CN102453535B - Hydrocracking method for reforming material yield increase - Google Patents
Hydrocracking method for reforming material yield increase Download PDFInfo
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Abstract
The invention relates to a hydrocracking method for reforming material yield increase. Raw oil and hydrogen gas are mixed and then the mixture is sequentially subjected to hydrorefining reaction and hydrocracking reaction, reaction effluent is cooled and separated, and then, the obtained light diesel fractions with the volume percentage being 10 to 100 percent and the distillation range being 220 to 320 DEG C return to a hydrocracking reaction vessel for continuous reaction. Because the arene content and cyclane content of the part of fractions are high, the fractions are proper fractions for high-quality heavy naphtha yield increase, and the yield of aviation fuel and the cetane number of the diesel fractions can also be improved through recycling the fractions. When the method provided by the invention is adopted, the recycled light diesel fractions enter the hydrocracking reaction vessel instead of a raw material tank and do not pass through a hydrorefining reaction vessel, so few arene and cyclane parts take hydrosaturation reaction, the potential arene of the heavy naphtha is favorably improved, and the hydrogen consumption is favorably reduced.
Description
Technical field
The invention belongs to a kind of is the method that obtains low boiler cut cracking hydrocarbon ils in the situation that there is hydrogen, more particularly, is a kind of method for hydrogen cracking of low cost volume increase reformer feed.
Background technology
Reformer is the important secondary processing device of refinery, for the production of stop bracket gasoline blend component or for the production of aromatic hydrocarbons basic material.It is high that reformed gasoline has octane value, and or not containing alkene, the not feature such as sulfur-bearing, nitrogen impurity, is not the gasoline blend component of high-quality.Compared with American-European countries, during current domestic gasoline forms, reformed gasoline component is on the low side, and catalytically cracked gasoline component proportion is higher, causes that domestic goods gasoline sulfur and olefin(e) centent are high, aromaticity content is relatively low; The ratio that increases reformed gasoline in gasoline pool is conducive to reduce sulphur and olefin(e) centent, meets the environmental regulation requirement of increasingly stringent.Benzene,toluene,xylene is the basic material of petrochemical industry, and reformer generates in oil and is rich in benzene, toluene and dimethylbenzene, by separating the aromatic hydrocarbon product that can obtain high value.In addition, crude oil heaviness and oil refining enterprise produce the dual-pressure of clean fuel, make hydrogenation process become application processing means more and more widely, reformer can a large amount of cheap hydrogen of by-product, refinery also expects to obtain more hydrogen by expanding reformer scale, meets the hydrogen balance of full factory.
Virgin naphtha is the main source of reformer charging.For a long time, crude oil in China yield of light oil is lower, and virgin naphtha is one of raw material of ethylene unit, and reformer feed deficiency becomes one of principal element of restriction reformer development.Hydrocracking process is a kind of important means of heavy oil lighting, and it is high that the heavy naphtha obtaining has aromaticity content, and sulphur, the feature that nitrogen impurity content is low can, directly as the reformer charging of high-quality, make up the deficiency of virgin naphtha.
Hydrocracking process is taking inferior raw materials such as decompressed wax oils as charging, can obtain the products such as light, heavy naphtha, intermediate oil and tail oil.For once by the hydroeracking unit under flow process, for improving heavy naphtha productive rate, can take to improve the method for transformation efficiency, heavy ends is more converted into light-end products, decline but also can cause heavy naphtha selectivity and virtue to be dived simultaneously, hydrogen gas consumption increases.
CN 101210198A discloses a kind of method of hydrotreating of producing fine-quality diesel oil and high-quality reformer feed, diesel oil and/or light wax oil raw material separate without middle with hydrocracking catalyst contact reacts with Hydrobon catalyst after mixing with hydrogen successively, resultant of reaction is through cooling, after separation, obtain light naphtha fraction, heavy naphtha fraction, diesel oil distillate and tail oil cut, described kerosene(oil)fraction and/or tail oil cut can directly be extracted out or part circulates or all loop back reactive system, the present invention adopts single hop connect one-pass flow process and non-precious metal catalyst, can produce the reformer feed of Gao Fangqian and the diesel oil distillate of high hexadecane value, the reformer feed yield that wherein obtained is greater than 20 % by weight.
USP4,172,815 disclose the single hop circulation method for hydrogen cracking of simultaneously producing rocket engine fuel and diesel oil, and the initial boiling point of raw material is greater than 500 °F (approximately 260 DEG C).Its technical process is briefly described as follows: stock oil is through hydrocracking, temperature of reaction is lower than 900 °F (approximately 482 DEG C), pressure is greater than 1000psig (about 6.9Mpa), reaction effluent is through fractionation, obtain naphtha fraction, rocket engine fuel cut, diesel oil distillate and tail oil, rocket engine fuel cut is all or part of to be mixed with tail oil, sends cracking reaction district back to.The method, under the hydrocracking condition comparatively relaxing, can reach the object that maximum is produced rocket engine fuel and diesel oil simultaneously, and the quality of boat coal also improves.The method for be to produce qualified rocket engine fuel and diesel oil, do not refer to the variation of heavy naphtha.
CN101173189A discloses a kind of method for hydrogen cracking of producing industrial chemicals, its feature is to enter one-stage hydrogenation treatment zone after heavy raw oil mixes with hydrogen, one section of effluent separates the hydrogen-rich gas obtaining and directly enters secondary hydrogenation cracking reaction district, liquid enters separation column and carries out fractionation, obtain gas, petroleum naphtha and tail oil and go out system as industrial chemicals, separately or be mixed into secondary hydrogenation treatment zone with other inferior distillate oil and carry out cracking, two sections of gas circulation that obtain are used intermediate oil.This invention can obtain heavy naphtha by circulation freshening intermediate oil, but has adopted two-stage hydrocracking, and facility investment is larger, and freshening part is whole intermediate oils in addition.
Summary of the invention
The object of the invention is to provide on the basis of existing technology a kind of method for hydrogen cracking of low cost reforming material yield increase.
Method provided by the invention comprises:
(1) stock oil enters hydrofining reactor and follow-up hydrocracking reactor after mixing with hydrogen, under the effect of Hydrobon catalyst and hydrocracking catalyst, reacts;
(2) reaction effluent through cooling, separate after, the hydrogen-rich gas of gained recycles as circulating hydrogen, the liquid phase stream of gained enters fractionating system, obtains light naphtha fraction, heavy naphtha fraction, kerosene(oil)fraction, solar oil cut and tail oil cut through fractionation;
(3) the solar oil cut of step (2) gained turns back to hydrocracking reactor continuation reaction, and the percent by volume that the solar oil cut that wherein circulates accounts for total solar oil cut is 10%～100%.
Adopt the method provided by the invention can low cost reforming material yield increase, circulate 10%～100%220 DEG C～320 DEG C solar oil cuts to hydrocracking reactor, it is carried out to freshening, in the heavy naphtha that raises productivity and improves the quality, keep the selectivity of heavy naphtha: reduced hydrogen consumption.Adopt method provided by the invention, select above-mentioned cut instead of other cut, its naphthenic hydrocarbon and aromaticity content are high, are the natural cuts of heavy naphtha of raising productivity and improving the quality.The above-mentioned cut of freshening increases production compared with other cut of method and freshening of scheelite brain and the method for raising reaction conversion ratio to cracking case, and its scheelite virtue is dived higher, and cost is lower.
Brief description of the drawings
Accompanying drawing is the reforming material method for hydrogen cracking schematic flow sheet that raises productivity and improves the quality provided by the invention.
Embodiment
Stock oil enters hydrofining reactor with new hydrogen and recycle hydrogen, under the effect of Hydrobon catalyst, carry out hydrogenating desulfurization, hydrodenitrification, olefin saturated and the reaction of part aromatic saturation, reaction conditions is: 250 DEG C～450 DEG C of temperature of reaction, preferably 300 DEG C～420 DEG C, hydrogen dividing potential drop 5.0～18.0MPa, preferably 8.0～15.0MPa, volume space velocity 0.2～10.0h when liquid
-1, preferably 0.4～3.0h
-1, hydrogen to oil volume ratio 100～3000Nm
3/ m
3, preferably 600～2000Nm
3/ m
3;
After mixing, 10%～100%220 DEG C～320 DEG C solar oil cuts of whole cuts of hydrofining gained and freshening and recycle hydrogen enter hydrocracking reactor, contact and react with hydrocracking catalyst, reaction conditions is: 250～450 DEG C of temperature of reaction, preferably 300～420 DEG C, hydrogen dividing potential drop 5.0～18.0MPa, preferably 8.0～15.0MPa, volume space velocity 0.2～10.0h when liquid
-1, preferably 0.4～3.0h
-1, hydrogen to oil volume ratio 50～3000Nm
3/ m
3, preferably 600～2000Nm
3/ m
3.
The reaction effluent of hydrocracking reaction, after cooling, enter successively high-pressure separator and light pressure separator and carries out gas-liquid separation, and separating obtained hydrogen-rich gas turns back to hydrofining and hydrocracking reactor entrance after circulating hydrogen compressor boosts; The liquid phase stream of gained enters fractionating system, obtains light, heavy naphtha fraction, kerosene(oil)fraction, solar oil cut and tail oil cut after fractionation.More than 10% 220 DEG C～320 DEG C solar oil cuts are circulated to cracking case and after mixing, jointly pass through hydrocracking reactor with refining raw material afterwards, the percent by volume that circulation solar oil cut accounts for total solar oil cut is 10%～100%, preferably 30%～50%.
Obtain light naphtha fraction (65 DEG C of <), heavy naphtha fraction (65～175 DEG C), kerosene(oil)fraction (175～220 DEG C), solar oil cut (220～320 DEG C) and tail oil cut (320 DEG C of >) according to voluminous tail oil cutting mode through fractionation; Obtain light naphtha fraction (65 DEG C of <), heavy naphtha fraction (65～175 DEG C), kerosene(oil)fraction (175～220 DEG C), solar oil cut (220～320 DEG C), heavy gas oil cut (320～370 DEG C) and tail oil cut (370 DEG C of >) according to high-yield diesel oil cut cutting mode through fractionation.The solar oil cut of freshening can directly not go out device or be incorporated to heavy gas oil cut as diesel oil distillate.
Described stock oil is selected from one or more mixtures of decompressed wax oil, wax tailings, and its boiling range scope is 280～560 DEG C.
Described Hydrobon catalyst, taking catalyzer as benchmark, it consists of: the heavy % of nickel oxide 1～10, molybdenum oxide and Tungsten oxide 99.999 sum are 10～50 heavy %, the heavy % of fluorine 1～10, the heavy % of phosphorus oxide 0.5～8, surplus is silica-alumina; Taking carrier as benchmark, by weight, the content of the silicon oxide in described silica-alumina is 2%～45%, and the content of aluminum oxide is 55%～98%.The preferred Hydrobon catalyst of the present invention has been strengthened hydrogenating function, this catalyzer can show stronger hydrogenating desulfurization, hydrodenitrification ability under medium reaction pressure, in treated oil after this catalyst treatment, nitrogen content, lower than 10 μ g/g, meets the charging requirement of cracking zone catalyzer completely.The hydrogenation saturated reaction of aromatic hydrocarbons be its open loop cracking must be through step, the Hydrobon catalyst that the present invention adopts also has good aromatic saturation performance, especially the hydrogenation of polycyclic aromatic hydrocarbons is saturated can to promote aromatic hydrocarbons in stock oil, for cracking zone provides the charging that is easy to occur cracking reaction, make on the one hand in kerosene(oil)fraction aromaticity content low, smoke point is high, makes on the other hand hydrocracking tail oil aromaticity content extremely low, there is low BMCI value, can be used as the raw material of the preparing ethylene by steam cracking of high-quality.
Described hydrocracking catalyst, contain a kind of carrier and load on molybdenum and/or tungsten and nickel and/or the cobalt on this carrier, in oxide compound and taking catalyzer total amount as benchmark, the content of molybdenum and/or tungsten is 10～35 heavy %, the heavy % of content 1～15 of nickel and/or cobalt, this carrier is made up of aluminum oxide and zeolite, and the weight ratio of aluminum oxide and zeolite is 90: 10～50: 50.
Described aluminum oxide is the aluminum oxide being composited according to the weight ratio of 75: 25～50: 50 by little porous aluminum oxide and macroporous aluminium oxide, wherein, little porous aluminum oxide is that the pore volume that diameter is less than 80 dust holes accounts for more than 95% aluminum oxide of total pore volume, and macroporous aluminium oxide is that the pore volume in diameter 60-600 dust hole accounts for more than 70% aluminum oxide of total pore volume.
The total acid content of described zeolite be 0.02 to be less than 0.5 mmole/gram.The preferred hydrocracking catalyst performance of the present invention is good, can under lower pressure, transform nitrogen content and the higher raw material of aromaticity content.
The per pass conversion of control hydrocracking of the present invention is 60%～68%.Fresh feed is transformed into certain depth through reaction, no longer Returning reacting system of unconverted oil after reaction, but set it as ethylene raw and fcc raw material, lube stock etc., this technological process is called once-through operation.Per pass conversion refers to that stock oil (macromole) is converted into the percentage ratio of light-end products (small molecules), and per pass conversion of the present invention refers to 350 DEG C of cut per pass conversion of >, and formulate is as follows:
Accompanying drawing is the method for hydrotreating schematic diagram of low cost reforming material yield increase provided by the invention.Below in conjunction with accompanying drawing, method provided by the present invention is further detailed, has omitted much equipment in figure, as pump, interchanger, compressor etc., but this is known to those of ordinary skill in the art.
Method of hydrotreating technical process provided by the invention is described in detail as follows: enter storage tank 1 from the stock oil of pipeline 15, new hydrogen is sneaked in reaction raw materials through pipeline 23, enter hydrofining reactor 2 by pipeline 16 again, under the effect of Hydrobon catalyst, react, its reaction effluent enters hydrocracking reactor 3 after mixing with the freshening solar oil cut from pipeline 14, under the effect of hydrocracking catalyst, react, resultant of reaction is after pipeline 19 is extracted out, enter high-pressure separator 5 and carry out gas-liquid separation, the hydrogen rich stream at high-pressure separator 5 tops enters circulating hydrogen compressor 4 by pipeline 7, point two-way after circulating hydrogen compressor supercharging, enter respectively hydrofining reactor 2 and hydrocracking reactor 3 along pipeline 17 and 18 respectively.The liquid phase stream of high-pressure separator 5 bottoms enters light pressure separator 6 through pipeline 20, carries out further gas-liquid separation at this, and isolated gas is extracted out through pipeline 21; The liquid of light pressure separator 8 bottoms enters separation column 7 through pipeline 22.Enter the liquid phase stream of separation column 7 after fractionation, light naphtha fraction, heavy naphtha fraction, kerosene(oil)fraction and the tail oil cut cutting into extracted out through pipeline 13,10,8 and 12 successively.Solar oil cut is extracted out through pipeline 11, and part solar oil cut is circulated to hydrocracking reactor 3 entrances through pipeline 14, and all the other solar oil cuts are via pipeline 9 withdrawing devices.
In accompanying drawing, fractionation part has only been enumerated the product cutting mode of voluminous tail oil, but this does not hinder this invention can adopt the cutting mode of high-yield diesel oil in fractionation part.
Advantage of the present invention is:
1, adopt method provided by the invention, can effectively improve the productive rate of heavy naphtha, and can keep the selectivity of heavy naphtha.This is because part solar oil cut, after circulation freshening, further carries out cracking, thereby has increased the productive rate of heavy naphtha; Owing to not improving the severity of reaction, can keep high heavy naphtha selectivity.
2, compared with other intermediate oil, 220～320 DEG C of solar oil cuts selecting in the present invention due to naphthenic hydrocarbon and aromaticity content high, be desirable freshening fecund heavy naphtha component.The heavy naphtha virtue that this cut of freshening obtains is dived higher.Select freshening solar oil cut, can also improve the output of kerosene and the cetane value of diesel oil distillate.
3, solar oil cut, without refining reaction device, direct cycles to cracking case entrance, has alleviated the degree of saturation of this cut, is more conducive to prepare the latent petroleum naphtha of high virtue after cracking.In order to increase production heavy naphtha, under available technology adopting high conversion condition, carry out hydrocracking.Compared with adopting high conversion condition, adopt the method for the above-mentioned cut of freshening, scheelite virtue is dived high, and hydrogen consumption is lower.
The following examples will, to method provided by the invention, be further described, but not thereby limiting the invention.
In embodiment, the trade names of Hydrobon catalyst used are RN-32V, and the trade names of hydrocracking catalyst are RHC-3, are China Petrochemical Corp.'s catalyzer Chang Ling branch office and produce.In embodiment, stock oil A used is a kind of VGO, and its main character is as shown in table 1.
Embodiment 1
Be 13.0MPa in reaction pressure, 373 DEG C of hydrofining reactor temperature of reaction, air speed 1.2h
-1, 367 DEG C of hydrocracking reactor temperature of reaction, air speed 2.0h
-1, under the reaction conditions that hydrogen to oil volume ratio is 1200.With method provided by the invention, adopt raw material A to test, wherein 220～320 DEG C of solar oil cuts that account for whole solar oil mass percents 40% are circulated to hydrocracking reactor entrance, test-results is as shown in table 2.
As can be seen from Table 2, under the condition that is 61% at 350 DEG C of transformation efficiencys of >, the yield of heavy naphtha fraction is 31.77% (to fresh feed), and the yield of kerosene(oil)fraction is 12.59%; In addition, the selectivity of heavy naphtha is 86%.
Comparative example 1
Be 13.0MPa in reaction pressure, 373 DEG C of hydrofining reactor temperature of reaction, air speed 1.2h
-1, 367 DEG C of hydrocracking reactor temperature of reaction, air speed 2.0h
-1, under the reaction conditions that hydrogen to oil volume ratio is 1200.With conventional method for hydrogen cracking, adopt raw material A to test to produce heavy naphtha, test-results is as shown in table 3.
As can be seen from Table 3, under the condition of 350 DEG C of transformation efficiencys 61% of >, the yield of heavy naphtha fraction is only 27.93% (to fresh feed), and the yield of kerosene(oil)fraction is 10.75%; In addition, the selectivity of heavy naphtha is 86%.The test-results explanation of embodiment 1 and comparative example 1 can increase by circulation solar oil cut the productive rate of heavy naphtha under identical transformation efficiency condition, and the selectivity of heavy naphtha do not decline, and also can improve in addition the productive rate of the coal that navigates.
Embodiment 2
Adopt method provided by the invention, controlling 350 DEG C of transformation efficiencys of > is 65%, is 13.0MPa in reaction pressure, 375 DEG C of hydrofining reactor temperature of reaction, air speed 1.2h
-1, 373 DEG C of hydrocracking reactor temperature of reaction, air speed 2.0h
-1, under the reaction conditions that hydrogen to oil volume ratio is 1200.With method provided by the invention, adopt raw material A to test, wherein 220～320 DEG C of solar oil cuts that account for fresh feed A massfraction 10% are circulated to hydrocracking reactor entrance, the quality product data of heavy naphtha, boat coal and diesel oil distillate are listed in table 4.From table 4, it is 59.2 that the heavy naphtha virtue that freshening obtains is dived, and boat coal smoke point is 27.3mm, and the cetane value of solar oil is 62.4.
Comparative example 2
Controlling 350 DEG C of transformation efficiencys of > is 65%, is 13.0MPa in reaction pressure, 375 DEG C of hydrofining reactor temperature of reaction, air speed 1.2h-1,372 DEG C of hydrocracking reactor temperature of reaction, air speed 2.0h
-1hydrogen to oil volume ratio is under 1200 reaction conditions, adopt raw material A to test, the intermediate oil (kerosene(oil)fraction+solar oil cut) that accounts for fresh feed A massfraction 10% is recycled to hydrocracking reactor entrance, and the quality product data of heavy naphtha, boat coal and diesel oil distillate are listed in table 5.From table 4 and table 5, embodiment 2 (the solar oil cut of freshening same amount) is compared with comparative example 2 (freshening middle runnings oil distillate), obtain heavy naphtha product virtue and dive high approximately 2 percentage points, boat coal smoke point is substantially suitable, the cetane value high approximately 2 of solar oil.
Embodiment 3
Improve transformation efficiency and freshening solar oil and can increase production heavy naphtha productive rate; In order to be further familiar with the difference of two schemes, first reach 34% as target taking heavy naphtha yield, adopt method provided by the invention, carry out the mass percent 60% solar oil cut fraction hydrogenation cracking test that freshening accounts for whole solar oil cuts, reaction pressure is 10.5MPa, 373 DEG C of hydrofining reactor temperature of reaction, air speed 1.2h
-1, hydrocracking reactor air speed 2.0h
-1, under the reaction conditions that hydrogen to oil volume ratio is 1200.With method provided by the invention, adopt raw material A to test, product distributes and hydrogen consumption the results are shown in table 6.
Comparative example 3
Reach 34% as target taking heavy naphtha yield, adopt conventional method for hydrogen cracking, carried out improving the simultaneous test of transformation efficiency fecund heavy naphtha, 373 DEG C of hydrofining reactor temperature of reaction, air speed 1.2h
-1, hydrocracking reactor air speed 2.0h
-1, under the reaction conditions that hydrogen to oil volume ratio is 1200.With method provided by the invention, adopt raw material A to test, product distributes and hydrogen consumption the results are shown in table 7.
The test-results of embodiment 3 and comparative example 3 shows, relatively once pass through flow process, in the time that heavy naphtha yield (to fresh feed) all reaches 34% left and right, the required cracking reaction temperature of freshening solar oil cut of the present invention reduces by 3 DEG C, 350 DEG C of cut transformation efficiencys of > decline obviously, are down to 60% from 69%; The yield of kerosene has declined approximately 4.8%, and the yield of diesel oil reduces approximately 2.0%, and tail oil yield has risen approximately 9%, is equivalent to reduce kerosene, production of diesel oil and the tail oil output that increased; From the heavy naphtha selectivity of the two, once poor by the heavy naphtha selectivity under condition.
Distribute and can see from actual product, compared with improving transformation efficiency, freshening solar oil has changed product distribution on the one hand, and in the time that heavy naphtha yield reaches 34%, the productive rate of kerosene, solar oil declines, and tail oil productive rate rises; Freshening solar oil has reduced the transformation efficiency of fresh feed on the other hand, has therefore reduced the generation of the low value such as gas, light naphthar, high hydrogen-carbon ratio product, is conducive to reduce hydrogen consumption.The result of actual analysis shows that freshening solar oil and one-pass hydrogen consumption is respectively 2.60% and 2.90%, has illustrated that freshening solar oil can realize the object that reduces hydrogen consumption simultaneously reaching voluminous heavy naphtha.
Table 1 stock oil character
| Stock oil numbering | A |
| Density (20 DEG C)/(g/cm 3) | 0.9197 |
| C/ % by weight | 85.89 |
| H/ % by weight | 11.96 |
| Condensation point/DEG C | 24 |
| Aniline point/DEG C | 77.4 |
| Carbon residue/% by weight | 0.07 |
| Boiling range ASTM D-1160/ DEG C | |
| IBP | 267 |
| 10％ | 376 |
| 50％ | 436 |
| 90％ | 474 |
| FBP | 517 |
Table 2 embodiment 1 freshening solar oil product distributes
| Raw material | 40% solar oil cut circulates |
| Product boiling range D-1160/ DEG C | |
| Initial boiling point | 89 |
| 10％ | 124 |
| 50％ | 231 |
| 90％ | 431 |
| Final boiling point | 509 |
| Liquid hydrocarbon product distribution/% by weight | |
| 65 DEG C of light naphthars of < | 5.13 |
| 65～175 DEG C of heavy naphtha | 31.77 |
| 175～220 DEG C of kerosene | 12.59 |
| 220～320 DEG C of diesel oil | 9.71 |
| 320 DEG C of tail oils of > | 40.80 |
| Scheelite selectivity/% | 86.1 |
| 350 DEG C of transformation efficiency/% of > | 60.99 |
Table 3 comparative example 1 is once by the product contrast that distributes
| Raw material | Raw material A is once passed through |
| Product boiling range D-1160/ DEG C | |
| Initial boiling point | 82 |
| 50％ | 269 |
| 90％ | 438 |
| Final boiling point | 510 |
| Liquid hydrocarbon product distribution/% by weight | |
| 65 DEG C of light naphthars of < | 4.82 |
| 65～175 DEG C of heavy naphtha | 27.93 |
| 175～220 DEG C of kerosene | 10.75 |
| 220～320 DEG C of diesel oil | 16.21 |
| 320 DEG C of tail oils of > | 40.29 |
| Scheelite selectivity/% | 85.3 |
| 350 DEG C of transformation efficiency/% of > | 61.31 |
Table 4 embodiment 2 freshening solar oil cuts are to cracking case product property (350 DEG C of transformation efficiencys of > are 65%)
Table 5 comparative example 2 freshening intermediate oils are to cracking case product property (350 DEG C of transformation efficiencys of > are 65% left and right)
Table 6 embodiment 3 freshening solar oil cut test products distribute and hydrogen consumption (yield of heavy naphtha is 34%)
| Raw material | 60% solar oil cut circulates |
| Hydrocracking reactor temperature of reaction/DEG C | 368 |
| Liquid product distribution/% | |
| 65 DEG C of light naphthars of < | 5.08 |
| 65～175 DEG C of heavy naphtha | 33.77 |
| 175～220 DEG C of kerosene | 13.00 |
| 220～320 DEG C of diesel oil | 6.35 |
| 320 DEG C of tail oils of > | 41.80 |
| Scheelite selectivity/% | 86.9 |
| 350 DEG C of transformation efficiency/% of > | 60.21 |
| Hydrogen consumption/% | 2.60 |
The contrast (yield of heavy naphtha is about 34%) that table 7 comparative example 3 once distributes by test products and hydrogen consumes
| Raw material | Raw material A |
| Hydrocracking reactor temperature of reaction/DEG C | 371 |
| Liquid product distribution/% | |
| 65 DEG C of light naphthars of < | 6.64 |
| 65～175 DEG C of heavy naphtha | 33.86 |
| 175～220 DEG C of kerosene | 17.83 |
| 220～320 DEG C of diesel oil | 8.46 |
| 320 DEG C of tail oils of > | 33.21 |
| Scheelite selectivity/% | 83.6 |
| 350 DEG C of transformation efficiency/% of > | 69.48 |
| Hydrogen consumption/% | 2.90 |
Claims (9)
1. a method for hydrogen cracking for reforming material yield increase, comprising:
(1) stock oil enters hydrofining reactor and follow-up hydrocracking reactor after mixing with hydrogen, under the effect of Hydrobon catalyst and hydrocracking catalyst, reacts;
(2) reaction effluent through cooling, separate after, the hydrogen-rich gas of gained recycles as circulating hydrogen, the liquid phase stream of gained enters fractionating system, obtains light naphtha fraction, heavy naphtha fraction, kerosene(oil)fraction, solar oil cut and tail oil cut through fractionation;
(3) the solar oil cut of step (2) gained turns back to hydrocracking reactor continuation reaction, and the percent by volume that the solar oil cut that wherein circulates accounts for total solar oil cut is 10%～100%;
The boiling range of described solar oil cut is 220 DEG C～320 DEG C;
The boiling range scope of described stock oil is 280～560 DEG C, and described stock oil is selected from one or more in decompressed wax oil, normal pressure wax oil, wax tailings, deasphalted oil.
2. in accordance with the method for claim 1, it is characterized in that, the percent by volume that circulation solar oil cut accounts for total solar oil cut is 30%～50%.
3. in accordance with the method for claim 1, it is characterized in that, hydrofining reactor reaction conditions is: 250 DEG C～450 DEG C of temperature of reaction, hydrogen dividing potential drop 5.0～18.0MPa, volume space velocity 0.2～10.0h when liquid
-1, hydrogen to oil volume ratio 100～3000Nm
3/ m
3;
Hydrocracking reactor reaction conditions is: 250～450 DEG C of temperature of reaction, hydrogen dividing potential drop 5.0～18.0MPa, volume space velocity 0.2～10.0h when liquid
-1, hydrogen to oil volume ratio 50～3000Nm
3/ m
3.
4. in accordance with the method for claim 3, it is characterized in that, hydrofining reactor reaction conditions is: 300 DEG C～420 DEG C of temperature of reaction, hydrogen dividing potential drop 8.0～15.0MPa, volume space velocity 0.4～3.0h when liquid
-1, hydrogen to oil volume ratio 600～2000Nm
3/ m
3;
Hydrocracking reactor reaction conditions is: 300～420 DEG C of temperature of reaction, hydrogen dividing potential drop 8.0～15.0MPa, volume space velocity 0.4～3.0h when liquid
-1, hydrogen to oil volume ratio 600～2000Nm
3/ m
3.
5. in accordance with the method for claim 1, it is characterized in that described Hydrobon catalyst, taking catalyzer as benchmark, it consists of: the heavy % of nickel oxide 1～10, and molybdenum oxide and Tungsten oxide 99.999 sum are 10～50 heavy %, the heavy % of fluorine 1～10, the heavy % of phosphorus oxide 0.5～8, surplus is silica-alumina; Taking carrier as benchmark, by weight, the content of the silicon oxide in described silica-alumina is 2%～45%, and the content of aluminum oxide is 55%～98%.
6. in accordance with the method for claim 1, it is characterized in that, described hydrocracking catalyst, contain a kind of carrier and load on molybdenum and/or tungsten and nickel and/or the cobalt on this carrier, in oxide compound and taking catalyzer total amount as benchmark, the content of molybdenum and/or tungsten is 10～35 heavy %, the heavy % of content 1～15 of nickel and/or cobalt, this carrier is made up of aluminum oxide and zeolite, and the weight ratio of aluminum oxide and zeolite is 90:10～50:50.
7. in accordance with the method for claim 6, it is characterized in that, described aluminum oxide is the aluminum oxide being composited according to the weight ratio of 75:25～50:50 by little porous aluminum oxide and macroporous aluminium oxide, wherein, little porous aluminum oxide is that the pore volume that diameter is less than 80 dust holes accounts for more than 95% aluminum oxide of total pore volume, and macroporous aluminium oxide is that the pore volume in diameter 60-600 dust hole accounts for more than 70% aluminum oxide of total pore volume.
8. in accordance with the method for claim 7, it is characterized in that, the total acid content of described zeolite be 0.02 to be less than 0.5 mmole/gram.
9. in accordance with the method for claim 1, it is characterized in that, the per pass conversion of hydrocracking is 60%～68%.
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| CN103773476B (en) * | 2012-10-24 | 2015-06-17 | 中国石油化工股份有限公司 | Method for producing high-viscosity-index lubricant base oil by hydrocracking-isodewaxing combination |
| CN104560169B (en) * | 2013-10-29 | 2016-05-25 | 中国石油化工股份有限公司 | A kind of method for hydrogen cracking of producing heavy naphtha from high-nitrogen stock |
| CN109694732B (en) * | 2017-10-23 | 2021-02-09 | 中国石油化工股份有限公司 | Process for processing heavy diesel fuel |
| CN108277044A (en) * | 2018-03-02 | 2018-07-13 | 中国石化青岛炼油化工有限责任公司 | A kind of system and method improving hydrocracking process Air China coal, yield of gasoline |
| WO2020069472A1 (en) * | 2018-09-29 | 2020-04-02 | Uop Llc | Process for maximizing production of heavy naphtha from a hydrocarbon stream |
| CN116064136A (en) * | 2021-10-30 | 2023-05-05 | 中国石油化工股份有限公司 | Wax oil hydrocracking and diesel hydrofining combined process and system |
| CN116410781A (en) * | 2021-12-29 | 2023-07-11 | 中国石油天然气股份有限公司 | Method for producing ethylene raw material by diesel hydrocracking |
| CN116410787A (en) * | 2021-12-29 | 2023-07-11 | 中国石油天然气股份有限公司 | Method for producing light weight reforming material and ethylene cracking raw material by diesel oil hydrotreating selective recycle |
| CN115537231B (en) * | 2022-10-18 | 2024-02-09 | 浙江石油化工有限公司 | Method for realizing oil reduction and oil increase by changing material flow direction |
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