CN105694972A - Flexible hydro-upgrading method for catalytic cracking diesel - Google Patents
Flexible hydro-upgrading method for catalytic cracking diesel Download PDFInfo
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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
- C10G67/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only
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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
- 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
- C10G2300/202—Heteroatoms content, i.e. S, N, O, P
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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
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/30—Physical properties of feedstocks or products
- C10G2300/305—Octane number, e.g. motor octane number [MON], research octane number [RON]
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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
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/02—Gasoline
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Abstract
The invention discloses a flexible hydro-upgrading method for catalytic cracking diesel. The method comprises the following steps: enabling a raw material, hydrogen and a circulating liquid hydrogenation product to perform hydrogen gas saturation in a pipeline to form a liquid-phase mixture of the raw material, the hydrogenation product and the hydrogen, and introducing the liquid-phase mixture of saturated dissolved hydrogen into a non-noble metal hydro-refining reactor for hydro-refining under a hydrogenation process condition; recycling a part of a reaction product produced by the hydro-refining reactor back to the inlet of the reactor, and introducing a part of reaction product into a low-pressure noble metal hydro-upgrading reactor for hydro-upgrading to obtain clean diesel or gasoline. Hydrogen circulation is not required in a hydro-refining segment, so that the equipment investment and operation cost can be lowered; a hydro-upgrading segment has the characteristic of flexible operation; a proper reaction temperature is adopted, so that a finial reaction product can be controlled as a single sulfur-free high-cetane-number diesel product or a mixed product of sulfur-free high-octane-number clean gasoline and sulfur-free high-cetane-number gasoline.
Description
Technical field
The method that the present invention relates to the flexible hydro-upgrading of a kind of catalytic cracking diesel oil, specifically, relates to a kind of method that catalytic cracking diesel oil produces high-octane rating ultra-clean gasoline or high cetane number super clean diesel oil。
Background technology
Development low-carbon economy, recycling economy, realize sustainable development situation under, China oil quality upgrading paces are substantially accelerated, and the requirement of arene content in diesel oil is also more and more stricter。Produce one of clear gusoline emphasis becoming the development of petroleum refining industry of current China。During China's diesel oil is constituted, having 25～30% is catalytic cracking diesel oil。The feature that catalytic cracking diesel oil has arene content height (arene content > 60%), Cetane number is low, its inferior quality, it is necessary to just can be used as fuel oil blend component by hydrofinishing or hydro-upgrading。Catalytic cracking diesel oil produces the bottleneck of high standard cleaning diesel oil owing to arene content height becomes restriction relevant unit, how to reduce arene content in catalytic cracking diesel oil, thus improving its Cetane number to become a difficult problem of puzzlement refinery。
Present stage, the industrial main method improving catalytic cracking diesel oil quality is hydrofinishing and hydro-upgrading, and hydrorefined research is relatively many, is also significantly improved on the basis of tradition Hydrofining Technology。Although hydrofinishing can realize deep desulfuration denitrogenation, but Cetane number is generally only capable of improving 4～8, and especially for the poor quality catalytic cracking diesel that arene content is high, hydrofining diesel oil Cetane number is still less than 35, it is difficult to make desirable diesel oil blending component。Another kind of through frequently with method be hydro-upgrading, generally first pass through hydrofinishing desulfurization removing nitric, diesel cetane-number is improved then through hydro-upgrading, the hydro-upgrading of this poor quality catalytic cracking diesel needs consume substantial amounts of hydrogen and adopt relatively low reaction velocity, corresponding operating cost is high, therefore in catalytic cracking diesel oil during arene content high (Cetane number < 25), taking hydrogenation modification method to produce diesel oil has not been an economically viable route in some cases, and a large amount of aromatic hydrocarbon resources wherein contained fail to make full use of。
CN1064988C discloses a kind of diesel oil fraction hydrogenation converting process, the method adopts a kind of hydrogenation conversion catalyst containing molecular sieve, adopting one-stage process, series connection one-stage process and two-stage method hydrogenation technique flow process to poor ignition quality fuel, particularly catalytic diesel oil (LCO) carries out Porous deproteinized bone, desulfurization and improves diesel cetane-number。But the diesel oil regulation index that the method produces is relatively low, if sulfur content is less than 0.05 weight %, arene content is less than 20 weight %。
US6623628B1 discloses a kind of method adopting two-stage method to produce low-sulfur, low aromatic hydrocarbons and high cetane number diesel oil。The method adopts two reactors, one anti-in catalyst adopt at least one from vib and at least one element in group VIII be active component, two anti-in catalyst adopt at least one noble metal in group VIII to be active component。It is provided with stripper, by clean for the gaseous impurities eliminations such as the hydrogen sulfide instead produced and ammonia, to protect two anti-noble metal catalysts between two reactors。The method can process the intermediate oil that boiling range is 150 DEG C～370 DEG C, produces low-sulfur, low aromatic hydrocarbons and high cetane number diesel oil。But in the method, the hydrogen gas circulating system of two-stage reaction must separate, and work flow is more complicated, equipment investment is high, and operating flexibility declines。
CN101724454A discloses a kind of method adopting catalytic diesel oil and/or coal tar to produce high-knock rating gasoline。Adopting one-stage serial formula hydrogenation technique, raw oil passes sequentially through traditional Hydrobon catalyst and light oil type hydrogen cracking catalyst, unconverted diesel oil distillate complete alternation or part and is recycled into hydrofinishing district or hydrocracking zone。The method can produce high-knock rating gasoline, and improves diesel-fuel cetane number, and then the deficiency of the method is that the yield of diesel oil is low and Cetane number amplification is little。
CN103184073A discloses a kind of method for hydrogen cracking producing high-knock rating gasoline blend component。The method adopts one-stage serial technique, and the high aromatic hydrocarbons poor-quality diesel-oil by cut fraction oil Hydrobon catalyst through the first reaction zone carries out hydrodesulfurization, denitrogenation, aromatic hydrocarbons saturated reaction, and controls aromatic hydrocarbons saturation depth；Refined products enters the hydrocracking catalyst of second reaction zone, carries out hydrocracking reaction, obtains sulfur content less than 50 μ g/g, the research octane number (RON) gasoline fraction higher than 90。But this technique is under low pressure, the Cetane number of the diesel oil distillate oil obtained is low, is not suitable for as the above standard diesel oil blend component of state IV。
The above-mentioned processing method for catalytic cracking diesel oil, no matter it is hydrofinishing, hydro-upgrading or hydrogenation cracking, the recycle hydrogen hydrogenation technique of domestic most main flow is taked in an anti-hydrofinishing section, typically to the sulfur in elimination raw material, nitrogen, oxygen, metal impurities, or the catalytic reaction process carried out to reduce the size of raw molecule。In this process, in order to control the reaction temperature of beds and avoid catalyst carbon deposit to inactivate, generally adopt bigger hydrogen-oil ratio。In addition being absorbed in the improvement of catalytic cracking diesel oil character, the process means taked is with hydrogenated diesel oil or gasoline and diesel product for target, once after flow process determines, it is impossible to realize the flexible modulation of diesel oil or gasoline and diesel product。
Summary of the invention
For overcoming prior art not enough, the invention provides a kind of low cost, easy and simple to handle, products scheme hydro-upgrading flexibly production cleaning diesel oil method。
The present invention is the method for the flexible hydro-upgrading of a kind of catalytic cracking diesel oil, the method includes: raw material, it is saturated that hydrogen and circulation liquid hydrogenation products carry out hydrogen in pipeline, form the liquid phase mixture of a kind of raw material/hydrogenation products/hydrogen, under hydrogenation process conditions, the liquid phase mixture of saturated dissolved hydrogen enters a non-noble metal hydrogenation refining reaction device, for catalytic cracking diesel oil cut fraction hydrogenation desulfurization, denitrogenation, described hydrofining reactor product part out loops back reactor inlet, partial reaction product enters high-pressure separator, refined products bottom high-pressure separator enters a noble metal hydrogenation reforming reactor after mixing with hydrogen and carries out hydro-upgrading, obtain hydro-upgrading product, the de-virtue of the degree of depth for catalytic cracking diesel oil produces high cetane number diesel product or the mild cracking for catalytic cracking diesel oil produces high octane gasoline products；
The noble metal hydrogenation modifying catalyst composition selected in described noble metal hydrogenation reforming reactor includes: carrier is the mixture of HY type molecular sieve, HZSM-5 molecular sieve and aluminium oxide, wherein HY type molecular sieve 25～40wt%, HZSM-5 molecular sieve 5～10wt%, all the other components are aluminium oxide, in carrier quality, active metal Pt content is 0.05～0.1wt%, Ru content is 1～3wt%；
When producing high cetane number diesel product for the de-virtue of the degree of depth of catalytic cracking diesel oil, the process conditions that described noble metal hydrogenation reforming reactor is selected are: reaction pressure 1.5～4.0MPa, during liquid, volume space velocity is 0.8～2.0h-1, reaction temperature is 220～280 DEG C, and hydrogen to oil volume ratio is 200:1～400:1；
When producing high octane gasoline products for the mild cracking of catalytic cracking diesel oil, the process conditions that described noble metal hydrogenation reforming reactor is selected are: reaction pressure 1.5～4.0MPa, during liquid, volume space velocity is 0.8～2.0h-1, reaction temperature is 320～380 DEG C, and hydrogen to oil volume ratio is 200:1～400:1；
Described non-noble metal hydrogenation refining reaction device is single reactor bed or two or more reactor bed, and each reactor bed is provided with discharge byproduct of reaction H2S、NH3The release QI KOU of release gas, adopts hydrotreated product liquid phase circulation system；Described noble metal hydrogenation reforming reactor is single reactor bed or two or more reactor bed, adopts hydrogen gas circulating system。
The method of the flexible hydro-upgrading of catalytic cracking diesel oil of the present invention, described non-noble metal hydrogenation process for refining condition is preferably: reaction dividing potential drop is 5.0～10.0MPa, and fresh feed volume space velocity is 0.5～2.0h-1, reaction temperature is 280～400 DEG C, and by volume, the ratio of circulating load and raw material is 1:1～5:1 to circulation hydrogenation products。
Compared with prior art, this have the advantage that:
(1) hydrofinishing section saves hydrogen gas circulating system and circulating hydrogen compressor；
(2) hydro-upgrading section reaction pressure is low, can reduce equipment investment further；
(3) noble metal hydrogenation upgrading efficiency control high, easily operated, products scheme are flexible；
(4) cleaning petrol and diesel oil product all reaches the sulfur content level without sulfur less than 1 μ g/g。
Accompanying drawing explanation
Fig. 1 is the process flow diagram of a kind of optimal way of method of the flexible hydro-upgrading of catalytic cracking diesel oil of the present invention。
In figure, 1 is hydrofining reactor, and 2 is high-pressure separator, and 3 is hydro-upgrading reactor。
Detailed description of the invention
Technical scheme is expanded on further below in conjunction with example。
As it is shown in figure 1, after the pressurization of fresh catalyst cracked diesel oil raw material and after the mixing of partial hydrogenation refined products, carry out hydrogen presaturation in pipeline with new hydrogen。After saturated hydrogen, liquid enters reactor from hydrofining reactor 1 first bed top, at beds generation hydrofining reaction, carry out with new hydrogen downwards saturated after enter back into hydrofining reactor the second bed, continue hydrofining reaction。Bottom hydrofining reactor 1, a hydrotreated product part out returns and mixes with fresh catalyst cracked diesel oil raw material, another part hydrotreated product enters a high-pressure separator 2, high-pressure separator 2 bottoms material mixes hydrogen gas stream mixing with new hydrogen and recycle hydrogen, it is downwardly into hydro-upgrading reactor 3 first bed, there is hydro-upgrading reaction, hydro-upgrading reactor 3 second bed it is advanced under material, continue hydro-upgrading reaction, finally give diesel modifying product or enter subsequent fractionation process, fractionate out clean gasoline and cleaning diesel product further。
Wherein hydrofining reactor is mounted with non-noble metal hydrogenation catalyst, this non-noble metal hydrogenation refining reaction device can be single reactor bed or two or more reactor bed, they are arranged in each reactor, each reactor beds interlayer fills into a small amount of hydrogen and is dissolved in reaction mass, release QI KOU is arranged at each reactor bed top simultaneously, regulates discharge by control threshold switch size and comprises byproduct of reaction H2S、NH3Release gas, and monitor hydrogen content in release gas。The required hydrogen of reaction is to be provided by the hydrogen of the saturated dissolving in liquid charging stock, it is not necessary to recycle hydrogen system required during conventional hydrogenation process design, whole system no longer sets hydrogen gas circulating system and circulating hydrogen compressor。Hydro-upgrading reactor is mounted with noble metal hydrogenation modifying catalyst, and this noble metal hydrogenation reforming reactor can be single reactor bed or two or more reactor bed, adopts hydrogen gas circulating system。
High-pressure separator top is provided with release QI KOU, separates for high pressure and comprises H2S、NH3Etc. hydrogenation byproduct。
Hydrofinishing section in hydrofining reactor in the inventive method, for catalytic cracking diesel oil cut fraction hydrogenation desulfurization, denitrogenation。By this area general knowledge, it is preferable that hydrofining technology condition be: reaction dividing potential drop is 5.0～10.0MPa, and fresh feed volume space velocity is 0.5～2.0h-1, reaction temperature is 280～400 DEG C, and by volume, the ratio of circulating load and raw material is 1:1～5:1 to circulation hydrogenation products。
The present invention adopts partial hydrogenation product circulation and raw material, hydrogen mixing, is dissolved in distillate by saturated in advance for hydrogen, then enters in fixed bed hydrogenation reactor dissolved with the saturated liquid raw material exceeding the required amounts of hydrogen of reaction and carries out liquid-solid two-phase hydrogenation refining reaction。The reaction mass entering each reactor is the liquid phase feed of dissolved hydrogen, and liquid-solid phase haptoreaction occurs in reactor。The part circulation of hydrogenation products adds molten hydrogen amount, can meet hydrogenation reaction needs and dilute impurity content in raw material。The process operation parameters such as reaction temperature and hydrogenation circulation products circulating load, should require be adjusted less than 10 μ g/g less than 10 μ g/g, nitrogen content according to polishing diesel oil sulfur content。Similarly, each reactor bed inner catalyst loadings also can be evenly distributed, it is possible to has difference。Such as these many variations, are all protection scope of the present invention。
Hydro-upgrading section in hydro-upgrading reactor of the present invention, by the modulation of reaction temperature, it may be achieved two kinds of products scheme。When the de-virtue of the degree of depth for catalytic cracking diesel oil produces without sulfur high cetane number diesel product, the process conditions of selection are: reaction pressure 1.5～4.0MPa, and during liquid, volume space velocity is 0.8～2.0h-1, reaction temperature is 220～280 DEG C, and hydrogen to oil volume ratio is 200:1～400:1。When the mild cracking for catalytic cracking diesel oil produces without sulfur high octane gasoline products, the process conditions selected are: reaction pressure 1.5～4.0MPa, during liquid, volume space velocity is 0.8～2.0h-1, and reaction temperature is 320～380 DEG C, and hydrogen to oil volume ratio is 200:1～400:1。
The noble metal hydrogenation modifying catalyst composition that hydro-upgrading section of the present invention is selected includes: carrier is the mixture of HY type molecular sieve, HZSM-5 molecular sieve and aluminium oxide, wherein HY type molecular sieve 25～40wt%, HZSM-5 molecular sieve 5～10wt%, all the other components are aluminium oxide, in carrier quality, active metal Pt content is 0.05～0.1%, and Ru content is 1～3%。
Researcher of the present invention finds to select described noble metal hydrogenation modifying catalyst, under relatively low reaction pressure and relatively low reaction temperature, can realizing the aromatic hydrocarbons in refined diesel oil saturated by the degree of depth, final upgrading aromatic content of diesel oil can be less than 5%, the sulfur content level less than 1 μ g/g；Under relatively low reaction pressure and higher reaction temperature, double ring arene selective opening and the disconnected side chain reaction of mononuclear aromatics occurring, yield of gasoline 50～60wt%, diesel yield 30～40wt% in purpose product, sulfur content all realizes less than 1 μ g/g。By the adjustment of reaction temperature, it is possible to obtain cleaning diesel oil or the purpose product based on clean gasoline, products scheme is suitable for the market demand of change flexibly。Embodiment 1
The preparation of noble metal hydrogenation modifying catalyst:
Kneading machine mixed grind 10min is put into after 40gHY molecular sieve (contents on dry basis 85%), 10gHZSM-5 molecular sieve (contents on dry basis 90%), 60g macroporous aluminium oxide (contents on dry basis 75%), the mixing of 3.0g sesbania powder, 120g is gradually added in dry powder by 3% aqueous solution of nitric acid, first kneading is to toothpaste-squeezable shape thing, it is that 8mm column type orifice plate respectively extrudes once then through orifice plate, diameter, is finally shaped to diameter 1.6mm cylinder strip；By wet for gained bar dry 8h in 120 DEG C of baking ovens, finally it is placed on Muffle furnace Program and is warming up to 500 DEG C of roasting 4h, namely obtain carrier。
The preparation of active metal impregnation liquid: be sequentially added into 0.3g chloroplatinic acid, 2gRuCl in 80g deionized water3Slaine, uniform stirring, to dissolving, is settled to 100mL and obtains stable impregnation liquid；
The load of active component: adopting in incipient impregnation active metal load carriers, the carrier after dipping, through 120 DEG C of oven drying 8h, 480 DEG C of roasting 3h, namely obtains finished product noble metal hydrogenation modifying catalyst PtRu-1；
Adopt the liquid phase circulation hydrofining reactor-high-pressure separator-hydro-upgrading reactor assembly (Fig. 1 is shown in by schematic diagram) of series connection, Hydrobon catalyst selects THDS-I Hydrobon catalyst (CNOOC Tianjin Chemical Research & Design Institute's production), noble metal hydrogenation modifying catalyst selects PtRu-1, and two kinds of loaded catalysts are 50mL。
Process conditions are in Table 1-2, and catalytic cracking diesel oil feedstock property is in Table 1-3。
Table 1-1 catalytic cracking diesel oil raw oil character
| Oil property | Raw oil 1 |
| Density (20 DEG C), g/cm3 | 0.9022 |
| Boiling range, DEG C | 168～367 |
| Sulfur, μ g/g | 8200 |
| Nitrogen, μ g/g | 830 |
| Existent gum, mg/100ml | 280 |
| Condensed-nuclei aromatics, m% | 17.4 |
| Total aromatic hydrocarbons, m% | 32.7 |
| Cetane number | 37.2 |
Table 1-2 process conditions
| Process conditions | Example 1 |
| Raw oil | Raw oil 1 |
| Hydrofining reactor | Two beds |
| Reaction temperature, DEG C | 340 |
| Reaction pressure, MPa | 6.0 |
| Circulation volume ratio (recycle oil: fresh feed) | 2 |
| Volume space velocity, h-1 | 4.0 |
| Hydro-upgrading reactor | Two beds |
| Reaction temperature, DEG C | 240 |
| Reaction pressure, MPa | 2.0 |
| Volume space velocity, h-1 | 1.6 |
Table 1-3 upgrading diesel product character
| Project | Generate oil 1 | Generate oil 2 | Generate oil 3 | Generate oil 4 | Generate oil 5 | Generate oil 6 |
| The duration of runs, h | 100 | 300 | 600 | 1200 | 1800 | 3000 |
| Density (20 DEG C), g/cm3 | 0.8201 | 0.8225 | 0.8218 | 0.8219 | 0.8216 | 0.8218 |
| Boiling range, DEG C | 170/365 | 170/366 | 170/365 | 170/366 | 170/365 | 170/366 |
| Sulfur, μ g/g | 0.2 | 0.5 | 0.8 | 0.4 | 0.5 | 0.7 |
| Nitrogen, μ g/g | 0.5 | 0.5 | 0.8 | 0.6 | 0.3 | 0.7 |
| Aromatic hydrocarbons, m% | 3.8 | 3.2 | 3.6 | 4.0 | 3.8 | 3.7 |
| Cetane number | 53 | 54 | 54 | 53 | 54 | 54 |
| Diesel yield, % | 98.3 | 98.4 | 98.5 | 98.4 | 98.2 | 98.5 |
Embodiment 2
Adopt the liquid phase circulation hydrofining reactor-high-pressure separator-hydro-upgrading reactor assembly (schematic diagram Fig. 1) of series connection, raw materials used in Table 2-1, Hydrobon catalyst selects THDS-I Hydrobon catalyst, noble metal hydrogenation modifying catalyst selects PtRu-1, and two kinds of loaded catalysts are 50mL。
Process conditions are in Table 2-2, and refined diesel oil character is in Table 2-3。
Table 2-1 catalytic cracking diesel oil raw oil character
| Oil property | Raw oil 2 |
| Density (20 DEG C), g/cm3 | 0.9135 |
| Boiling range, DEG C | 164～365 |
| Sulfur, μ g/g | 3140 |
| Nitrogen, μ g/g | 2040 |
| Existent gum, mg/100ml | 180 |
| Total aromatic hydrocarbons, m% | 57.2 |
| Cetane number | 28 |
Table 2-2 process conditions
| Process conditions | Example 2 |
| Raw oil | Raw oil 2 |
| Hydrofining reactor | Two beds |
| Reaction temperature, DEG C | 360 |
| Reaction pressure, MPa | 8.0 |
| Circulation volume ratio (recycle oil: fresh feed) | 2.5 |
| Volume space velocity, h-1 | 4.0 |
| Hydro-upgrading reactor | Two beds |
| Reaction temperature, DEG C | 360 |
| Reaction pressure, MPa | 3.0 |
| Volume space velocity, h-1 | 1.8 |
Table 2-3 upgrading petrol and diesel oil product property
| Project | Generate oil 1 | Generate oil 2 | Generate oil 3 | Generate oil 4 | Generate oil 5 | Generate oil 6 |
| The duration of runs, h | 100 | 300 | 600 | 1200 | 1800 | 3000 |
| Diesel product character | ||||||
| Density (20 DEG C), g/cm3 | 0.8126 | 0.8126 | 0.8134 | 0.8128 | 0.8132 | 0.8130 |
| Boiling range, DEG C | 165/360 | 164/362 | 162/360 | 165/362 | 162/360 | 163/361 |
| Sulfur, μ g/g | 0.5 | 0.8 | 0.4 | 0.2 | 0.3 | 0.4 |
| Nitrogen, μ g/g | 0.2 | 0.4 | 0.5 | 0.3 | 0.1 | 07.6 |
| Aromatic hydrocarbons, m% | 14.5 | 14.3 | 14.8 | 14.0 | 14.6 | 14.8 |
| Diesel cetane-number | 46 | 47 | 47 | 46 | 47 | 47 |
| Diesel oil liquid is received, % | 36.3 | 36.4 | 36.5 | 36.4 | 36.2 | 36.5 |
| Gasoline products character | ||||||
| Density (20 DEG C), g/cm3 | 0.7126 | 0.7128 | 0.7124 | 0.7128 | 0.7125 | 0.7122 |
| Boiling range, DEG C | 65/170 | 64/172 | 65/170 | 65/172 | 65/170 | 63/171 |
| Sulfur, μ g/g | 0.5 | 0.8 | 0.4 | 0.2 | 0.3 | 0.4 |
| Nitrogen, μ g/g | 0.2 | 0.4 | 0.5 | 0.3 | 0.1 | 07.6 |
| Aromatic hydrocarbons, m% | 41.5 | 41.3 | 41.8 | 41.0 | 41.6 | 41.8 |
| Octane number (RON) | 90.2 | 90.5 | 90.6 | 90.3 | 90.2 | 90.7 |
| Gasoline liquid is received, % | 54.1 | 54.6 | 54.5 | 54.2 | 54.4 | 54.3 |
Comparative example 1
Adopting the liquid phase circulation hydrofining reactor-high-pressure separator system of series connection, different from embodiment 1 is in that, does not adopt noble metal hydrogenation reforming reactor。Catalytic cracking diesel oil feedstock property used is in Table 2-1, and Hydrobon catalyst selects THDS-I Hydrobon catalyst。Process conditions are in Table 2-2, and refined diesel oil character is in Table 2-4。
Table 2-4 refined diesel oil character
| Project | Generate oil 1 | Generate oil 2 |
| The duration of runs, h | 100 | 300 |
| Diesel oil liquid is received, % | 99.8 | 99.7 |
| Density (20 DEG C), g/cm3 | 0.8831 | 0.8835 |
| Boiling range, DEG C | 165/360 | 164/362 |
| Sulfur, μ g/g | 8.1 | 8.3 |
| Nitrogen, μ g/g | 6.2 | 8.6 |
| Aromatic hydrocarbons, m% | 46.6 | 46.7 |
| Cetane number | 34 | 33 |
Comparative example 2
Adopt the liquid phase circulation hydrofining reactor-high-pressure separator-hydro-upgrading reactor assembly (schematic diagram Fig. 1) of series connection, catalytic cracking diesel oil feedstock property used is in Table 2-1, and Hydrobon catalyst selects existing industrial conventional FH-98 Hydrobon catalyst, catalyst for hydro-upgrading to select industrial 3963 conventional hydrogenation catalysts。Process conditions are in Table 2-2, and refined diesel oil character is in Table 2-5。
Table 2-5 purified product character
| Project | Generate oil 1 | Generate oil 2 |
| The duration of runs, h | 100 | 300 |
| Diesel oil liquid is received, % | 96.1 | 95.8 |
| Density (20 DEG C), g/cm3 | 0.8631 | 0.8635 |
| Boiling range, DEG C | 165/360 | 164/362 |
| Sulfur, μ g/g | 4.2 | 4.5 |
| Nitrogen, μ g/g | 3.2 | 3.3 |
| Aromatic hydrocarbons, m% | 32.1 | 34.6 |
| Cetane number | 38 | 37 |
By embodiment and comparative example result it can be seen that the method selecting the present invention, for catalytic cracking diesel oil hydro-upgrading, by controlling reaction process condition, it may be achieved to maximize diesel product scheme or petrol and diesel oil products scheme comparatively flexibly。And simple hydrofinishing can only obtain cleaning diesel product, although hydrofinishing-non-noble metal hydrogenation upgrading route can improve diesel product Cetane number, but still can only based on diesel product, and diesel product Cetane number improves limited。
Claims (2)
1. the method for the flexible hydro-upgrading of catalytic cracking diesel oil, it is characterized in that, including: raw material, it is saturated that hydrogen and circulation liquid hydrogenation products carry out hydrogen in pipeline, form the liquid phase mixture of a kind of raw material/hydrogenation products/hydrogen, under hydrogenation process conditions, the liquid phase mixture of saturated dissolved hydrogen enters a non-noble metal hydrogenation refining reaction device, for catalytic cracking diesel oil cut fraction hydrogenation desulfurization, denitrogenation, described hydrofining reactor product part out loops back reactor inlet, partial reaction product enters high-pressure separator, refined products bottom high-pressure separator enters a noble metal hydrogenation reforming reactor after mixing with hydrogen and carries out upgrading；
The noble metal hydrogenation modifying catalyst composition selected in described noble metal hydrogenation reforming reactor includes: carrier is the mixture of HY type molecular sieve, HZSM-5 molecular sieve and aluminium oxide, wherein HY type molecular sieve 25～40wt%, HZSM-5 molecular sieve 5～10wt%, all the other components are aluminium oxide, in carrier quality, active metal Pt content is 0.05～0.1wt%, Ru content is 1～3wt%；
When producing high cetane number diesel product for the de-virtue of the degree of depth of catalytic cracking diesel oil, the process conditions that described noble metal hydrogenation reforming reactor is selected are: reaction pressure 1.5～4.0MPa, during liquid, volume space velocity is 0.8～2.0h-1, reaction temperature is 220～280 DEG C, and hydrogen to oil volume ratio is 200:1～400:1；
When producing high octane gasoline products for the mild cracking of catalytic cracking diesel oil, the process conditions that described noble metal hydrogenation reforming reactor is selected are: reaction pressure 1.5～4.0MPa, during liquid, volume space velocity is 0.8～2.0h-1, reaction temperature is 320～380 DEG C, and hydrogen to oil volume ratio is 200:1～400:1；
Described non-noble metal hydrogenation refining reaction device is single reactor bed or two or more reactor bed, and each reactor bed is provided with discharge byproduct of reaction H2S、NH3The release QI KOU of release gas, adopts hydrotreated product liquid phase circulation system；Described noble metal hydrogenation reforming reactor is single reactor bed or two or more reactor bed, adopts hydrogen gas circulating system。
2. the method for the flexible hydro-upgrading of catalytic cracking diesel oil according to claim 1, it is characterised in that
Described non-noble metal hydrogenation process for refining condition is: reaction dividing potential drop is 5.0～10.0MPa, and fresh feed volume space velocity is 0.5～2.0h-1, reaction temperature is 280～400 DEG C, and by volume, the ratio of circulating load and raw material is 1:1～5:1 to circulation hydrogenation products。
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| CN103865575A (en) * | 2014-02-24 | 2014-06-18 | 中国海洋石油总公司 | Method for liquid-phase circulation hydrogenation and modification of high-nitrogen catalytic cracked diesel oil |
| CN104399520A (en) * | 2014-11-11 | 2015-03-11 | 中国海洋石油总公司 | Catalyst for producing high-octane-number gasoline composition from heavy aromatic hydrocarbons and preparation method of catalyst |
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| CN103865575A (en) * | 2014-02-24 | 2014-06-18 | 中国海洋石油总公司 | Method for liquid-phase circulation hydrogenation and modification of high-nitrogen catalytic cracked diesel oil |
| CN104399520A (en) * | 2014-11-11 | 2015-03-11 | 中国海洋石油总公司 | Catalyst for producing high-octane-number gasoline composition from heavy aromatic hydrocarbons and preparation method of catalyst |
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