CN1952067A - Two-segment hydrocracking method - Google Patents
Two-segment hydrocracking method Download PDFInfo
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- CN1952067A CN1952067A CN 200510047479 CN200510047479A CN1952067A CN 1952067 A CN1952067 A CN 1952067A CN 200510047479 CN200510047479 CN 200510047479 CN 200510047479 A CN200510047479 A CN 200510047479A CN 1952067 A CN1952067 A CN 1952067A
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Abstract
The invention disclosed a second-stage hydrocracking method of a kind of copious high-quality intermediate fraction. After mixing the material with hydrogen, the mixture enters the first stage hydrocracking reactor. The first stage adopts two catalysts in hydrocracking process, charge the refining agent from the top part and cracking agent from the below part. The oil from the end of the first stage enters the second stage hydrocracking reactor. The invention uses one suit hydrogen-recycling and separating system. The invention not only maintains the advantage of the one-stage and two catalysts hydrocracking technology such as high distillate yield, less consumption of chemical hydrogen and low catalyst cost, it also has the advantage of the one-stage and cascade hydrocracking technology such as strong adaptivity for the material, long catalyst's service life and good quality of the products. The invention is mainly applicable to the hydrocracking process which uses various heavy magnesium carbonate distillates as the material to produce high quality intermediate fraction.
Description
Technical field
The invention discloses the two-segment hydrocracking method of a kind of method for hydrogen cracking, particularly a kind of voluminous intermediate oil, i.e. the unconverted tail oil of first section hydrocracking carries out second section hydrocracking.
Background technology
In recent years, corresponding variation has taken place with expanding economy in the demand structure in petroleum products market, and the demand of vapour, coal, the diesel oil especially demand of intermediate oil such as coal, diesel oil rises, and the demand of oil fuel descends.The crude oil that the refinery processed is heaviness day by day also, and the specification of quality of motor spirits such as vapour, coal, bavin is but improved constantly, and environmental regulation is also strict day by day.The technology of therefore, production high-quality intermediate oil more and more comes into one's own.The wide scope of material that hydrocracking is processed, products scheme is flexible, and the liquid product yield height can obtain high-quality power fuel and industrial chemicals, and hydrocracking process and technology more and more are subjected to the generally attention of each major oil companies of the world.Hydrocracking process generally can be divided into one-stage process and two-stage method, and wherein one-stage process comprises single hop (also claiming the single hop potion) and single hop series connection again.Operating method mainly is divided into cyclical operation mode and once-through operation mode.Single hop technology is used a kind of hydrocracking catalyst of anti-organonitrogen, and directly by hydrocracking catalyst, technological process is the simplest for raw material, and the operation air speed is higher, but the raw material range of processing is narrow, and product Air China ature of coal amount is relatively poor.Hydrobon catalyst and hydrocracking catalyst series connection are used in the single hop series connection, the centre need not to separate, because used hydrocracking catalyst does not have the ability of anti-organonitrogen, requirement removes the sulphur nitrogen impurity totally at hydrofining reactor, so generally can only operate than under the low-speed, the plant construction investment cost is higher relatively and be subjected to the restriction of catalyst system therefor (hydrocracking catalyst that molecular sieve content is higher) performance, and the yield of the resulting intermediate oil of hydrocracking (boat coal and diesel oil) is the highest generally can only to be reached about 65m～70m%.Along with the maximization day by day of oil refining enterprise, the large-scale hydroeracking unit of planning construction is more and more, to reach scale and benefit.Single cover working ability of these devices is mostly more than 2,000,000 tons/year.If these large-scale hydroeracking units adopt conventional single hop series connection or single hop Technology by single covering device construction, because the ducts starting cost and the trucking costs of large equipments such as reactor, feedstock pump, interchanger are huge, the plant construction investment will be increased greatly, influence economic benefit of enterprises; And if build up two covering devices, then will increase owing to table of equipment digital display work, equally also will increase the construction investment of device, and will increase process cost.
Existing two-stage hydrocracking technology, as US3702818, relate to first section stock oil and at first remove impurity through the hydrofining section, isolating liquid enters the hydrocracking section, first section tail oil enters second section and continues cracking, and this is conventional two-stage hydrocracking technological process.US3549515 uses the one-stage serial flow process for first section, exists the deficiency of above-mentioned one-stage serial technology.US4404088 relates to increases a hydrocracking reaction section, improve liquid product yield when changing products scheme, but flow process is longer.Though these technology schemes are flexible, the technical process complexity, investment increases.
Summary of the invention
At the deficiencies in the prior art, the object of the present invention is to provide a kind of improved two-stage hydrocracking technology, both kept advantages such as the low and catalyzer total expenses of single-section two-catalyst hydrocracking technology intermediate oil yield height, chemical hydrogen consumption is few, had that single hop serial hydrocracking technology is strong to stock oil adaptability, the catalyst runs cycle is long simultaneously again and characteristics such as hydrocracking good product quality.Compare with existing two-stage hydrocracking technology, technical process is simple relatively again, and the intermediate oil yield is higher.
Those skilled in the art it is generally acknowledged that in single-stage hydrocracking technology, its catalyzer has anti-nitrogen, therefore can directly will not carry out hydrocracking reaction through hydrorefined raw material.But by the in-depth analysis of existing single-stage hydrocracking technology is learnt, though catalyzer has stronger nitrogen resistance in the single-stage hydrocracking technology, but at first the part catalyzer that contacts with not refining raw material is under the dense environment of organonitrogen, the acid sites of catalyzer (lytic activity center) is subjected to the strongly inhibited of organonitrogen, can not bring into play splitting action substantially.This part catalyzer generally only plays the effect of common catalyst for refining, promptly removes the impurity such as organonitrogen in the raw material, and after organonitrogen content in the logistics reduced, the hydrocracking catalyst of back was brought into play the cracking function gradually.That is to say that the nitrogen resistance of single-stage hydrocracking catalyzer is limited, just can not give full play of the hydrocracking performance when surpassing its anti-nitrogen limit, can only play common hydrofining effect.On the other hand, the single-stage hydrocracking catalyzer is not to design at the hydrofining purpose after all, its hydrofining performance and Hydrobon catalyst not as designing at the hydrofining purpose specially, and the cost of hydrocracking catalyst will be much higher than Hydrobon catalyst.
According to above research, the present invention proposes a kind of two-stage hydrocracking technological process, a kind of two-segment hydrocracking method of high-output qulified intermediate oil particularly, adopt the two-stage process flow process, under suitable hydroconversion condition, the heavy distillate raw material contacts with first section catalyzer with hydrogen, reaction effluent enters separation system, two doses of technologies of single hop are adopted in first section hydrocracking, reaction mass contacts with Hydrobon catalyst earlier, contacts with hydrocracking catalyst then, and first section isolated tail oil of reaction product is as second section hydrocracking charging, second section feeding contacts with second section hydrocracking catalyst with hydrogen, and reaction effluent enters separation system.Two doses of technologies of described single hop are on the basis of a kind of type of anti-organonitrogen hydrocracking catalyst of single-stage hydrocracking process using, part single-stage hydrocracking catalyzer is replaced with Hydrobon catalyst, reaction mass contacts with Hydrobon catalyst earlier, contacts with the single-stage hydrocracking catalyzer then.
Two-stage hydrocracking technological process of the present invention, particular content comprises:
A certain proportion of Hydrobon catalyst is loaded on (1) first section hydrocracking reactor top, and a certain proportion of hydrocracking catalyst is loaded in the bottom; (2) stock oil and hydrogen are mixed into first section hydrocracking reactor, at first in reactions such as Hydrobon catalyst reaction zone generation hydrogenating desulfurization, denitrogenation, deoxidation, aromatic hydrocarbons are full, directly enter the hydrocracking catalyst reaction zone through hydrorefined logistics, reactions such as the saturated and hydrocracking of aromatic hydrocarbons take place there; (3) first sections hydrocracking generate oil and enter high-pressure separator, and the gas circulation of separating is used, and the liquid product of separating enters fractionating system; (4) the unconverted tail oil that obtains of fractionating system and hydrogen are mixed enters second section hydrocracking reactor and continues cracking, to reach the purpose of voluminous intermediate oil.Wherein the hydrocracking catalyst that uses of first section hydrocracking is the single-stage hydrocracking catalyzer, and the single-stage hydrocracking catalyzer has the function of anti-organonitrogen, and raw material can directly contact with the single-stage hydrocracking catalyzer without hydrofining.Because it is less to enter the various impurity of the material of second section hydrocracking reactor, can use the hydrocracking catalyst of non-anti-organonitrogen.
In addition, according to the practical situation of equipment, the Hydrobon catalyst of first section hydrocracking process and single-stage hydrocracking catalyzer can be seated in the reactor in the inventive method, also can be seated in two or more reactors.Partly or entirely being seated in first reactor of Hydrobon catalyst, partly or entirely being seated in second reactor of single-stage hydrocracking catalyzer, reaction mass at first passes through the Hydrobon catalyst bed, passes through the single-stage hydrocracking beds then.But this mode is not identical with one-stage serial technology, because (one-stage serial technology is used the not hydrocracking catalyst of anti-organonitrogen to the type difference of hydrocracking catalyst, the present invention uses the single-stage hydrocracking catalyzer of anti-nitrogen), the technology controlling and process requirement is also different, and (the organonitrogen content of material needs strict control and detection after the hydrofining of one-stage serial technology, the present invention does not control, when adopting two kinds of catalyzer of single reactor charge, in fact also can't directly control and detect).But along with the development of equipment scale, and control is easy, generally can implement in a reactor, the reactor top Hydrobon catalyst of packing into, and the bottom single-stage hydrocracking catalyzer of packing into, stock oil enters reactor from top.In essence, single-section two-catalyst hydrocracking technology is to replace part single-stage hydrocracking catalyzer with Hydrobon catalyst; And one-stage serial hydrocracking technology is on the basis that keeps all hydrocracking catalysts, uses Hydrobon catalyst before it, and its cumulative volume air speed is lower when other condition is identical, and the organonitrogen content of strict control refined products.
Compared with prior art, characteristics of the present invention are: it can be in advantage such as keep that single-stage hydrocracking technical matters flow process is simple, volume space velocity big and the plant construction investment is relatively low, overcome again the stock oil bad adaptability, short, products production scheme of catalyst runs cycle is not a deficiency such as very flexible, but also have that intermediate oil yield height, chemical hydrogen consumption are low, characteristics such as good product quality, catalyzer total expenses are low.In addition, in first section of the present invention, adopt " two doses of single hops " (in single-stage hydrocracking technology, use two kinds of catalyzer: Hydrobon catalyst and single-stage hydrocracking catalyzer), make all single-stage hydrocracking catalyzer all give full play of its hydrocracking performance on the one hand, made full use of the hydrogenation performance that the single-stage hydrocracking catalyzer has on the other hand, the impurity process of taking off of the degree of depth was carried out in an enterprising step of single-stage hydrocracking catalyzer.So compare with existing one-stage serial hydrocracking technology, process makes full use of the present invention the hydrogenation performance of hydrocracking catalyst; Compare with existing single-stage hydrocracking technology, technology of the present invention has been given full play to the cracking performance of all hydrocracking catalysts, and all properties of hydrocracking catalyst is all made full use of.We can say, in single-stage hydrocracking technology of the present invention, employed Hydrobon catalyst, on actual functional capability, with the function of the single-stage hydrocracking catalyzer of existing single-stage hydrocracking technology same reaction position is identical, has promptly substituted part single-stage hydrocracking catalyzer with Hydrobon catalyst, does not only reduce reactivity worth on the result, also than former scheme obviously outstanding progress has been arranged, this is that those skilled in the art institute is beyond thought.
The present invention had both kept advantages such as the low and catalyzer total expenses of single-section two-catalyst hydrocracking technology intermediate oil yield height, chemical hydrogen consumption is few, had that single hop serial hydrocracking technology is strong to stock oil adaptability, the catalyst runs cycle is long simultaneously again and characteristics such as hydrocracking good product quality.In addition, the present invention adopts two doses of technology of single hop for first section, compares with conventional single hop technology, and the intermediate oil yield is higher, better quality; Compare with conventional single hop serial connection technology, the intermediate oil yield improves greatly.First section tail oil enters second section and continues cracking.Compare with existing two-stage hydrocracking technology, the intermediate oil yield is higher, and technical process is simple relatively.
Description of drawings
Fig. 1 is a kind of principle process flow sheet of the present invention.
Embodiment
Technical process of the present invention is: adopt the two-stage process flow process, under suitable hydroconversion condition, the heavy distillate raw material contacts with first section catalyzer with hydrogen, reaction effluent enters separation system, isolated tail oil is as second section feeding, second section feeding contacts with second section hydrocracking catalyst with hydrogen, and reaction effluent enters separation system.First section hydrocracking and second section hydrocracking can be adopted the common separation system.The cut point of tail oil can be adjusted according to product needed, is generally 320～410 ℃.
The used stock oil of the present invention can be one or more in the synthetic wet goods cut of straight-run gas oil, decompressed wax oil, wax tailings, catalytic cycle oil, deasphalted oil, shale oil and the coal of crude oil.
Employed Hydrobon catalyst can be conventional hydrorefining catalyst for heavy oil in first section hydrocracking, hydrocracking catalyst is conventional single-stage hydrocracking catalyzer, they all are made up of carrier and the hydrogenation metal that is loaded in above it, with the weight percent is benchmark, hydrogenation metal is a base metal, comprises group vib active metal component in the periodic table of elements, as tungsten and/or molybdenum, count 8%～35% with metal oxide weight, 12%～30% is better; And the group VIII reactive metal, as nickel and/or cobalt, count 1%～7% with metal oxide weight, 1.5%～6% is better.The carrier that Hydrobon catalyst uses is an inorganic refractory oxide, as aluminum oxide, amorphous silicon aluminium, silicon oxide, titanium oxide etc.The commercial Hydrobon catalyst that can select for use mainly contains: HC-K, the HC-T that Uop Inc. develops, HC-P and Fushun Petrochemical Research Institute develop 3936,3996, FF-16, FF-26 etc.The carrier of hydrocracking catalyst is aluminum oxide, unformed silicon and molecular sieve etc., and molecular sieve content is generally 5%～60%.Use the single-stage hydrocracking catalyzer in first section hydrocracking, can select commercial single-stage hydrocracking catalyzer for use with anti-organonitrogen function, as ZHC-01, ZHC-02, ZHC-04, FC-14, the FC-28 that Fushun Petrochemical Research Institute develops, the ICR126 that CHEVRON company develops etc.The volume loadings of Hydrobon catalyst and single-stage hydrocracking catalyzer is 2: 8～8: 2 in first section hydrocracking, is preferably 3: 7～7: 3.Second section hydrocracking can be used conventional commercial hydrocracking catalyst, because the foreign matter content of charging is lower, must not adopt the hydrocracking catalyst of anti-nitrogen, operable commercial hydrocracking catalyst is except that one section used single-stage hydrocracking catalyzer, can also use as the DHC-32 of Uop Inc., DHC-39, HC-43, HC-115 etc., Fushun Petrochemical Research Institute develop 3971,3974,3976, FC-12, FC-16, FC-26 etc.
Hydrocracking process of the present invention comprises following detailed process and operational condition:
The heavy distillate raw material is under the condition that hydrogen exists, obtain first section effluent with first section catalyzer contact reacts, temperature of reaction is 330～480 ℃, and reaction pressure is 5.0～20.0MPa, hydrogen to oil volume ratio is 100～4000, and volume space velocity is 0.2～4.0h during liquid
-1
First section effluent is through separating product and tail oils such as obtaining gas and petroleum naphtha, kerosene, diesel oil.
Tail oil is as the raw material of second section hydrocracking, and temperature of reaction is 250～500 ℃, and reaction pressure is 5.0～20.0MPa, and hydrogen to oil volume ratio is 100～4000, and volume space velocity is 1.0～10.0h during liquid
-1
Second section effluent is through separating product and tail oils such as obtaining gas and petroleum naphtha, kerosene, diesel oil.First section reaction effluent and second section reaction effluent enter same separation system.
The reaction conditions of first section hydrocracking is preferably: temperature of reaction is 350～450 ℃, and reaction pressure is 8.0～17.0MPa, and hydrogen to oil volume ratio is 400～2000, and volume space velocity is 0.5～3.0h during liquid
-1
The reaction conditions of second section hydrocracking is preferably: temperature of reaction is 300～440 ℃, and reaction pressure is 8.0～17.0MPa, and hydrogen to oil volume ratio is 400～2000, and volume space velocity is 1.0～4.0h during liquid
-1
Second section hydrocracking selected for use has good anti-NH
3And H
2The hydrocracking catalyst of S performance, can be shared a cover recycle hydrogen system and a fractionating system, make process simplification of the present invention, simple to operate.
Further explain the present invention below in conjunction with drawings and Examples.
Stock oil along pipeline 1 with enter hydrofining reaction district 3 after the recycle hydrogen of pipeline 2 mixes, remove S, N, behind the impurity such as O, directly enter hydrocracking reaction district 4 without separating, on the single-stage hydrocracking catalyzer, react, reaction effluent enters separation system 6 along pipeline 5 to be separated, isolated gas is along pipeline 7, petroleum naphtha is along pipeline 8, kerosene is along pipeline 9, diesel oil goes out device along pipeline 10, tail oil mixes along the recycle hydrogen of pipeline 11 with pipeline 12, enters second section cracking case 13, and reaction effluent enters separation system 6 together along the logistics of pipeline 14 and pipeline 5 to be separated.
Below by embodiment the present invention program and effect are described.
Two doses of recycle to extinction flow implementations of table 1 single hop example
| |
Reference example 1 | |
| Stock oil character | VGO in the sand | VGO in the sand |
| Density/kgm -3 | 924.9 | 924.9 |
| Boiling range/℃ | 337～539 | 337～539 |
| Sulphur content/m% | 2.53 | 2.53 |
| Nitrogen content/μ gg -1 | 766 | 766 |
| The hydrocracking process condition | ||
| Catalyzer | 3996/ZHC-02 | ZHC-02 |
| Catalyst loading specific volume example | 40∶60 | / |
| Pressure/MPa | 15.7 | 15.7 |
| Temperature/℃ | 407/410 | 415 |
| Volume space velocity/h -1 | 1.0 | 1.0 |
| Hydrogen to oil volume ratio | 1240∶1 | 1240∶1 |
| Per pass conversion, m% | 60.0 | 60.0 |
| The heavy naphtha yield, m% | 10.6 | 14.2 |
| The heavy naphtha virtue is dived | 62.8 | 59.9 |
| The boat yield of coal, m% | 33.7 | 32.8 |
| Boat coal smoke point/mm | 30 | 27 |
| Diesel yield, m% | 46.0 | 42.6 |
| Diesel cetane-number | 68.9 | 64.5 |
Table 2 stock oil one way is by the flow implementation example
| | Embodiment | 2 | Reference example 2 | Reference example 3 | Reference example 4 |
| Stock oil character | Iran VGO | Iran VGO | Iran VGO | Iran VGO | |
| Density/kgm -3 | 913.5 | 913.5 | 913.5 | 913.5 | |
| Boiling range/℃ | 285～537 | 285～537 | 285～537 | 285～537 | |
| Sulphur content/m% | 1.74 | 1.74 | 1.74 | 1.74 | |
| Nitrogen content/μ gg -1 | 1514 | 1514 | 1514 | 1514 | |
| The hydrocracking process condition | |||||
| Catalyzer | FF-1 6/FC-14 | FC-14 | FF-16/3976 | FF-1 6/3976 | |
| The catalyst loading volume ratio | 42∶58 | / | 1∶1 | 42∶58 | |
| Pressure/MPa | 15.7 | 15.7 | 15.7 | 15.7 | |
| Temperature/℃ | 402/403 | 409 | 396/401 | 402/403 | |
| Total air speed/h -1 | 1.5 | 1.5 | 0.8 | 1.5 | |
| Hydrogen to oil volume ratio | 1000∶1 | 1000∶1 | 1000∶1 | 1000∶1 | |
| Per pass conversion, m% | 81.7 | 82.0 | 82.6 | 56.3 | |
| The heavy naphtha yield, m% | 6.2 | 10.5 | 17.6 | 9.4 | |
| The heavy naphtha virtue is dived | 52.9 | 50.3 | 49.1 | 49.8 | |
| The boat yield of coal, m% | 32.9 | 30.5 | 40.3 | 28.7 | |
| Boat coal smoke point/mm | 25 | 22 | 27 | 24 | |
| Diesel yield, m% | 39.0 | 36.3 | 12.8 | 12.3 | |
| Diesel cetane-number | 59.2 | 48.2 | 60.3 | 61.2 | |
| The tail oil yield, m% | 18.3 | 18.0 | 17.4 | 44.7 |
The main character of two sections recycle to extinction embodiment of table 3 and stock oil that comparative example uses
| Density (20 ℃)/kgm -3 | 920.5 |
| The boiling range scope/℃ | 325～520 |
| Sulphur content, m% | 2.45 |
| Nitrogen content/μ gg -1 | 842 |
| Condensation point/℃ | 32 |
| The BMCI value | 49.8 |
The reaction conditions of two sections recycle to extinction embodiment of table 4 and comparative example and product distribute
| Technical process | Two-stage hydrocracking,＞385 ℃ of cuts are recycled to second section | Two-stage hydrocracking,＞385 ℃ of cuts are recycled to second section | Two-stage hydrocracking,＞385 ℃ of cuts are recycled to second section | Two-stage hydrocracking,＞385 ℃ of cuts are recycled to second | ||||
| Numbering | Embodiment | |||||||
| 3 | |
Reference example 5 | Reference example 6 | |||||
| Conversion zone | First section | Second section | First section | Second section | First section | Second section | First section | Second section |
| Catalyzer | FF-26 /FC-14 | FC-28 | FF-26 /FC-14 | FC-28 | FF-26 /FC-26 | FC-28 | FC-14 | FC-28 |
| Hydrogen to oil volume ratio | 900∶1 | 900∶1 | 900∶1 | 900∶1 | 900∶1 | 900∶1 | 900∶1 | 900∶1 |
| Reaction stagnation pressure/MPa | 13.7 | |||||||
| Volume space velocity/h -1 | 1.20 | 2.40 | 1.20 | 2.44 | 0.90 | 2.40 | 1.20 | 2.40 |
| Temperature of reaction/℃ | 400/40 8 | 365 | 397/40 5 | 370 | 400/39 6 | 363 | 407 | 367 |
| ＞385 ℃ of per pass conversion, m% | 60 | 60 | 55 | 65 | 60 | 60 | 60 | 60 |
| Product distributes, m% | ||||||||
| ＜79℃ | 7.31 | 7.19 | 9.11 | 7.40 | ||||
| 79～130℃ | 11.84 | 11.61 | 14.03 | 12.05 | ||||
| 130～230℃ | 27.94 | 26.77 | 29.94 | 26.83 | ||||
| 230～385℃ | 48.23 | 49.90 | 40.42 | 48.10 | ||||
| 130～385 ℃ of intermediate oil yields | 76.17 | 76.67 | 70.36 | 74.93 | ||||
| Chemistry hydrogen consumption, m% | 2.49 | 2.45 | 2.64 | 2.52 | ||||
Annotate: first section hydrocracking Hydrobon catalyst of embodiment and single-stage hydrocracking catalyst loading ratio are 44: 56 (v%), and Comparative Examples 5 Hydrobon catalysts and hydrocracking catalyst filling ratio are 50: 50 (v%).
The character of kerosene and diesel oil in two sections recycle to extinction embodiment of table 5 and the comparative example
| Numbering | |
|
Reference example 5 | Reference example 6 |
| 130～230 ℃ of boat coals | ||||
| Freezing point/℃ | ＜-60 | ＜-60 | ＜-60 | ＜-60 |
| Smoke point/mm | 29 | 28 | 30 | 25 |
| Aromatic hydrocarbons, v% | 10.4 | 10.1 | 8.2 | 12.3 |
| Naphthalene is a hydrocarbon, v% | 0.08 | 0.06 | 0.05 | 0.12 |
| 230～385 ℃ of diesel oil | ||||
| Condensation point/℃ | -30 | -28 | -34 | -21 |
| Cetane value | 61.3 | 57.4 | 56.6 | 54.3 |
Show by above embodiment, adopt two-stage hydrocracking technology, first section reactor adopts two doses of single hops (using hydrofining and two kinds of catalyzer of hydrocracking in the single-stage hydrocracking technology), second section reactor adopts hydrocracking catalyst, both kept advantages such as the low and catalyzer total expenses of single-section two-catalyst hydrocracking technology intermediate oil yield height, chemical hydrogen consumption is few, had that single hop serial hydrocracking technology is strong to stock oil adaptability, the catalyst runs cycle is long simultaneously again and characteristics such as hydrocracking good product quality.In addition, the present invention adopts two doses of technology of single hop for first section, compares with conventional single hop technology, and the intermediate oil yield is higher, better quality; Compare with conventional single hop serial connection technology, the intermediate oil yield improves greatly.Compare with one-stage serial technology, the inventive method can improve the processing air speed greatly, under close condition, the inventive method air speed can reach 1.2～1.5 times of one-stage serial technology, be 1.2～1.5 times that amount of finish can reach one-stage serial technology, and middle distillates oil selectivity obviously also is higher than one-stage serial technology.If adopt close air speed (reference example 4) in the one-stage serial technology, because volume space velocity is bigger, the requirement that refining back organonitrogen does not reach cracking catalyst, cracking activity obviously reduces, and the deactivation rate of hydrocracking catalyst is very fast.Compare with existing two-stage hydrocracking technology, the inventive method intermediate oil yield is higher, and technical process is simple relatively.
Claims (9)
1, a kind of two-segment hydrocracking method of high-output qulified intermediate oil, adopt the two-stage process flow process, under suitable hydroconversion condition, the heavy distillate raw material contacts with first section catalyzer with hydrogen, reaction effluent enters separation system, it is characterized in that two doses of technologies of first section hydrocracking employing single hop, reaction mass contacts with Hydrobon catalyst earlier, contact with hydrocracking catalyst then, first section isolated tail oil of reaction product is as second section hydrocracking charging, second section feeding contacts with second section hydrocracking catalyst with hydrogen, and reaction effluent enters separation system; Wherein the hydrocracking catalyst in first section hydrocracking is the single-stage hydrocracking catalyzer.
2, in accordance with the method for claim 1, it is characterized in that described stock oil can be one or more in straight-run gas oil, decompressed wax oil, wax tailings, catalytic cycle oil, shale oil, deasphalted oil and the coal synthetic oil of crude oil.
3, in accordance with the method for claim 1, it is characterized in that described single-stage hydrocracking catalyzer has the function of anti-organonitrogen, raw material can directly contact with the single-stage hydrocracking catalyzer without hydrofining.
4, in accordance with the method for claim 1, the volume ratio that it is characterized in that described first section Hydrobon catalyst and single-stage hydrocracking catalyzer is 2: 8～8: 2.
5, in accordance with the method for claim 1, the volume ratio that it is characterized in that described first section Hydrobon catalyst and single-stage hydrocracking catalyzer is 3: 7～7: 3.
6, in accordance with the method for claim 1, it is characterized in that described first section reaction conditions is: working pressure is 5.0MPa～20.0MPa, and volume space velocity is 0.2h during total liquid
-1～4.0h
-1, hydrogen to oil volume ratio is 100: 1～4000: 1, average reaction temperature is 330～480 ℃; Second section reaction conditions is: working pressure is 5.0～20.0MPa, and volume space velocity is 1.0～10.0h during liquid
-1, hydrogen to oil volume ratio is 100～4000: 1, average reaction temperature is 250～500 ℃.
7, in accordance with the method for claim 1, it is characterized in that described first section reaction conditions is: working pressure is 8.0MPa～17.0MPa, and volume space velocity is 0.5h during total liquid
-1～3.0h
-1, hydrogen to oil volume ratio is 400: 1～2000: 1, average reaction temperature is 350～450 ℃; Second section reaction conditions is: working pressure is 8.0～17.0MPa, and volume space velocity is 1.0～4.0h during liquid
-1, hydrogen to oil volume ratio is 400～2000: 1, average reaction temperature is 300～440 ℃.
8, in accordance with the method for claim 1, it is characterized in that described first section reaction effluent and second section reaction effluent enter same separation system.
9, in accordance with the method for claim 1, it is characterized in that described first section hydrocracking process adopts a reactor, or two reactors, or two above reactors.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101333459B (en) * | 2007-06-26 | 2012-03-07 | 中国石油化工股份有限公司 | Hydrogenation conversion process |
| CN104560173A (en) * | 2013-10-29 | 2015-04-29 | 中国石油化工股份有限公司 | Heavy oil hydro-conversion method |
| CN105018137A (en) * | 2014-04-23 | 2015-11-04 | 中国石油化工股份有限公司 | Hydrocracking method of low-energy-consumption, productive and high-quality jet fuel |
| CN110709492A (en) * | 2017-06-05 | 2020-01-17 | 沙特基础工业全球技术公司 | Conversion of crude oil to low boiling chemical feedstocks |
-
2005
- 2005-10-19 CN CNB2005100474795A patent/CN100526433C/en active Active
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101333459B (en) * | 2007-06-26 | 2012-03-07 | 中国石油化工股份有限公司 | Hydrogenation conversion process |
| CN104560173A (en) * | 2013-10-29 | 2015-04-29 | 中国石油化工股份有限公司 | Heavy oil hydro-conversion method |
| CN104560173B (en) * | 2013-10-29 | 2016-11-16 | 中国石油化工股份有限公司 | A kind of heavy oil hydrogenation conversion method |
| CN105018137A (en) * | 2014-04-23 | 2015-11-04 | 中国石油化工股份有限公司 | Hydrocracking method of low-energy-consumption, productive and high-quality jet fuel |
| CN105018137B (en) * | 2014-04-23 | 2017-05-17 | 中国石油化工股份有限公司 | Hydrocracking method of low-energy-consumption, productive and high-quality jet fuel |
| CN110709492A (en) * | 2017-06-05 | 2020-01-17 | 沙特基础工业全球技术公司 | Conversion of crude oil to low boiling chemical feedstocks |
| US11130919B2 (en) | 2017-06-05 | 2021-09-28 | Sabic Global Technologies B.V. | Conversion of crude oil into lower boiling point chemical feedstocks |
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