oil after straight-run gas oil, decompressed wax oil, hydrotreating, diesel oil, catalytic cycle oil, coal tar, liquefied coal coil and/or several.
Method the most according to claim 1, it is characterised in that: the process conditions being hydrocracked pretreatment reaction district are: reaction pressure is 4.0MPa ~ 20.0MPa, and hydrogen to oil volume ratio is 300:1 ~ 2500:1, and volume space velocity is 0.1h-1~4.0h-1, average reaction temperature is 200 DEG C ~ 450 DEG C.
Method the most according to claim 1, it is characterised in that: the process conditions in hydrocracking reaction district are: reaction pressure is 4.0MPa ~ 20.0MPa, and hydrogen to oil volume ratio is 300:1 ~ 2500:1, and volume space velocity is 0.2h-1~6.0h-1, average reaction temperature is 280 DEG C ~ 445 DEG C.
Method the most according to claim 1, it is characterised in that: in step (e), low pressure back end hydrogenation finishing reactor is the reactor of filling back end hydrogenation catalyst for refining, and operation pressure is 1 ~ 6MPa.
Method the most according to claim 1, it is characterised in that: in step (e), low pressure back end hydrogenation finishing reactor is the reactor of filling back end hydrogenation catalyst for refining, and operation pressure is 1 ~ 4MPa.
Method the most according to claim 1, it is characterised in that: the temperature of back end hydrogenation refining reaction is 60～280 DEG C；The hydrogen to oil volume ratio of back end hydrogenation refining reaction is 30:1～500:1:1；The volume space velocity that back end hydrogenation refines is calculated as 1～30h to be hydrocracked liquid charging stock-1。
Method the most according to claim 1, it is characterised in that: the temperature of back end hydrogenation refining reaction is 100～260 DEG C；The hydrogen to oil volume ratio of back end hydrogenation refining reaction is 50:1～300:1；The volume space velocity that back end hydrogenation refines is calculated as 5～20h to be hydrocracked liquid charging stock-1。
11. methods according to claim 1, it is characterised in that: hot high score refers to high pressure hot separator, and operation pressure is identical with the pressure of reaction system, and operation temperature is that hydrocracking reactor outlet temperature is to 180 DEG C.
12. methods according to claim 1, it is characterised in that: the hydrogeneous material of high temperature comes from one or more in the gas phase drawn in hydrocracking reaction effluent, high pressure hot separator gas phase, hydrocracking reactor.
13. methods according to claim 12, it is characterized in that: the gas phase drawn in hydrocracking reactor, refer in hydrocracking reactor at least provided with two beds, gas phase is set between at least one adjacent catalyst bed and draws pipeline, partial gas phase is drawn hydrocracking reactor.
14. methods according to claim 13, it is characterised in that: arranging 2～8 beds in hydrocracking reactor, after raw material reaction, rate of gasification arranges gas phase more than the catalyst bed interlayer of 30 mass % and draws pipeline extraction gaseous stream at reaction conditions.
15. methods according to claim 13, it is characterised in that: arranging 2～8 beds in hydrocracking reactor, after raw material reaction, rate of gasification arranges gas phase more than the catalyst bed interlayer of 50 mass % and draws pipeline extraction gaseous stream at reaction conditions.
16. methods according to claim 13, it is characterised in that: gas phase is drawn pipeline and is arranged on catalyst bed interlayer gas-liquid partition tray or the lower section of cold hydrogen box, and gas phase is drawn pipeline and is provided with flow control valve.
17. methods according to claim 13, it is characterised in that: the gaseous phase materials flow drawing pipeline extraction of gas phase is the 10%～80% of circulating hydrogen flow by volume.
18. methods according to claim 13, it is characterised in that: the gaseous phase materials flow drawing pipeline extraction of gas phase is the 30%～60% of circulating hydrogen flow by volume.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3716476A (en) * | 1970-12-28 | 1973-02-13 | Texaco Inc | Effluent cooling in a hydrocracking and hydrodesulfurizing process |
| CN1508230A (en) * | 2002-12-19 | 2004-06-30 | 中国石油化工股份有限公司 | Hydrocracking process for producing clean product |
| CN102234542A (en) * | 2010-04-23 | 2011-11-09 | 中国石油化工股份有限公司 | Hydrocracking method for blending ethylene tar |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3716476A (en) * | 1970-12-28 | 1973-02-13 | Texaco Inc | Effluent cooling in a hydrocracking and hydrodesulfurizing process |
| CN1508230A (en) * | 2002-12-19 | 2004-06-30 | 中国石油化工股份有限公司 | Hydrocracking process for producing clean product |
| CN102234542A (en) * | 2010-04-23 | 2011-11-09 | 中国石油化工股份有限公司 | Hydrocracking method for blending ethylene tar |
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