CN102453537B - Method for maximum production of clean diesel oil by shale oil whole fraction hydrogenation - Google Patents
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- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 23
- 239000002283 diesel fuel Substances 0.000 title claims abstract description 18
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 17
- 238000004517 catalytic hydrocracking Methods 0.000 claims abstract description 45
- 238000006243 chemical reaction Methods 0.000 claims abstract description 37
- 239000001257 hydrogen Substances 0.000 claims abstract description 21
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 21
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- 229910052751 metal Inorganic materials 0.000 claims description 12
- 239000002184 metal Substances 0.000 claims description 12
- 238000007670 refining Methods 0.000 claims description 12
- 239000002808 molecular sieve Substances 0.000 claims description 8
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical group [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 8
- 238000005336 cracking Methods 0.000 claims description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 6
- LKTZODAHLMBGLG-UHFFFAOYSA-N alumanylidynesilicon;$l^{2}-alumanylidenesilylidenealuminum Chemical compound [Si]#[Al].[Si]#[Al].[Al]=[Si]=[Al] LKTZODAHLMBGLG-UHFFFAOYSA-N 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- 239000007789 gas Substances 0.000 claims description 4
- 150000002431 hydrogen Chemical class 0.000 claims description 4
- 229910044991 metal oxide Inorganic materials 0.000 claims description 4
- -1 metal oxide compound Chemical class 0.000 claims description 4
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical group O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 4
- 229910017052 cobalt Inorganic materials 0.000 claims description 3
- 239000010941 cobalt Substances 0.000 claims description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 3
- 229910052721 tungsten Inorganic materials 0.000 claims description 3
- 239000010937 tungsten Substances 0.000 claims description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 2
- 239000004480 active ingredient Substances 0.000 claims description 2
- 150000004706 metal oxides Chemical class 0.000 claims description 2
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
- 239000011733 molybdenum Substances 0.000 claims description 2
- 239000003870 refractory metal Substances 0.000 claims description 2
- 239000000047 product Substances 0.000 abstract description 19
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- 125000004435 hydrogen atom Chemical class [H]* 0.000 abstract 1
- 239000003921 oil Substances 0.000 description 38
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 7
- 239000000295 fuel oil Substances 0.000 description 7
- 229910052760 oxygen Inorganic materials 0.000 description 7
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- 150000001336 alkenes Chemical class 0.000 description 6
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- 150000002430 hydrocarbons Chemical class 0.000 description 3
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- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 3
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- 208000019901 Anxiety disease Diseases 0.000 description 2
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- 239000000084 colloidal system Substances 0.000 description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical class O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229910017318 Mo—Ni Inorganic materials 0.000 description 1
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- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- PFRUBEOIWWEFOL-UHFFFAOYSA-N [N].[S] Chemical compound [N].[S] PFRUBEOIWWEFOL-UHFFFAOYSA-N 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
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- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
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- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention discloses a method for maximum production of clean diesel oil by shale oil whole fraction hydrogenation. The method adopts a technology combined hydrofining and hydrocracking. The method comprises the following steps of mixing a whole fraction of shale oil and hydrogen, feeding the mixture into a hydrofining reaction section, carrying out heat exchange cooling of effluence obtained by the hydrofining, feeding the cooled effluence into a separator, carrying out gas-liquid separation, feeding the separated liquid into a product fractionating tower, carrying out cutting to obtain products of naphtha, diesel oil and the like, feeding unconverted oil in the bottom of the product fractionating tower into a hydrocracking reaction section for hydrocracking to obtain hydrocracked effluent, and circulating all the hydrocracked effluent as a hydrofinishing raw material. Compared with the prior art, the method realizes production of clean diesel oil meeting the European V standard by shale oil whole fraction hydrogenation, has a product yield of 85% and can obtain a low-sulfur high-quality naphtha by-product as an ethylene production raw material, and thus providing a beneficial technology approach for shale oil deep processing and alleviating the situation of short supply of petroleum-based diesel oil.
Description
Technical field
The present invention relates to a kind of method of maximum production of clean diesel oil by shale oil whole fraction hydrogenation.Specifically, taking the full cut of shale oil as raw material, produce high-quality light-weight fuel oil by the method for hydrofining-hydrocracking.
Background technology
World petroleum resource shortage, the technology that makes various non-conventional oil resources processings produce light-weight fuel oil becomes focus, and wherein one of technology is taking shale oil as producing clean fuel.
Shale oil is that resinous shale is after hot-work, the product that its organic decomposes generates, similar natural oil, but contain more unsaturated hydro carbons and dredge, the non-hydrocarbons organic compound such as nitrogen, oxygen, and these unsaturated hydro carbons and non-hydrocarbons organic compound are to cause that oil product colloid increases, sediment forms and the major cause that causes stability variation, color blackening.So, no matter with the further processing oil fuel of shale oil, still produce other products, all needing to remove non-hydrocarbon compound, saturation of olefins ensures quality product.
Hydrotreatment foot oil product carries out the process of catalytic reforming under catalyzer and hydrogen existence, by oil product is carried out to desulfurization, denitrogenation, deoxidation, olefin saturated, aromatic saturation and demetalization and diasphaltene impurity etc., improves oil quality.Hydrotreatment technology has the advantages such as the raw material range of processing is wide, liquid yield is high, good product quality, is the indispensable a kind of processing means of production high-quality oil product.
Processing shale oil recovery light-weight fuel oil by the method for hydrogenation has been reported.A kind of method of having introduced hydrogenation of shale oil and producing diesel oil as US4419218, the method is, with conventional method of hydrotreating, shale oil is carried out to pre-treatment, the generation oil obtaining, without separating all directly as cracking stock, carries out cracking with ZSM-12 molecular sieve catalyst, production diesel oil.Its shortcoming is that the generation oil of hydrotreatment directly enters cracking unit without separating, and in face shale oil, oxygen and nitrogen content is higher, and this is very large on the impact of cracking catalyst performance, is easy to inactivation, can not assurance device long-term operation.
US4344840 has introduced a kind of method of hydrogenation of shale oil production rocket engine fuel and diesel oil, and the method is, with ebullated bed reactor, shale oil is carried out to demetalization, then processes with fixed bed hydrogenation treatment unit, obtains qualified rocket engine fuel and diesel oil.Its shortcoming is that hydrogen consumption is high, process cost is high, construction investment is high, and boiling bed process is not mature enough.
CN101067089 discloses a kind of working method of shale oil, and this technique is to adopt hydrotreatment and the series connection of hydrogenation catalytic conversion of heavy oil, by shale oil recovery light-weight fuel oil and low-carbon alkene.Its shortcoming is that the residual oil and the coke ratio that produce are more, will inevitably shorten the running period of device.
Summary of the invention
In order to overcome the deficiencies in the prior art, the invention provides a kind of method of shale oil hydrogenation of total effluent maximum production clean diesel.This method not only can make shale oil hydrogenation of total effluent produce the clean diesel that meets Europe V standard, product yield can reach 85%, the low-sulfur high-quality petroleum naphtha of by-product can be used as ethylene raw processed simultaneously, thereby for shale oil deep processing provides useful technological approaches, alleviate the present situation of petroleum base diesel oil supply and demand anxiety.
Hydrogenation of shale oil maximum of the present invention is produced the method for the cleaning diesel oil that disappears, comprise that the full cut of shale oil and hydrogen are mixed into hydrofining reaction section, effluent after refining carries out gas-liquid separation through the cooling separator that enters of heat exchange, the liquid stream separating enters product separation column, cuts out the product such as petroleum naphtha, diesel oil.Fractionator Bottom unconverted oil enters hydrocracking reaction section and carries out hydrocracking, and the hydrocracking reaction effluent of gained all enters hydrofining reaction section.
In the present invention, the reaction effluent of hydrofining and hydrocracking shares a set of separation system, can reduce like this facility investment.Hydrogen-rich gas by separation system gained can be circulated to hydrocracking reactor as recycle hydrogen after purifying.Sewage is discharged reactive system.
Unconverted oil of the present invention is as the criterion with diesel oil, counts light oil than the component that diesel oil is lighter, overweights bavin oil fraction and counts unconverted oil.
Shale oil properties of the present invention (taking massfraction): oxygen level is 0.5%～5.0%, nitrogen content is 1.0%～2.0%, sulphur content is 0.5%～1.0%, and density (20 DEG C) is 1.0g/cm3 left and right, also contains more unsaturated hydrocarbons and colloid.Determine hydrogenation combination technique process of the present invention according to shale oil properties.
Described shale oil whole fraction oil hydrotreating technology, to remove oxygen carrier and the olefin impurities such as alcohol, ketone, fat.Hydrofining reaction section is for the Deep Hydrotreating of fresh feed and soaking section effluent, and hydrofining reaction section can adopt a reactor, preferably includes two tandem reactors.When hydrofining reaction section adopts two tandem reactors, the first reactor charge high voidage Hydrobon catalyst, the conventional Hydrobon catalyst of the second reactor charge, can only fill a kind of Hydrobon catalyst or two kinds and multiple Hydrobon catalyst grading loading, its pore volume is 0.2～0.6ml/g, and specific surface area is 100～350m
2/ g.The first reactor can be identical with the composition of the Hydrobon catalyst of the second reactor charge, taking group vib metal and/or group VIII metal as active metal component, be preferably one or more in cobalt, molybdenum, nickel and tungsten, carrier is inorganic refractory metal oxide compound, is generally aluminum oxide or silicon-containing alumina.Taking the weight of catalyzer as benchmark, in oxide compound, the content of active metal is 10%～40%.The first reactor is different from granular size and the shape of the Hydrobon catalyst of the second reactor charge, there is different bed voidages: the Hydrobon catalyst of the first reactor is the shapes such as Raschig ring shape, porous spherical, bird-nest-shaped, and bed voidage is 0.45～0.85.When hydrofining reaction section is used two tandem reactors, hydrocracking reaction effluent can enter the first reactor, also can enter the second reactor.
Mainly there is demetalization, olefin saturated, aromatic saturation reaction in the first reactor of described hydrofining reaction section, there is a small amount of desulfurization, denitrification reaction simultaneously, therefore the catalyzer using has higher active metallic content, and the catalyzer that guard reactor in general hydrogenation process uses is protective material, protectant active metallic content is lower, temperature of reaction is lower, generally below 200 DEG C; Mainly there is the complete saturated reaction of deep desulfuration, denitrogenation and alkene in the second reactor.
Described hydrofining technology condition optimization is as follows: hydrogen dividing potential drop 5～19MPa, and hydrogen to oil volume ratio 500～1500, the first temperature of reactor is 200～280 DEG C, volume space velocity is 0.5～5.0h
-1, the second temperature of reactor is 300～450 DEG C, volume space velocity is 0.1～2.0h
-1.
Described hydrocracking is by the unconverted oil after shale oil whole fraction oil hydrotreating (last running) hydrocracking.Hydrocracking section can only fill a kind of hydrocracking catalyst or two kinds and multiple filling hydrocracking catalyst at different stages, also can be by Hydrobon catalyst and filling hydrocracking catalyst at different stages, unconverted oil is carried out to deep hydrogenation conversion, and hydrocracking catalyst can be selected the middle oil type hydrocracking catalyst of commodity.Conventional hydrocracking catalyst is taking group vib metal and/or group VIII metal as active metal component, is preferably one or more in cobalt, aluminium, nickel and tungsten, and carrier is aluminum oxide or amorphous aluminum silicide, and cracking component is molecular sieve.Because oxygen in the full cut of shale oil, nitrogen content are higher, oxide compound, the nitride composition more complicated in oil, so hydrocracking catalyst of the present invention is the hydrocracking catalyst taking amorphous aluminum silicide and molecular sieve as carrier, this catalyzer has again good naphthenic hydrocarbon selectivity and rises ring, isomerization of paraffinic hydrocarbons, the hydrocracking of last running appropriateness, aromatic saturation and heteroatoms and remove performance carrying the highly active while.Taking the weight of catalyzer as benchmark, the content of active metal oxide is 10%～35%, and molecular sieve content is 5%～40%.Its pore volume is 0.3～0.5ml/g, and specific surface area is 100～450m
2/ g.Molecular sieve is generally Modified Zeolite Y, and one or mixture in modified beta zeolite etc.
The processing condition of described hydrocracking are preferably as follows: hydrogen dividing potential drop 5～19MPa, 300～450 DEG C of temperature of reaction, hydrogen to oil volume ratio 500～1500, volume space velocity 0.2～4.0h when liquid
-1.
The catalyzer using in the inventive method can be selected suitable commercial catalyst as required, also can prepare by this area ordinary method.
The present invention has the following advantages:
1. in the present invention, the first reactor of hydrofining reaction section is due to a small amount of desulfurization, denitrification reaction occurring, thereby catalyst activity is higher, and this is just highly beneficial to alkene and aromatic hydrogenation saturated reaction; In the second reactor, under pyroreaction condition, the sulphur nitrogen impurity passing through in the aromatic hydrocarbons that hydrogenation is saturated is easy to remove, and then has improved desulfurization, denitrification effect, reaches the object of deep refining.
2. the present invention, because oxygen level in shale oil is higher, has dysgenic water therefore the separation system after refining can be discharged in time to hydrocracking catalyst, has ensured hydrocracking catalyst long-term operation; Hydrocracking effluent all circulates as hydrorefined charging, can improve hydrofining charging quality on the one hand, reduce refining reaction device green coke, ensure long-term operation, rear refining method for another side hydrocracking effluent, make not to be able to do in time in the raw material further hydrogenation of polynuclear compound of reaction is saturated, is more conducive to lighting, favourable to improving the quality of lightweight oil.
3. the present invention is directed to feed oxygen, feature that nitrogen content is high, select resistance to nitrogen and water resistance good, the hydrocracking catalyst containing amorphous aluminum silicide and molecular sieve that cracking performance is suitable, ensured the long-term operation of device.And can produce the clean diesel of high-quality.
4. present method is directly processed the full cut of shale oil, does not need raw material to carry out as pre-treatment such as cuttings, and the step that simplifies the operation, reduces production costs.
5. the present invention without sulphur clean diesel product, goes back by-product part high-quality petroleum naphtha except obtaining, and can be used as ethylene raw processed.Can alleviate current oil supply using shale oil as the raw material of producing clean diesel and occur global anxiety, for diesel production provides new method, the development of following shale oil industry be had to huge potentiality and application prospect.
Brief description of the drawings
Fig. 1 is principle process schematic diagram of the present invention.
Embodiment
As shown in the figure, shale oil raw material 1 and hydrogen 2 are mixed into the first reactor 3 of hydrofining reaction section, obtain hydrofining generation oil 4 and enter the second reactor 5 of hydrofining reaction section, obtain hydrofining generation oil 6 and carry out gas-liquid separation through the cooling separator 7 that enters of heat exchange, the hydrogen-rich gas 8, water 9 and the liquid oil 10 that obtain, hydrogen-rich gas 8 enters recycle compressor, can be used as recycle hydrogen uses, the direct extraction system of water 9, liquid oil 10 enters product separation column 11, obtains petroleum naphtha 12, diesel oil 13 and unconverted oil 14.Fractionator Bottom unconverted oil 14 enters hydrocracking reactor 15 and carries out hydrocracking, and the hydrocracking reaction effluent 16 of gained all enters hydrofining reaction section the first reactor 3.
Further set forth technical scheme of the present invention below in conjunction with embodiment.
Embodiment 1～3.
The stock oil character using in embodiment is in table 1.
The full cut character of table 1 shale oil (consisting of quality percentage composition)
First the full cut of shale oil and hydrogen and hydrocracking reaction effluent are mixed into hydrofining reactor, obtaining hydrofining generation oil separates, unconverted oil enters hydrocracking reactor and carries out hydrocracking, the hydrogenation reaction effluent of gained all returns hydrofining reactor as hydrorefined charging, obtains hydrofining generation oil and carries out fractionation.
The macrobead hydrotreating catalyst R-FF-26 of the first reactor charge Fushun Petrochemical Research Institute development of hydrofining reaction section, is shaped as the Raschig ring of diameter 10 × 10mm, and bed voidage is 0.60.The FF-36 hydrotreating catalyst of the second reactor charge Fushun Petrochemical Research Institute development and production.The composition of two kinds of catalyzer is identical, and taking aluminum oxide as carrier, taking Mo-Ni as active ingredient, its active metal counts 30% with oxide weight, the specific surface area>=160m of catalyzer
2/ g, pore volume is 0.35 ± 0.02mL/g.FF-36 catalyzer diameter is 1.2 ± 0.mm, the bar shaped of long 3～8mm, and bed voidage is 0.38.(conventional one section of process for refining refers to that two kinds of catalyst loadings are in a reactor to adopt respectively conventional one section of process for refining A, operational condition is identical with the present invention's the second reactor, volume space velocity is total air speed of two tandem reactors of refining stage of the present invention) and this technique refining stage B carry out simultaneous test, processing condition and correlation data are as table 2.
Table 2 processing condition and the contrast-hydrofining of generation oil nature
Note: A represents single reactor, B represents double-reactor series connection.
Shown by simultaneous test data, apply one-stage serial process for refining technology of the present invention, desulfurization removing nitric successful improves, and has good refining effect.
Table 3 processing condition and generation oil nature-hydrocracking
FC-14 is the hydrocracking catalyst of Fushun Petrochemical Research Institute's development and production.
The whole flow process product property of table 4 and yield-hydrofining/hydrocracking
Can be found out by embodiment data, by hydrogenation combination technique of the present invention, shale oil hydrogenation of total effluent is converted into high-quality clean fuel to greatest extent, especially can direct production meet the clean diesel of Europe V standard, product yield can reach 85%, and the low-sulfur high-quality petroleum naphtha of by-product can be used as ethylene raw processed, simultaneously can the work-ing life of extending catalyst and the runtime of device, improve treatment capacity, reduce plant energy consumption and production cost.
Claims (5)
1. the method for a maximum production of clean diesel oil by shale oil whole fraction hydrogenation, it is characterized in that: the full cut of shale oil and hydrogen are mixed into hydrofining reaction section, effluent after refining carries out gas-liquid separation through the cooling separator that enters of heat exchange, the liquid stream separating enters product separation column, cut out petroleum naphtha, diesel product, Fractionator Bottom unconverted oil enters hydrocracking reaction section and carries out hydrocracking, and the hydrocracking reaction effluent of gained all enters hydrofining reaction section;
Wherein hydrofining reaction section adopts two tandem reactors, the first reactor charge high voidage Hydrobon catalyst, the conventional Hydrobon catalyst of the second reactor charge, the Hydrobon catalyst of the first reactor is Raschig ring shape, porous spherical or bird-nest-shaped, and bed voidage is 0.45～0.85; The first reactor is identical with the composition of the Hydrobon catalyst of the second reactor charge, taking group vib metal and/or group VIII metal as active metal component, carrier is inorganic refractory metal oxide compound, taking the weight of catalyzer as benchmark, in oxide compound, the content of active metal is 10%～40%; Hydrogen dividing potential drop 5～19MPa, hydrogen to oil volume ratio 500～1500, the first temperature of reactor is 200～280 DEG C, volume space velocity is 0.5～5.0h
-1, the second temperature of reactor is 300～450 DEG C, volume space velocity is 0.1～2.0h
-1.
2. it is characterized in that in accordance with the method for claim 1: the hydrogen-rich gas by separation system gained is circulated to hydrocracking reactor as recycle hydrogen after purifying.
3. it is characterized in that in accordance with the method for claim 1: hydrocracking catalyst is selected middle oil type hydrocracking catalyst.
4. according to the method described in claim 1 or 3, it is characterized in that: hydrocracking catalyst is taking one or more in cobalt, molybdenum, nickel and tungsten as active ingredient, carrier is aluminum oxide or amorphous aluminum silicide, cracking component is molecular sieve, taking the weight of catalyzer as benchmark, the content of active metal oxide is 10%～35%, and molecular sieve content is 5%～40%.
5. according to the method described in claim 1 or 3, it is characterized in that the processing condition of hydrocracking are: hydrogen dividing potential drop 5～19MPa, 300～450 DEG C of temperature of reaction, hydrogen to oil volume ratio 500～1500, volume space velocity 0.2～4.0h when liquid
-1.
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|---|---|---|---|---|
| CN103497782B (en) * | 2013-10-16 | 2015-05-20 | 黑龙江省能源环境研究院 | Method of producing low-sulfur low freezing point diesel by full-range shale oil |
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