CN1415707A - Method for increasing prodn. of good quality diesel oil from distillation cut oil - Google Patents
Method for increasing prodn. of good quality diesel oil from distillation cut oil Download PDFInfo
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- CN1415707A CN1415707A CN 01133362 CN01133362A CN1415707A CN 1415707 A CN1415707 A CN 1415707A CN 01133362 CN01133362 CN 01133362 CN 01133362 A CN01133362 A CN 01133362A CN 1415707 A CN1415707 A CN 1415707A
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- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
A process for preparing high-quality diesel oil from fractional oil with high output rate features that the isomerizing catalyst is used between main cracking agent for hydrocracking and the post refining agent to lower the pour point of diesel oil fractional oil. The catalyst used by present invention possesses good anti NA3 and H2S ability, therefore the process flow and operation are rather simple.
Description
1, technical field
The present invention relates to the production method of diesel oil, particularly by the raise productivity and improve the quality method of diesel oil of heavy fraction of oil.
2, background technology
In recent years, respective change has taken place with Economic development in the demand structure in petroleum products market, and the demand of oil fuel and gasoline descends, and the diesel oil demand rises, and environmental regulation is strict day by day.Therefore, oil refining enterprise presses for to find and a kind ofly can improve the novel technique that diesel yield can be produced clean fuel again.
Along with the passing of Oil extraction time, crude oil is heaviness day by day.Improve the light-end products productive rate, must carry out deep processing crude oil.Catalytic cracking, coking and hydrocracking are three big heavy oil deep process technologies, wherein hydrocracking is because of its machinable wide scope of material, products scheme is flexible, good product quality, especially can direct production fine rocket engine fuel and fraction of diesel oil, have catalysis and coking technology incomparable advantage.No matter hydrocracking process is one-stage serial or single hop flow process, and all in industrial widespread use, technology maturation is reliable.But conventional hydrocracking process divides the coal fraction that sails from product after, gained diesel product condensation point is higher, desires the qualified diesel product of direct production, and then the cut point of diesel oil is forced to reach, thereby has reduced diesel yield to a certain extent.
U.S. Pat 5,935,414 have introduced a kind of method of producing low freezing point rocket engine fuel and low freezing point diesel fuel by the hydrocracking of fraction oil, this method adopts conventional hydrocracking process flow process, below the cracking zone hydrocracking catalyst, load the pour point depression catalyzer that partly dewaxes, filling back catalyst for refining under dewaxing catalyst.Its main purpose be the fraction oil more than 343 ℃ after hydrocracking, utilize the unique duct and the acid sites of the dewaxing contained molecular sieve of pour point depression catalyzer (as mesoporous molecular sieves such as ZSM-5), make paraffinic hydrocarbons, band short-side chain alkane and the cyclic hydrocarbon institute contour condensation point component of belt length side chain alkane in the crackate optionally be cracked into small molecules, thereby reduce the freezing point of rocket engine fuel and the condensation point of diesel oil.This method is by the mode to the crackate dewaxing, though condensation point of diesel oil can be fallen very low, but have following problem: 1. crackate is after dewaxing, though can reduce the freezing point of rocket engine fuel and the condensation point of diesel oil, but this is a cost with oily productive rate in sacrificing, in the time of pour point depression, middle oily productive rate descends, and gasoline yield rises.2. the active and stable matching problem of dewaxing catalyst and hydrocracking catalyst, promptly when reaching desired cracking severity, can the dewaxing degree of depth meet the requirements.If two kinds of desired temperature of reaction of process differ bigger, then will certainly cause the two to be difficult to take into account, cause difficulty to operation.The deactivation rate difference of other two kinds of catalyzer is bigger, can not be by the synchronous temperature raising of service requirements, and the one, can bring difficulty to operation, the 2nd, this combination process can't life-time service, and with the prolongation of runtime, pour-point depressing process descends very fast, can't be consistent with hydrocracking, effect variation gradually then.3. can produce a large amount of alkene when adopting the dewaxing mode to reach the pour point depression purpose, therefore the refining section in back must be set at pour point depression section rear portion, otherwise its quality product can't be up to standard, and back refining section air speed is lower than conventional hydrocracking, promptly to take more space reactor and load the back catalyst for refining, bring negative impact therefore for the reasonable utilization of reactor volume.
U.S. Pat 5,384,297 have introduced a kind of method of being produced low aromatic hydrocarbons low freezing point diesel fuel by the raw material hydrocracking of being rich in aromatic component.Because the hydrocracking catalyst that method adopted is the noble metal catalyst that contains three metal components such as ruthenium or palladium, raw material must carry out hydrofining earlier and remove impurity such as sulphur, nitrogen, and the refining oil that generates needs through separation removal H
2S and NH
3After, just can enter cracking zone and carry out hydrocracking.For reducing condensation point of diesel oil, at cracking zone second reactor cracking agent bottom filling pour point depression catalyzer, the contained molecular sieve of pour point depressant is ZSM-5.Because this patent is to utilize the pour point depressant that contains the ZSM-5 molecular sieve that isocrackate is dewaxed to reduce the condensation point of fraction of diesel oil, then this patent has U.S. Pat 5,935 equally, 414 existing deficiencies.In addition, the used hydrocracking catalyst of this patent is a noble metal catalyst, to H
2S and NH
3Very responsive, be easy to poisoning and deactivation.Therefore oil product must separate earlier with this catalyzer contact before, removes toxic impurities.The flow process that is adopted is two sections flow processs, this flow process than one-stage serial or single hop flow process complexity many, and investment cost is higher, operation easier is big.
3, summary of the invention
At the deficiencies in the prior art, the objective of the invention is to the problem that exists in the above-mentioned technology, the fraction oil of the developing a kind of simple possible method of diesel oil that raises productivity and improves the quality is produced under the prerequisite of fine-quality diesel oil guaranteeing, diesel yield is further enhanced.
Main design of the present invention is to look on the bright side of things to send out hydrocracking---isomerization combination process a kind of, promptly divide the isomery performance strong isomerization catalyst at the cracking agent back of cracking zone filling department, with paraffinic hydrocarbons, band short-side chain alkane and the optionally isomerization of the contour condensation point component of cyclic hydrocarbon institute belt length side chain alkane in the raw material, thereby reduce the condensation point of the diesel oil distillate of cracking generation, when guaranteeing to produce fine-quality diesel oil, will move behind the diesel oil cut point to improve diesel yield.Then according to the requirement of quality product, it is refining whether decision carries out the back for isomerized products, and industrial widely used hydrocracking catalyst all has good anti-NH at present
3And H
2The performance of S.Because the material that cracking produces directly carries out isomerization without heat exchange with separating, so flow process is simple, and is easy to operate, utilizes existing apparatus to realize.To achieve the object of the present invention, the major technique key that solves is the temperature matching problem between hydrocracking and isomerization, and selected isomerization catalyst and answer basically identical the work-ing life of cracking catalyst is in the time of just making the two be used in combination, inactivation synchronously, temperature raising synchronously.Isomerization catalyst is last bed or the next reactor that is contained in cracking zone in addition, so just can produce a desired effect, so the temperature matching problem between the two-stage process also can be resolved by the temperature of reaction of adjusting between bed or the cold hydrogen amount of reactor inlet is regulated isomery.
Based on above-mentioned design, the contriver searches out the practicable condition that is suitable for this design by a large amount of tests, and this inventive method comprises:
(1) fraction oil reaction raw materials contacts with hydrocracking catalyst under the condition that hydrogen exists, and carries out hydroconversion reactions in the hydrocracking reaction district, temperature of reaction is 250～500 ℃, reaction pressure is 3.0～20.0MPa, and hydrogen to oil volume ratio is 300～2000, and volume space velocity is 0.5～5.0h during liquid
-1
(2) reaction product after (1) step, the hydrocracking reaction district handled enters isomerization reaction zone, isocrackate is contacted with the heterogeneous catalyst with degree of depth isomery performance, make high condensation point content of wax component generation degree of depth isomerization reaction, thereby reduce the condensation point of oil product, temperature of reaction is 300～500 ℃, reaction pressure is 3.0～20.0MPa, and hydrogen to oil volume ratio is 300～2000, volume space velocity 2.0～10.0h during liquid
-1
(3) obtain the fine-quality diesel oil product by separation
The fraction oil reaction raw materials that processing method of the present invention is processed generally can be the petroleum fractions of cut scope in 200～580 ℃, and stock oil density is generally at 0.80～0.95g/cm
3Between, sulphur content is generally between 0～5w%, and nitrogen content for example can be selected from secondary processing diesel oil inferior, wax tailings, catalytic cracking turning oil, normal pressure fraction oil and the decompression fraction oil one or more generally between 100～3000 μ g/g.Substantially all contain paraffinic hydrocarbons, band short-side chain alkane and the contour condensation point component of cyclic hydrocarbon institute belt length side chain alkane in these raw materials, certainly because raw material properties is different or pretreated means difference, its content is also different, and high condensation point component is high more, can embody advantage of the present invention more.
The reaction conditions of hydrocracking is preferably: temperature of reaction is 330～440 ℃, and reaction pressure is 5.0～17.0MPa, and hydrogen to oil volume ratio is 700～1600, and volume space velocity is 1.0～4.0h during liquid
-1
Isomerized reaction conditions is preferably: 360～440 ℃ of temperature of reaction, reaction pressure 5.0～17.0MPa, hydrogen to oil volume ratio 700～1600, volume space velocity 4.0～8.0h during liquid
-1
Hydrocracking catalyst is to entering the restriction of foreign matter content in the cracking zone material, it mainly is requirement to nitrogen content, can according to circumstances before described hydrocracking reaction district, the hydrofining reaction district be set, to remove the deleterious impurity of hydrocracking catalyst, the nitrogen content in the general requirement hydrofining generation oil is between 0～2500 μ g/g.Hydrobon catalyst both can be with hydrocracking catalyst in same reactor, and be contained in the last bed of hydrocracking catalyst, reaction raw materials is at first carried out pre-treatment (we are commonly referred to as single-stage hydrocracking technology this situation), also can be before hydrocracking reactor, the reactor charge Hydrobon catalyst is set separately, after wherein reaction raw materials reacts through hydrofining reactor, can directly enter hydrocracking reactor (one-stage serial hydrocracking technology) without separating, the hydrogen sulfide that also can be at first hydrofining reaction be generated, behind the impurity removals such as ammonia, again other reaction product is sent into hydrocracking reaction district (secondary hydrogenation cracking technology).Because at present industrial hydrocracking catalyst anti-H 2 S, ammonia interference capability are stronger,, generally can select single-stage hydrocracking technology or one-stage serial hydrocracking technology so, reduce investment in order to simplify the operation.For two sections and one-stage serial hydrocracking technology, the operational condition of unifining process is: 250～500 ℃ of temperature of reaction, optimum range are 330～420 ℃; Reaction pressure 3.0～20.0MPa, optimum range are 5.0～17.0MPa, and hydrogen to oil volume ratio 300～2000, optimum range are 600～1200; Volume space velocity 0.5～4.0h
-1, optimum range 0.7～2.5h
-1
In addition, can be according to the character of reaction raw materials, to the particular cases such as requirement of product index, to consider isomerized reaction product of the present invention is carried out back refinement treatment, main purpose is to remove mercaptan to reach that unsaturated hydrocarbons is carried out hydrogenation is saturated.So described back refinement treatment generally can adopt hydrofining technology commonly used, temperature of reaction is generally 250～500 ℃, and optimum range is 330～440 ℃; Reaction pressure is generally 3.0～20.0MPa, and optimum range is 5.0～17.0MPa, and hydrogen to oil volume ratio is generally 300～2000, and optimum range is 700～1600; Volume space velocity is generally 6～20h
-1, optimum range 8～16h
-1Back catalyst for refining can be seated in the same reactor with isomerization catalyst, also can be seated in the different reactors.
Described hydroisomerizing cracking catalyst can certainly be contained in the different beds of a reactor together with hydrocracking catalyst, or is divided in the different reactors.
Reaction product after the described hydrocracking also can be as the case may be, consideration is at first sent reaction product into separation system, fraction of diesel oil is told, make it to enter isomerization reaction zone, tail oil can all or part ofly loop back the hydrocracking reaction district, also can be once by the hydrocracking reaction district, at this moment, all the other tail oils of tail oil part circulation time, and the once logical whole tail oils of out of date of tail oil can enter other device processing.Certainly, the reaction product after the hydrocracking also can directly enter isomerization reaction zone without separating, and except the diesel product quality that finally obtains improves, indexs such as the condensation point of other products or smoke point also will improve like this.
Before the hydrocracking reaction of the present invention district and isomerization reaction zone after Hydrobon catalyst can be catalyzer of the same race, also can in conjunction with both the reaction different situations, select different catalyzer.Described Hydrobon catalyst can be any suitable catalyzer that comprises prior art, and its major function is under the condition that hydrogen exists, and removes impurity such as sulphur in the raw material, nitrogen.Generally being to be carrier with inorganic porous refractory oxide, is the hydrogenation activity component with group vib and/or group VIII metal component, and relatively Chang Yong Hydrobon catalyst generally is with γ-Al
2O
3Be carrier, catalyst activity component is W, the Mo of VI family in the periodic table of elements and group VIII metal component, among Ni, the Co one or more.For example can adopt the Hydrobon catalyst with following composition: the weight with catalyzer is benchmark, WO
3Or MoO
3Content account for 20%～30%, NiO accounts for 3%～12%.
Hydrocracking catalyst of the present invention is to comprise any suitable catalyzer of prior art, the dual-function catalyst of forming by hydrogenation component and acidic components, its carrier mainly is a pure aluminium silicate, Magnesium Silicate q-agent, inorganic refractory oxides such as aluminum oxide, and the sial dispersion on the inorganic refractory oxide etc., cracking activity is mainly provided by the molecular sieve or the amorphous silicon aluminium that add wherein each type, the present invention recommends a kind of hydrocracking catalyst with following character, with the aluminum oxide is carrier, add modification Y type, one or both acidic components in modification β type and the modified zsm-5 zeolite, the hydrogenation activity component is W and/or the Mo in the group vib that is selected from the periodic table of elements, and Ni in the group VIII component and/or Co, weight percent with catalyzer is a benchmark, the content of described molecular sieve component on catalyzer is 3%-50%, WO
3And/or MoO
3Content account for 15%～30%, the content of NiO and/or CoO accounts for 3%～7%.
Isomerization catalyst of the present invention also can be any suitable catalyzer with isomery function, the present invention recommends a kind of catalyzer with following character: this catalyzer is carrier with the amorphous silicon aluminium, is the hydrogenation activity component with group vib and/or group VIII metal component.Wherein the hydrogenation active metals component preferably is selected from the W or the Mo of described group vib metal component and is selected from the Ni or the Co of group VIII metal component, in oxide compound, and WO wherein
3Or MoO
3Account for 20%～30% of total catalyst weight, NiO or CoO account for 3%～8% of total catalyst weight, the pore volume 0.2～0.5ml/g of catalyzer, and optimum range is 0.28～0.34, specific surface area is generally 180～500m
2/ g, preferably 210～400m
2/ g, infrared acidity is generally 0.2～0.7mM/g, is preferably 0.30～0.50mM/g, and wherein the acidity of L acid is generally 0.1～0.5mM/g, is preferably 0.1～0.4mM/g.The pore distribution of this catalyzer preferably hole of 3～8nm accounts for 85%～90% of total pore volume.This Preparation of catalysts method can be with reference to any suitable method in the prior art.The present invention recommends the preparation of a kind of glue method altogether, preparation process can be: (1) is prepared aluminum salt solution respectively, is contained the compound solution and the silicon-containing compound solution of described hydrogenation active metals component, and with it mixing, add precipitation agent, carry out co-precipitation, be characterized in filter cake that common glue obtains without conventional pulping and washing, and directly carry out drying and dehydrating, treat that material carries out extruded moulding behind partial dehydration, and then wash removal impurity.Work in-process wet bar drying and roasting again in washing back promptly obtains finished catalyst.The isocracking performance of this hydroisomerizing cracking catalyst is mainly provided by the more weak aprotic acid of acidity (L acid), and pore distribution concentration, so this catalyzer has the cracking performance of good isomery performance and appropriateness, have higher middle distillates oil selectivity, diesel product yield height and the low-temperature performance produced are good.
Compared with prior art, advantage of the inventive method and characteristics are:
1. in the cracking catalyst back of hydrocracking process filling part hydroisomerizing cracking catalyst, can effectively reduce the condensation point of fraction of diesel oil in the isocrackate, thereby the diesel product that the direct production low-temperature performance is good, or guaranteeing under the prerequisite of diesel quality, after prolong the cut point of diesel oil to improve diesel yield.Because the hydroisomerizing cracking catalyst itself has the middle distillates oil selectivity height, the raising of oily productive rate in more helping.And, diesel yield is declined to a great extent the cut point reach for guaranteeing qualified being forced to of condensation point of diesel oil not as conventional hydrocracking process.
2. utilize the distinctive degree of depth isomery of isomerization catalyst function, reduce condensation point of diesel oil, but the productive rate of fraction of diesel oil is constant substantially.And the dewaxing pour point depression catalyzer that adopts usually (containing ZSM series molecular sieve) more, be by to the paraffinic hydrocarbons cracking, remove high condensation point component and reduce the condensation point of diesel oil, so in pour point depression, can reduce the productive rate of diesel oil significantly, thereby increase the productive rate of non-purpose product light naphthar.
3. utilizing isomerization catalyst to reduce condensation point of diesel oil, is to realize by the mode to high condensation point paraffinic hydrocarbons degree of depth isomery.If make this catalyzer have good hydrogenation performance again, there is not unsaturated hydrocarbons so in the isomerization product substantially.Therefore.Can be according to the degree that requires to quality product, catalyst for refining after the filling of hydroisomerizing cracking catalyst back is a small amount of, or simply need not the back catalyst for refining.Usually the pour point depression catalyzer that adopts produces a large amount of alkene in cracking alkane, and the hydrogenation performance of this catalyzer self a little less than, therefore.Guarantee the quality and the stability of various products behind the pour point depression, must load the back catalyst for refining of some amount after the pour point depression section, it is saturated that the alkene that produces in the pour point depression process is carried out hydrogenation, reduced the utilization ratio of reactor useful volume therefrom.
4. the basically identical in work-ing life of selected hydrocracking catalyst and isomerization catalyst, the two deactivation rate is basic identical, can reach synchronous inactivation, temperature raising synchronously, stable operation is simple.And conventional dewaxing pour point depression catalyzer is bigger with the deactivation rate difference of hydrocracking catalyst, and with the prolongation of runtime, pour-point depressing process descends very fast, can't with the synchronous on request temperature raising of hydrocracking, the net effect of combination process is variation gradually.
5. selected hydrocracking and isomerization catalyst have good anti-NH
3And H
2The ability of S, therefore, raw material can directly enter cracking zone and isocracking section without separating after with hydrofining, makes process simplification of the present invention, and is simple to operate.
4, description of drawings
Fig. 1 is employed a kind of schema in the embodiment of the invention, and the one-stage serial flow process is partly adopted in hydrocracking wherein and hydrofining, last isolated tail oil recycle to extinction.
Fig. 2 is an employed another kind of schema in the embodiment of the invention, and hydrocracking wherein and hydrofining partly are the single-stage hydrocracking technical process, and last isolated tail oil all effluxes.
5, embodiment
Be further explained in detail the present invention below in conjunction with drawings and Examples.
Embodiment 1-4 and comparative example 1-2
Table the-1st uses the raw material oil properties in the embodiment of the invention
Table 1
| The stock oil numbering | Raw material-1 | Raw material-2 | Raw material-3 | Raw material-4 |
| Density (20 ℃), g/cm 3The boiling range scope, ℃ sulphur, μ g/g nitrogen, μ g/g condensation point, ℃ BMCI value | ????0.9083 ????329～543 ????15800 ????1450 ????36 ????44 | ????0.9133 ????319～531 ????22000 ????790 ????29 ????47 | ????0.8471 ????179～417 ????677 ????267 ????5 ????27.1 | ??0.9024 ??321～528 ??10100 ??1138 ??37 ??41.1 |
Table 2 is used Hydrobon catalyst physico-chemical properties in the embodiment of the invention
Table 2
| The catalyzer numbering | ????HT-1 | ????HT-2 | ????HT-3 | ????HT-4 |
| Chemical constitution, w% NiO MoO
3?γ-Al
2O
3Pore volume, ml/g specific surface, m
2/ g bulk density, g/ml profile mean particle size, | 3 19 surpluses, 0.38 200 0.73 clover φ 1.2 * (3-8) | 3～5 22～26 surpluses, 0.3 120 0.85～0.93 bunge bedstraw herb φ 1.2 * (3-8) | 3～5 23～26 surpluses 0.3～0.4＞160 0.88～0.94 bunge bedstraw herb φ 1.3 * (3-8) | 4 24 surpluses, 0.35 180 0.85～0.95 clover φ 1.3 * (3-8) |
Table 3 is physico-chemical properties of used hydrocracking catalyst in the embodiment of the invention
Table 3
| The catalyzer numbering | ????HC-1 | ????HC-2 | ????HC-3 | ????HC-4 |
| Chemical constitution, w% NiO WO 3MoO 3SiO 2Support modification zeolite content w% zeolite Si/Al atomic ratio pore volume, the ml/g specific surface, m 2/ g bulk density, g/ml profile mean particle size, mm | ? ????4.5 ????23.5 ? ????50.0 ????SiO 2-Al 2O 3+ chemical dealuminization Y 45 5～6 0.27 385 0.70～0.80 garden post bar φ 1.5-1.7 * (3-8) | ? ????9.0 ????23.0 ? ????32.0 ????SiO 2-Al 2O 3+ dealuminzation Y 20 5～6 0.34 255 0.85～0.95 garden post bar φ 1.5-1.7 * (3-8) | ? ????9.2 ????24.1 ? ????6.5 ????Al 2O 3+ deep sealumination modified Y 5 5.5～7.5 0.31 215 0.90～1.05 garden post bar φ 1.5-1.8 * (3-8) | ? ????6.02 ? ????20.4 ????13.2 ????Al 2O 3+ super steady Y 18 2.5～3.5 0.35 290 0.75～0.85 garden post bar φ 1.5-1.7 * (3-8) |
Table 4 is the character (this catalyzer also possesses the hydrogenation performance simultaneously) of used isomerization catalyst in the embodiment of the invention
Table 4
| The catalyzer numbering | ????IHC-1 |
| Chemical constitution, w% NiO WO 3SiO 2γ-Al 2O 3Pore volume, ml/g specific surface, m 2/ g bulk density, g/ml profile mean particle size, the infrared L acid of the infrared acidity mM/g catalyzer of mm catalyzer mM/g | 9.0 22.5 17.0 surpluses, 0.32 253 0.98 garden post bar φ 1.5-1.8 * (3-8) 0.45 0.25 |
Table 5 is the character of used back catalyst for refining in the embodiment of the invention.
Table 5
| The catalyzer numbering | ????HT-2 | ????HT-3 |
| Chemical constitution, w% NiO MoO 3SiO 2Carrier A l 2O 3Pore volume, ml/g specific surface, m 2/ g bulk density, g/ml profile mean particle size, mm | 4 22～26 6 surpluses, 0.3 120 0.85～0.93 bunge bedstraw herb φ 1.2 * (3-8) | 5 23～26 4 surpluses 0.3～0.4 165 0.88～0.94 bunge bedstraw herb φ 1.3 * (3-8) |
Below be employed several flow process introductions in embodiment and the comparative example: wherein flow process 1-3 is an employed flow process in the embodiment of the invention, and flow process 4-5 is employed flow process in the comparative example of the present invention.
Flow process 1: as shown in Figure 1, stock oil along pipeline 1 with enter hydrofining reaction bed 3 after the recycle hydrogen of pipeline 2 mixes, remove sulphur, nitrogen, behind the impurity such as oxygen, without separation, along pipeline 4 with after the recycle hydrogen of pipeline 5 mixes, directly enter cracking reaction bed 7 successively along pipeline 6, isomerization reaction bed 8, back refining reaction bed 9, successively carry out hydrocracking, isomerization, replenish hydrofining reaction, the final reaction effluent enters separation system 11 along pipeline 10 to be separated, isolated petroleum naphtha is along pipeline 12, kerosene is along pipeline 13, and diesel oil goes out device along pipeline 14, and tail oil enters the reaction product of pipeline 4 after hydrofining reaction bed 3 is handled along pipeline 16 and handles.We claim that usually this technology is one-stage serial tail oil recycle to extinction technology.
Flow process 2: this flow process is similar substantially to flow process 1, and just the tail oil of separation system 11 is by pipeline 16 return mechanism front portions, and directly disposablely goes out device.We claim that usually this technology is that one-stage serial once passes through technology.
Flow process 3: as shown in Figure 2, stock oil along pipeline 1 with enter hydrofining reaction bed 3, hydrocracking reaction bed 7, isomerization reaction bed 8, back refining reaction bed 9 after the recycle hydrogen of pipeline 2 mixes successively, reaction product enters separation system 11 by pipeline 10 at last, and the gas that has separated respectively goes out device along pipeline 15, tail oil along pipeline 17 along pipeline 14, diesel oil along pipeline 13, kerosene along pipeline 12, petroleum naphtha.We claim that usually this technology is that single hop once passes through technology.
More than several flow processs some embodiments that are general plotting of the present invention, conceive according to the present invention and on flow process, to also have other a lot of variations certainly.For example with regard to flow process 1, tail oil can not circulate, and once by by device, perhaps partly circulates, and part goes out device etc.In addition, tail oil also can according to circumstances select the reaction product after hydrofining is handled to mix processing again, also can directly enter hydrofining reaction bed 3 again with the stock oil mixing and begin to handle.For another example, also can separate earlier through the reaction product after 7 processing of hydrocracking reaction bed, selectively products such as portion of product such as diesel oil, petroleum naphtha are carried out next step isomerization as the case may be and handle, tail oil then return mechanism forward circulation is handled, or directly goes out device etc.Concerning flow process 3, also can select tail oil all to circulate, or part round-robin scheme etc.
Flow process 4: similar substantially to above-mentioned flow process 1, just there is not the isomerization treating part.
Flow process 5: similar substantially to above-mentioned flow process 1, just do not have the isomerization treating part, and tail oil passes through once, do not circulate.
Table 6 is embodiment of the invention test conditionss
Table 6
| Example | Embodiment | Comparative example | |||||
| Numbering | ????1 | ????2 | ????3 | ????4 | ????1 | ????2 | |
| Technical process stock oil reaction stagnation pressure, MPa | Flow process 1 one-stage serial＞370 ℃ of tail oil recycle to extinction stock oils-1 15.7 | Flow process 2 one-stage serials＞370 ℃ of tail oil one way are by stock oil-2 15.7 | Flow process 2 one-stage serials＞370 ℃ of tail oil one way are by stock oil-3 6.86 | Flow process 3 single hops＞370 ℃ of tail oils are once by stock oil-4 15.7 | Flow process 4 one-stage serials＞370 ℃ of recycle to extinction stock oils-1 15.7 | Flow process 5 one-stage serials＞370 ℃ of tail oil one way are by stock oil-3 6.86 | |
| Hydrofining | Catalyzer numbering hydrogen-oil ratio (v) volume space velocity h -1Temperature of reaction ℃ | ?HT-3 ?900∶1 ?1.0 ?379 | ?HT-2 ?950∶1 ?0.92 ?366 | ?HT-3 ?800∶1 ?2.0 ?368 | ?HT-3 ?1240∶1 ?11.5 ?406 | ??HT-3 ??900∶1 ??1.0 ??379 | ?HT-3 ?800∶1 ?2.0 ?368 |
| Hydrocracking | Catalyzer numbering hydrogen-oil ratio (v) volume space velocity h -1Temperature of reaction ℃ | ?HC-2 ?1100∶1 ?1.5 ?383 | ?HC-4 ?1200∶1 ?1.19 ?373 | ?HC-1 ?1000∶1 ?2.89 ?375 | ?HC-3 ?1240∶1 ?1.13 ?406 | ??HC-2 ??1100∶1 ??1.2 ??380 | ?HC-1 ?1000∶1 ?2.0 ?371 |
| Isomerization | Catalyzer numbering hydrogen-oil ratio (v) volume space velocity h -1Temperature of reaction ℃ | ?IHC-1 ?1100∶1 ?6.0 ?383 | ?IHC-1 ?1200∶1 ?7.0 ?373 | ?IHC-1 ?1000∶1 ?6.5 ?375 | ?IHC-1 ?1240∶1 ?5.0 ?406 | ||
| The back is refining | Catalyzer numbering hydrogen-oil ratio (v) volume space velocity h -1Temperature of reaction ℃ | ?HT-3 ?1100∶1 ?15.0 ?383 | ?HT-2 ?1200∶1 ?13.8 ?373 | ?HT-3 ?1000∶1 ?15.0 ?375 | ?HT-3 ?1240∶1 ?12.9 ?406 | ??HT-3 ??1100∶1 ??15.0 ??380 | ?HT-3 ?1000∶1 ?15.0 ?375 |
Table 7 is the diesel yield and the character of the embodiment of the invention and comparative example
Table 7
| Example | Embodiment | Comparative example | ||||||
| Numbering | ??????????1 | ????2 | ???????????3 | ????4 | ??????1 | ????2 | ||
| Fraction of diesel oil scope ℃ productive rate w% condensation point ℃ cetane value | 282～370 21.82 -12 65.8 | ?282～385 ?25.78 ?-4 ?67.9 | ??282～350 ??11.76 ??-22 ??61.4 | ??180～340 ??47.40 ??-29 ??49.0 | ??180～360 ??55.42 ??-18 ??52.7 | ??249～371 ??24.52 ??-24 ??58.2 | ??282～370 ??21.92 ??0 ??68.1 | ??180～340 ??47.2 ??-16 ??50.1 |
As seen adopting hydrocracking---hydroisomerizing cracking combination process can effectively reduce the condensation point of fraction of diesel oil, under the prerequisite that guarantees diesel quality, can reach the purpose of increasing output of diesel oil.
Claims (10)
1, a kind of by the raise productivity and improve the quality method of diesel oil of fraction oil, comprising:
(1) the distillate reaction raw materials contacts with hydrocracking catalyst under the condition that hydrogen exists, and carries out hydroconversion reactions in the hydrocracking reaction district, temperature of reaction is 250～500 ℃, reaction pressure is 3.0～20.0MPa, and hydrogen to oil volume ratio is 300～2000, and volume space velocity is 0.5～5.0h during liquid
-1
(2) reaction product after (1) step, the hydrocracking reaction district handled enters isomerization reaction zone, isocrackate is contacted with the isomerization catalyst with degree of depth isomery performance, make high condensation point content of wax component generation degree of depth isomerization reaction, thereby reduce the condensation point of oil product, temperature of reaction is 300～500 ℃, reaction pressure is 3.0～20.0MPa, and hydrogen to oil volume ratio is 300～2000, volume space velocity 2.0～10.0h during liquid
-1
(3) obtain the fine-quality diesel oil product by separation.
2, described according to claim 1 by the raise productivity and improve the quality method of diesel oil of fraction oil, it is characterized in that described distillate reaction raw materials is the petroleum fractions of boiling range scope in 200～580 ℃.
3, described according to claim 1 by the raise productivity and improve the quality method of diesel oil of fraction oil, the reaction conditions that it is characterized in that described hydrocracking is: temperature of reaction is 330～440 ℃, reaction pressure is 5.0～17.0MPa, and hydrogen to oil volume ratio is 700～1600, and volume space velocity is 1.0～4.0h during liquid
-1
4, described according to claim 1 by the raise productivity and improve the quality method of diesel oil of fraction oil, it is characterized in that described isomerized reaction conditions is: 360～440 ℃ of temperature of reaction, reaction pressure 5.0～17.0MPa, hydrogen to oil volume ratio 700～1600, volume space velocity 4.0～8.0h during liquid
-1
5, described according to claim 1 by the raise productivity and improve the quality method of diesel oil of fraction oil, it is characterized in that also being provided with the hydrofining reaction district before the described hydrocracking reaction district, to remove to the deleterious impurity of hydrocracking catalyst.
6, it is characterized in that by the raise productivity and improve the quality method of diesel oil of fraction oil described isomerized reaction product also needs to carry out the back refinement treatment according to claim 1 is described, remove mercaptan and unsaturated hydrocarbons is carried out hydrogenation saturated.
7, described according to claim 1 by the raise productivity and improve the quality method of diesel oil of fraction oil, it is characterized in that described hydrocracking catalyst is is carrier with the aluminum oxide, in interpolation modification Y type, modification β type and the modified zsm-5 zeolite one or more are as acidic components, the hydrogenation activity component is W and/or the Mo in the group vib that is selected from the periodic table of elements, and Ni in the group VIII component and/or Co, weight percent with catalyzer is a benchmark, the content of described molecular sieve component on catalyzer is 3%-50%, WO
3And/or MoO
3Content account for 15%～30%, the content of NiO and/or CoO accounts for 3%～7%.
8, described according to claim 1 by the raise productivity and improve the quality method of diesel oil of fraction oil, it is characterized in that described isomerization catalyst is is carrier with the amorphous silicon aluminium, with W or the Mo that is selected from the group vib metal component, with Ni that is selected from the group VIII metal component or Co be the hydrogenation activity component, in oxide compound, WO wherein
3Or MoO
3Account for 20%～30% of total catalyst weight, NiO or CoO account for 3%～12% of total catalyst weight, and the pore volume of catalyzer is 0.2～0.5ml/g, and specific surface area is 180～500m
2/ g, infrared acidity is 0.2～0.7mM/g, wherein the acidity of L acid is 0.1～0.5mM/g.
9, described according to claim 5 by the raise productivity and improve the quality method of diesel oil of fraction oil, it is characterized in that described unifining process is to carry out under the condition of hydrogen and Hydrobon catalyst existence, operational condition is: 250～500 ℃ of temperature of reaction, reaction pressure 3.0～20.0MPa, hydrogen to oil volume ratio 300～2000, volume space velocity 0.5～4.0h during liquid
-1
10, described according to claim 6 by the raise productivity and improve the quality method of diesel oil of fraction oil, it is characterized in that described back refinement treatment is the hydrofining technology, in the presence of hydrogen and Hydrobon catalyst, carry out, temperature of reaction is 250～500 ℃, reaction pressure is 3.0～20.0MPa, hydrogen to oil volume ratio is 300～2000, and volume space velocity is 6～20h during liquid
-1
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