CN103059986B - Hydrocracking method for producing chemical materials - Google Patents
Hydrocracking method for producing chemical materials Download PDFInfo
- Publication number
- CN103059986B CN103059986B CN201110324623.0A CN201110324623A CN103059986B CN 103059986 B CN103059986 B CN 103059986B CN 201110324623 A CN201110324623 A CN 201110324623A CN 103059986 B CN103059986 B CN 103059986B
- Authority
- CN
- China
- Prior art keywords
- hydrocracking
- hydrogen
- oil
- aluminum oxide
- reaction
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Abstract
The invention discloses a hydrocracking method for producing chemical materials. The method comprises the steps of: orderly entering material oil and hydrogen into a hydrorefining reactor and a first hydrocracking reactor to react after being mixed; and cooling and separating reactants, and then entering obtained 10-100% of diesel fraction with the temperature of 175-320 DEG C into a second hydrocracking reactor to further react, wherein a hydrocracking catalyst II is a hydrocracking catalyst with low metal content; the metal content of the hydrocracking catalyst II is lower than that of a hydrocracking catalyst I. By adopting the hydrocracking method, the yield and the selectivity of heavy naphtha can be effectively improved; the aromatic latent of the heavy naphtha is improved, and hydrogen consumption is reduced.
Description
Technical field
The invention belongs to a kind of method obtaining cracking hydrocarbon ils in the presence of hydrogen, more particularly, is a kind of method for hydrogen cracking producing industrial chemicals.
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, not containing alkene, the not feature such as sulfur-bearing, nitrogen impurity, is the gasoline blending component of high-quality.Compared with American-European countries, during current domestic gasoline is formed, reformed gasoline component is on the low side, and catalytically cracked gasoline component proportion is higher, causes domestic goods gasoline sulfur and olefin(e) centent is high, aromaticity content is relatively low; The ratio increasing reformed gasoline in gasoline pool is conducive to reducing 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 being separated 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, hydrogenation process is made to 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 obtained has aromaticity content, sulphur, the feature that nitrogen impurity content is low, directly as the reformer charging of high-quality, can make up the deficiency of virgin naphtha.
The products such as hydrocracking process, can obtain gently for charging with inferior raw materials such as decompressed wax oils, heavy naphtha, intermediate oil and tail oil.For once by the hydroeracking unit under flow process, for improving heavy naphtha productive rate, the method improving transformation efficiency can be taked, heavy ends is more converted into light-end products, but heavy naphtha selectivity and virtue also can be caused to dive decline, hydrogen gas consumption increases simultaneously.
Increase heavy naphtha and also can carry out circulation freshening to whole intermediate oil, the method effectively can increase the yield of heavy naphtha, but on the one hand, under the prerequisite that catalytic amount does not increase, a large amount of intercycle distillate will inevitably increase volume space velocity greatly, high-speed will affect the long-term operation of hydroeracking unit, on the other hand, if do not improve volume space velocity, then need aggrandizement apparatus volume and catalyst levels, economically may not be suitable; The more important thing is, and not all intermediate oil is suitable recycle fraction, the virtue adopting recycle to extinction may reduce heavy naphtha fraction is dived and selectivity.
CN 101210198A discloses a kind of method of hydrotreating producing fine-quality diesel oil and high-quality reformer feed, be separated without centre with hydrocracking catalyst contact reacts with Hydrobon catalyst successively after diesel oil and/or light wax oil raw material mix with hydrogen, resultant of reaction is through cooling, light naphtha fraction is obtained after separation, heavy naphtha fraction, diesel oil distillate and tail oil fraction, described kerosene(oil)fraction and/or tail oil fraction can directly be extracted out or component loops or all loop back reactive system, the present invention adopts single hop to connect one-pass flow process and non-precious metal catalyst, the reformer feed of Gao Fangqian and the diesel oil distillate of high hexadecane value can be produced, wherein obtained reformer feed yield is greater than 20 % by weight.
USP4,172,815 disclose the single hop circulation method for hydrogen cracking simultaneously producing rocket engine fuel and diesel oil, and the initial boiling point of raw material is greater than 500 °F (about 260 DEG C).Its technical process is briefly described as follows: stock oil is through hydrocracking, temperature of reaction is lower than 900 °F (about 482 DEG C), pressure is greater than 1000psig (about 6.9Mpa), reaction effluent is through fractionation, obtain naphtha fraction, jet fuel fraction, diesel oil distillate and tail oil, jet fuel fraction is all or part of to be mixed with tail oil, sends cracking reaction district back to.The method is under the hydrocracking condition comparatively relaxed, and can reach maximum simultaneously and produce the object of rocket engine fuel and diesel oil, the quality of boat coal also improves.The method for be produce qualified rocket engine fuel and diesel oil, do not refer to the change of heavy naphtha.
CN101173189A discloses a kind of method for hydrogen cracking producing industrial chemicals, its feature is to enter one-stage hydrogenation treatment zone after heavy raw oil mixes with hydrogen, one section of effluent is separated the hydrogen-rich gas obtained 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 obtained use intermediate oil.This invention can obtain heavy naphtha by circulation freshening intermediate oil.
CN1955261A has opened the oil circulation method for hydrogen cracking of a kind of middle runnings, after being characterized in poor quality being urged bavin to mix with heavy hydrogenated cracking stock, first carry out hydrocracking, gained intermediate oil carries out secondary hydrogenation cracking, obtains the tail oil of the latent heavy naphtha of high virtue and low BMCI value.
Summary of the invention
The object of the invention is to provide a kind of method for hydrogen cracking producing industrial chemicals on the basis of existing technology.
Method provided by the invention comprises:
(1) stock oil enters hydrofining reactor and the first follow-up hydrocracking reactor after mixing with hydrogen, reacts under the effect of Hydrobon catalyst and hydrocracking catalyst I;
The reaction effluent of (2) first hydrocracking reactors and the second hydrocracking reactor is after cooling, being separated, 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, diesel oil distillate and tail oil fraction through fractionation;
(3) diesel oil distillate of step (2) gained enters into the second hydrocracking reactor, under the effect of hydrocracking catalyst II, continue reaction, the percent by volume that the diesel oil distillate wherein entering the second hydrocracking reactor accounts for the total diesel oil distillate of step (2) gained is 10% ~ 100%.
Described hydrocracking catalyst II is the hydrocracking catalyst that low metal is measured, and the metal of hydrocracking catalyst II is measured on the metal lower than hydrocracking catalyst I and measures.
With hydrocracking catalyst II for entirety, with oxide basis, on its metal, amount is less than or equal to 22 % by weight.
The boiling range of the diesel oil distillate of step (2) gained is 175 ~ 320 DEG C.
Adopt method provided by the invention effectively can increase production reformer feed, extract 10% ~ 100%175 ~ 320 DEG C of diesel oil distillates out to the second hydrocracking reactor, freshening is carried out to it, while the heavy naphtha that raises productivity and improves the quality, also can improve the selectivity of heavy naphtha.Naphthenic hydrocarbon and the aromaticity content of described diesel oil distillate are high, carry out hydrocracking again, and the heavy naphtha virtue of acquisition is dived higher, and selectivity is better.In addition, the second hydrocracking reactor loads the hydrocracking catalyst II that low metal is measured, and the Hydrogenation that itself and cracking performance match is lower, from reaction process, be conducive to increasing the aromaticity content in heavy naphtha, thus the virtue improving heavy naphtha fraction is dived, reduce hydrogen consumption; On the other hand, the reaction raw materials of the second hydrocracking reactor is 175 ~ 320 DEG C of diesel oil distillates, its nitrogen content is low, boiling range is relatively light, more not easily dehydrogenation pyrogenic reaction is there is compared with wax oil cut, adopt the hydrocracking catalyst II that low metal is measured, can not have an impact to the long-term operation of device.
Accompanying drawing explanation
Accompanying drawing is production industrial chemicals method for hydrogen cracking schematic flow sheet provided by the invention.
Embodiment
In step (1), stock oil and (mixed gas of recycle hydrogen and new hydrogen) enter hydrofining reactor, hydrogenating desulfurization, hydrodenitrification, olefin saturated and the reaction of part aromatic saturation is carried out under the effect of Hydrobon catalyst, reaction conditions is as follows: temperature of reaction 250 DEG C ~ 450 DEG C, 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 during liquid
-1, preferably 0.4 ~ 3.0h
-1, hydrogen to oil volume ratio 100 ~ 3000Nm
3/ m
3, preferably 600 ~ 2000Nm
3/ m
3.
Enter the first hydrocracking reactor after whole cut of hydrofining gained mixes with component loops hydrogen to contact with hydrocracking catalyst I and react, reaction conditions is as follows: temperature of reaction 250 ~ 450 DEG C, 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 during liquid
-1, preferably 0.4 ~ 3.0h
-1, hydrogen to oil volume ratio 50 ~ 3000Nm
3/ m
3, preferably 600 ~ 2000Nm
3/ m
3.
In step (2), the reaction of the first hydrocracking reactor generates oil after cooling, enter high-pressure separator successively and light pressure separator carries out gas-liquid separation, separating obtained hydrogen-rich gas turns back to the entrance of hydrofining reactor, the first hydrocracking reactor and the second hydrocracking reactor after circulating hydrogen compressor boosting; The liquid phase stream of gained enters fractionating system, obtains light naphtha fraction, heavy naphtha fraction, diesel oil distillate (175 ~ 320 DEG C) and tail oil fraction after fractionation.
In step (3), by percent by volume be the diesel oil distillate (175 ~ 320 DEG C) of 10% ~ 100% through boosting Posterior circle to the second hydrocracking reactor, contact with hydrocracking catalyst II in the presence of hydrogen gas and carry out cracking reaction.Reaction conditions is: temperature of reaction 250 ~ 450 DEG C, 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 during liquid
-1, preferably 1 ~ 4.0h
-1, hydrogen to oil volume ratio 50 ~ 3000Nm
3/ m
3, preferably 600 ~ 2000Nm
3/ m
3.The reaction generation oil of the second hydrocracking reactor enters follow-up high-pressure separator, light pressure separator and fractionating system to carry out being separated and fractionation.The reaction preferably obtained with the first hydrocracking reactor generates oil and enters same high-pressure separator, light pressure separator and follow-up fractionating system.
Described stock oil is selected from decompressed wax oil, wax tailings, deasphalted oil, coal are produced in oil one or more, its boiling range scope is 260 ~ 610 DEG C.
Described Hydrobon catalyst, be benchmark with catalyzer, 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, and surplus is silica-alumina; Take 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 enhances hydrogenating function, this catalyzer can show stronger hydrogenating desulfurization, hydrodenitrification ability under medium and above reaction pressure, in treated oil after this catalyst treatment, nitrogen content is lower than 10 μ g/g, meets the feed needs of cracking zone catalyzer completely.Aromatic hydrocarbons hydrotreated lube base oil reaction be its open loop cracking must through step, the Hydrobon catalyst that the present invention adopts also has excellent aromatic saturation performance, the hydrotreated lube base oil of the especially polycyclic aromatic hydrocarbons of aromatic hydrocarbons in stock oil can be promoted, for cracking zone provides the charging being easy to cracking reaction occurs, hydrocracking tail oil aromaticity content can be made extremely low, there is low BMCI value, can be used as the raw material of the preparing ethylene by steam cracking of high-quality.
In described first hydrocracking reactor load hydrocracking catalyst I, containing a kind of carrier and load molybdenum on this carrier and/or tungsten and nickel and/or cobalt, with oxide basis and with catalyzer total amount for 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 ~ 10: 90.
Described aluminum oxide be by little porous aluminum oxide and macroporous aluminium oxide according to 75: 25 ~ 50: 50 the aluminum oxide that is composited of weight ratio, wherein, little porous aluminum oxide is the aluminum oxide that pore volume that diameter is less than 80 dusts accounts for total pore volume more than 95%, and macroporous aluminium oxide is the aluminum oxide that the pore volume of diameter 60-600 dust accounts for total pore volume more than 70%.
The total acid content of described zeolite be 0.02 to be less than 0.5 mmole/gram.The present invention preferred hydrocracking catalyst I performance is good, can transform nitrogen content and the higher raw material of aromaticity content at lower pressures.
In described second hydrocracking reactor load hydrocracking catalyst II, containing a kind of carrier and load molybdenum on this carrier and/or tungsten and nickel and/or cobalt, with oxide basis and with catalyzer total amount for benchmark, the content of molybdenum and/or tungsten is 10 ~ 21 heavy %, preferably 15 ~ 20 heavy %, the heavy % of content 1 ~ 6 of nickel and/or cobalt, preferably 2 ~ 4 heavy %, this carrier is made up of aluminum oxide, zeolite, and the weight ratio of aluminum oxide and zeolite is 90: 10 ~ 10: 90.
Described hydrocracking catalyst II is the hydrocracking catalyst that low metal is measured, the metal of hydrocracking catalyst II is measured on the metal lower than hydrocracking catalyst I and measure, i.e. the active metallic content of hydrocracking catalyst II load is lower than the active metallic content of hydrocracking catalyst I load.With hydrocracking catalyst II for entirety, with oxide basis, on its metal, amount is less than or equal to 22 % by weight.
Described aluminum oxide be by little porous aluminum oxide and macroporous aluminium oxide according to 75: 25 ~ 50: 50 the aluminum oxide that is composited of weight ratio, wherein, little porous aluminum oxide is the aluminum oxide that pore volume that diameter is less than 80 dusts accounts for total pore volume more than 95%, and macroporous aluminium oxide is the aluminum oxide that the pore volume of diameter 60-600 dust accounts for total pore volume more than 70%.
The total acid content of described zeolite be 0.02 to be less than 0.5 mmole/gram.The present invention preferred hydrocracking catalyst II excellent property, be conducive to the heavy naphtha fraction obtaining Gao Fangqian, and selectivity is good.Heavy naphtha selectivity of the present invention to refer under certain depth of conversion that cracking generates heavy naphtha fraction yield in oil and accounts for the massfraction of whole naphtha fraction yield, and formulate is as follows:
Heavy naphtha selectivity=(heavy naphtha fraction yield/all naphtha yield) × 100%
The per pass conversion that the present invention controls the first hydrocracking reactor is 50% ~ 80%.Fresh feed is transformed into certain depth through reaction, unconverted oil no longer Returning reacting system after reaction, but it can be used as ethylene raw and fcc raw material, lube stock etc., and 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, and formulate is as follows:
Accompanying drawing is the method for hydrogen cracking schematic diagram of production industrial chemicals provided by the invention.Be described further method provided by the present invention below in conjunction with accompanying drawing, eliminate equipment component in figure, as pump, interchanger etc., but this is known to those of ordinary skill in the art.
Method for hydrogen cracking technical process provided by the invention is described in detail as follows: the stock oil from pipeline 1 enters hydrofining reactor 2 with the new hydrogen from pipeline 16 and after mixing from the recycle hydrogen of pipeline 17, react under the effect of Hydrobon catalyst, its reaction effluent enters the first hydrocracking reactor 3 after mixing with the component loops hydrogen from pipeline 17, react under the effect of hydrocracking catalyst I, its resultant of reaction enters high-pressure separator 4 through pipeline 18 and carries out gas-liquid separation, the hydrogen-rich gas at high-pressure separator 4 top enters circulating hydrogen compressor 6, through pipeline 17 point of three tunnel after circulating hydrogen compressor supercharging, enter hydrofining reactor 2 and the first hydrocracking reactor 3 and the second hydrocracking reactor 15 respectively.The liquid phase thing of high-pressure separator 4 bottom enters light pressure separator 5, carries out further gas-liquid separation at this; The liquid phase stream of light pressure separator 5 bottom enters separation column 8.The liquid phase stream entering separation column 8, after fractionation, cuts into the light naphtha fraction, heavy naphtha fraction, diesel oil distillate and the tail oil fraction that obtain and extracts out through pipeline 9,10,11 and 13 successively.Diesel oil distillate is after pipeline 11 is extracted out, and part or all of diesel oil distillate is pressurized to the second hydrocracking reactor 15 entrance through pipeline 12, and all the other diesel oil distillates go out device.Diesel oil distillate to contact with hydrocracking catalyst II at the second hydrocracking reactor 15 and reacts, and the resultant of reaction of gained enters high-pressure separator 4 and carries out gas-liquid separation.New hydrogen, is extracted out by pipeline 16 through pipeline 6 after make-up hydrogen compressor 7 pressurizes.
Advantage of the present invention is:
1, adopt method provided by the invention, effectively can improve the productive rate of heavy naphtha, and improve the selectivity of heavy naphtha.Because described diesel oil distillate, after circulation freshening, carries out cracking further, thus adds the productive rate of heavy naphtha; Owing to not improving the severity of reaction, high heavy naphtha selectivity can be kept.
2, compared with other middle runnings, 175 ~ 320 DEG C of diesel oil distillates that the present invention selects due to naphthenic hydrocarbon and aromaticity content high, heavy naphtha that this cut of freshening obtains virtue is dived higher, and heavy naphtha selectivity is good.
3, the second hydrocracking reactor have employed the hydrocracking catalyst II that low metal is measured, and the heavy naphtha obtained virtue is dived high, and hydrogen consumption is low.
The following examples to method provided by the invention, will be further described, but not thereby limiting the invention.
The trade names of Hydrobon catalyst used in embodiment are RN-32V, and the trade names of the first hydrocracking reactor hydrocracking catalyst I used are RHC-3, are China Petrochemical Corp.'s catalyzer Chang Ling branch office and produce.
Hydrocracking catalyst II consists of: with oxide basis, and with hydrocracking catalyst II total amount for benchmark, the content of molybdenum is 18 heavy %, and the heavy % of content 2 of nickel, on total metal, amount is 20%.Its carrier is: aluminum oxide 50 % by weight, zeolite (Y zeolite) 30 % by weight.
Stock oil A used in embodiment is a kind of VGO, and its main character is as shown in table 1.
Embodiment 1
Adopt method provided by the invention, at reaction pressure 13.0MPa, hydrofining reactor temperature of reaction 365 DEG C, air speed 1.0h
-1; First hydrocracking reactor temperature of reaction 368 DEG C, air speed 1.5h
-1; Second hydrocracking reactor temperature 368 DEG C, air speed 1.5h
-1; One anti-entrance criterion state hydrogen to oil volume ratio is under the reaction conditions of 1200, adopts raw material A (the second hydrocracking reactor used catalyst is that low metal measures hydrocracking catalyst II) to carry out hydrocracking tests.In process of the test, the diesel oil distillate of 50% (accounting for whole 175 ~ 320 DEG C of diesel oil distillate volume numbers) is circulated to the second hydrocracking reactor entrance, and test-results is as shown in table 2.
As can be seen from Table 2, under the first hydrocracking reactor > 350 DEG C of transformation efficiencys are about the condition of 58%, the productive rate of heavy naphtha fraction is 34.06% (accounting for the mass percent of liquid hydrocarbon product), the productive rate of diesel oil distillate is 18.42%, and tail oil productive rate is 42.03%; In addition, the selectivity of heavy naphtha is 86.1%.The heavy naphtha virtue obtained is dived and is reached 65.3%.
Comparative example 1
At reaction pressure 13.0MPa, hydrofining reactor temperature of reaction 365 DEG C, air speed 1.0h
-1; Hydrocracking reactor temperature of reaction 368 DEG C, air speed 1.5h
-1, an anti-entrance criterion state hydrogen to oil volume ratio is under the reaction conditions of 1200.With conventional hydrocracking method, adopt raw material A to carry out hydrocracking tests, test-results is as shown in table 4.
Can obtain from table 4, under > 350 DEG C of transformation efficiencys are about the condition of 58%, the productive rate of product heavy naphtha (65 ~ 175 DEG C) cut is only 19.23% (accounting for the mass percent of liquid hydrocarbon), comparatively embodiment 1 is low about 15 percentage points, the yield of diesel oil distillate (175 ~ 320 DEG C) is 36.02%, and tail oil (> 320 DEG C) yield is 41.10%; In addition, the selectivity of heavy naphtha is only 84.0%, and comparatively embodiment 1 is low about 2 percentage points, and it is 61.5% that the virtue of heavy naphtha is dived, and comparatively embodiment 1 is low by 3.8%.The test-results of embodiment 1 and comparative example 1 illustrates, adopts method of the present invention, effectively can increase the productive rate of heavy naphtha under once identical by transformation efficiency condition, and the selectivity of heavy naphtha and virtue are dived and also improved a lot.
Comparative example 2
Controlling the first hydrocracking reactor > 350 DEG C of transformation efficiencys is 58%, at reaction pressure 13.0MPa, hydrofining reactor temperature of reaction 366 DEG C, air speed 1.0h
-1; First hydrocracking reactor temperature of reaction 369 DEG C, air speed 1.5h
-1; Second hydrocracking reactor temperature of reaction 369 DEG C, air speed 1.5h
-1; One anti-entrance criterion state hydrogen to oil volume ratio is under the reaction conditions of 1200, adopts raw material A (the second hydrocracking reactor filling hydrocracking catalyst II) to carry out hydrocracking tests.Under control heavy naphtha productive rate is about the condition of 34%, be that the part diesel oil distillate (internal circulating load is substantially identical with the circulation diesel oil amount in embodiment 1) of 175 ~ 370 DEG C is recycled to the second hydrocracking reactor entrance by boiling range, product slates and heavy naphtha product character data list in table 4.From table 2 and table 4, embodiment 1 (freshening 175 ~ 320 DEG C of diesel oil distillates) is compared with comparative example 2 (175 ~ 370 DEG C of diesel oil distillates of the identical amount of freshening), embodiment 1 obtains heavy naphtha product virtue and dives than the height about 1 percentage point of comparative example 2, embodiment 1 heavy naphtha selectivity ratios comparative example 2 height about 0.6 percentage point in addition.
Embodiment 2
Adopt method provided by the invention, control the first hydrocracking reactor > 350 DEG C of transformation efficiencys 72%, at reaction pressure 13.0MPa, hydrofining reactor temperature of reaction 365 DEG C, air speed 1.0h
-1; First hydrocracking reactor temperature of reaction 374 DEG C, air speed 1.5h
-1; One anti-entrance criterion state hydrogen to oil volume ratio is under the reaction conditions of 1200, adopts raw material A (the second hydrocracking reactor filling hydrocracking catalyst II) to carry out hydrocracking tests.50% 175 ~ 320 DEG C of diesel oil distillates are circulated to the second hydrocracking reactor entrance, and the temperature of reaction of the second hydrocracking reactor is 370 DEG C, and the quality product data of product slates and heavy naphtha list in table 2.From table 2, under the condition of the first hydrocracking reactor > 350 DEG C of transformation efficiencys about 72%, the heavy naphtha productive rate that freshening obtains can reach 43.43%, and it is 64.5% that virtue is dived.Compared with embodiment 1, owing to having increased substantially depth of conversion, under the condition that freshening diesel fuel ratio is identical, the productive rate of heavy naphtha can be increased, but virtue is dived and can be declined to some extent.
Embodiment 3
Adopt method provided by the invention, control the first hydrocracking reactor > 350 DEG C of transformation efficiencys about 59%, reaction pressure 13.0MPa, hydrofining reactor temperature of reaction 365 DEG C, air speed 1.0h
-1; First hydrocracking reactor temperature of reaction 369 DEG C, air speed 1.5h
-1; One anti-entrance criterion state hydrogen to oil volume ratio is under the reaction conditions of 1200, adopts raw material A (the second hydrocracking reactor filling hydrocracking catalyst II) to carry out hydrocracking tests.Obtain 100% 175 ~ 320 DEG C of diesel oil distillates are circulated to the second hydrocracking reactor entrance, and the temperature of reaction of the second hydrocracking reactor is 377 DEG C, and the quality product data of product slates and heavy naphtha list in table 3.From table 3, under the condition of the first hydrocracking reactor > 350 DEG C of transformation efficiencys about 59%, the diesel oil distillate (175 ~ 320 DEG C) that whole freshening obtains, heavy naphtha productive rate can reach 51.01%, heavy naphtha selectivity is 86.5%, and virtue is dived up to 67.2%.
Embodiment 4
Adopt method provided by the invention, control the first hydrocracking reactor > 350 DEG C of transformation efficiencys 68%, at reaction pressure 13.0MPa, hydrofining reactor temperature of reaction 365 DEG C, air speed 1.0h
-1; First hydrocracking reactor temperature of reaction 372 DEG C, air speed 1.5h
-1; One anti-entrance criterion state hydrogen to oil volume ratio is under the reaction conditions of 1200, adopts raw material A (the second hydrocracking reactor filling hydrocracking catalyst II) to carry out hydrocracking tests.Obtain 100% 175 ~ 320 DEG C of diesel oil distillates are circulated to the second hydrocracking reactor entrance, and the temperature of reaction of the second hydrocracking reactor is 376 DEG C, and the quality product data of product slates and heavy naphtha list in table 3.From table 3, under the condition of the first hydrocracking reactor > 350 DEG C of transformation efficiencys about 68%, diesel oil (175 ~ 320 DEG C) cut that whole freshening obtains, heavy naphtha productive rate can reach 57.53%, scheelite selectivity is 85.4%, and it is 66.5% that virtue is dived.
Comparative example 3
The first hydrocracking catalyst I (RHC-3) is at catalyzer that first, second hydrocracking reactor is filled out, control the first hydrocracking reactor > 350 DEG C of transformation efficiencys about 69%, at reaction pressure 13.0MPa, hydrofining reactor temperature of reaction 366 DEG C, air speed 1.0h
-1; First hydrocracking reactor temperature of reaction 373 DEG C, air speed 1.5h
-1; One anti-entrance criterion state hydrogen to oil volume ratio is under the reaction conditions of 1200, adopts raw material A to carry out hydrocracking tests.Obtain 100% 175 ~ 320 DEG C of diesel oil distillates are circulated to the second hydrocracking reactor entrance by test, the temperature of reaction of the second hydrocracking reactor second hydrocracking reactor is 376 DEG C, and the quality product data of product slates and heavy naphtha list in table 5.From table 5, under the condition of the first hydrocracking reactor > 350 DEG C of transformation efficiencys about 69%, the diesel oil distillate (175 ~ 320 DEG C) that whole freshening obtains, heavy naphtha productive rate is 57.88%, heavy naphtha selectivity is 85.3%, and it is 62.6% that virtue is dived.Owing to not selecting the hydrocracking catalyst II that low metal is measured in second hydrocracking reactor of this comparative example, when whole freshening diesel oil (175 ~ 320 DEG C) cut, compared with embodiment 4, the virtue of the heavy naphtha of this comparative example is dived and is declined obviously, have dropped 3.9 percentage points, in addition, hydrogen consumption adds about 0.1%.
Table 1 stock oil character
| Stock oil is numbered | A |
| Density (20 DEG C)/(g/cm 3) | 0.9197 |
| Carbon content/% | 85.89 |
| Hydrogen richness/% | 11.96 |
| Condensation point/DEG C | 24 |
| Aniline point/DEG C | 77.4 |
| Carbon residue/% | 0.07 |
| Boiling range ASTM D-1160/ DEG C | |
| IBP | 267 |
| 10％ | 376 |
| 50％ | 436 |
| 90％ | 474 |
| FBP | 517 |
Table 2 embodiment 1, embodiment 2 processing condition, product slates and heavy naphtha character
Table 3 embodiment 3, embodiment 4 processing condition, product slates and heavy naphtha character
Table 4 comparative example 1, comparative example 2 processing condition, product slates and heavy naphtha character
Table 5 comparative example 3 processing condition, product slates and heavy naphtha character
Claims (13)
1. produce a method for hydrogen cracking for industrial chemicals, comprising:
(1) stock oil enters hydrofining reactor and the first follow-up hydrocracking reactor after mixing with hydrogen, reacts under the effect of Hydrobon catalyst and hydrocracking catalyst I;
The reaction effluent of (2) first hydrocracking reactors and the second hydrocracking reactor is after cooling, being separated, 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, diesel oil distillate and tail oil fraction through fractionation;
(3) diesel oil distillate of step (2) gained enters into the second hydrocracking reactor, under the effect of hydrocracking catalyst II, continue reaction, the percent by volume that the diesel oil distillate wherein entering the second hydrocracking reactor accounts for the total diesel oil distillate of step (2) gained is 10% ~ 100%;
Described hydrocracking catalyst II is the hydrocracking catalyst that low metal is measured, and the metal of hydrocracking catalyst II is measured on the metal lower than hydrocracking catalyst I and measures.
2. in accordance with the method for claim 1, it is characterized in that, with hydrocracking catalyst II for entirety, with oxide basis, on its metal, amount is less than or equal to 22 % by weight.
3. in accordance with the method for claim 1, it is characterized in that, the boiling range of described step (2) gained diesel oil distillate is 175 ~ 320 DEG C.
4. in accordance with the method for claim 1, it is characterized in that,
The reaction conditions of hydrofining reactor: temperature of reaction 250 DEG C ~ 450 DEG C, hydrogen dividing potential drop 5.0 ~ 18.0MPa, volume space velocity 0.2 ~ 10.0h during liquid
-1, hydrogen to oil volume ratio 100 ~ 3000Nm
3/ m
3;
The reaction conditions of the first hydrocracking reactor: temperature of reaction 250 ~ 450 DEG C, hydrogen dividing potential drop 5.0 ~ 18.0MPa, volume space velocity 0.2 ~ 10.0h during liquid
-1, hydrogen to oil volume ratio 50 ~ 3000Nm
3/ m
3;
The reaction conditions of the second hydrocracking reactor is: temperature of reaction 250 ~ 450 DEG C, hydrogen dividing potential drop 5.0 ~ 18.0MPa, volume space velocity 0.2 ~ 10.0h during liquid
-1, hydrogen to oil volume ratio 50 ~ 3000Nm
3/ m
3.
5. in accordance with the method for claim 1, it is characterized in that,
The reaction conditions of hydrofining reactor: temperature of reaction 300 DEG C ~ 420 DEG C, hydrogen dividing potential drop preferably 8.0 ~ 15.0MPa, volume space velocity 0.4 ~ 3.0h during liquid
-1, hydrogen to oil volume ratio 600 ~ 2000Nm
3/ m
3;
The reaction conditions of the first hydrocracking reactor: temperature of reaction 300 ~ 420 DEG C, hydrogen dividing potential drop 8.0 ~ 15.0MPa, volume space velocity 0.4 ~ 3.0h during liquid
-1, hydrogen to oil volume ratio 600 ~ 2000Nm
3/ m
3;
The reaction conditions of the second hydrocracking reactor is: temperature of reaction 300 ~ 420 DEG C, hydrogen dividing potential drop 8.0 ~ 15.0MPa, volume space velocity 1 ~ 4.0h during liquid
-1, hydrogen to oil volume ratio 600 ~ 2000Nm
3/ m
3.
6. in accordance with the method for claim 1, it is characterized in that, described stock oil be selected from decompressed wax oil, wax tailings, deasphalted oil, coal are produced in oil one or more, its boiling range scope is 260 ~ 610 DEG C.
7. in accordance with the method for claim 1, it is characterized in that, described Hydrobon catalyst, be benchmark with catalyzer, 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; Take 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%.
8. in accordance with the method for claim 1, it is characterized in that, hydrocracking catalyst I, containing a kind of carrier and load molybdenum on this carrier and/or tungsten and nickel and/or cobalt, with oxide basis and with catalyzer total amount for 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 ~ 10: 90; 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 8, it is characterized in that, described aluminum oxide be by little porous aluminum oxide and macroporous aluminium oxide according to 75: 25 ~ 50: 50 the aluminum oxide that is composited of weight ratio, wherein, little porous aluminum oxide is the aluminum oxide that pore volume that diameter is less than 80 dusts accounts for total pore volume more than 95%, and macroporous aluminium oxide is the aluminum oxide that the pore volume of diameter 60-600 dust accounts for total pore volume more than 70%.
10. according to the method described in claim 1 or 2, it is characterized in that, described hydrocracking catalyst II, containing a kind of carrier and load molybdenum on this carrier and/or tungsten and nickel and/or cobalt, with oxide basis and with catalyzer total amount for benchmark, the content of molybdenum and/or tungsten is 10 ~ 21 heavy %, the heavy % of content 1 ~ 6 of nickel and/or cobalt, this carrier is made up of aluminum oxide, zeolite, the weight ratio of aluminum oxide and zeolite is 90: 10 ~ 10: 90, the total acid content of described zeolite be 0.02 to be less than 0.5 mmole/gram.
11. in accordance with the method for claim 10, it is characterized in that, with oxide basis and with catalyzer total amount for benchmark, the content of molybdenum and/or tungsten is 15 ~ 20 heavy %, the heavy % of content 2 ~ 4 of nickel and/or cobalt.
12. in accordance with the method for claim 10, it is characterized in that, described aluminum oxide be by little porous aluminum oxide and macroporous aluminium oxide according to 75: 25 ~ 50: 50 the aluminum oxide that is composited of weight ratio, wherein, little porous aluminum oxide is the aluminum oxide that pore volume that diameter is less than 80 dusts accounts for total pore volume more than 95%, and macroporous aluminium oxide is the aluminum oxide that the pore volume of diameter 60-600 dust accounts for total pore volume more than 70%.
13. in accordance with the method for claim 1, it is characterized in that, the per pass conversion controlling the first hydrocracking reactor is 50% ~ 80%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110324623.0A CN103059986B (en) | 2011-10-24 | 2011-10-24 | Hydrocracking method for producing chemical materials |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110324623.0A CN103059986B (en) | 2011-10-24 | 2011-10-24 | Hydrocracking method for producing chemical materials |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103059986A CN103059986A (en) | 2013-04-24 |
| CN103059986B true CN103059986B (en) | 2015-02-25 |
Family
ID=48102891
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201110324623.0A Active CN103059986B (en) | 2011-10-24 | 2011-10-24 | Hydrocracking method for producing chemical materials |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103059986B (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105018139B (en) * | 2014-04-23 | 2016-10-26 | 中国石油化工股份有限公司 | A kind of method for hydrogen cracking of the high-output qulified industrial chemicals of low energy consumption |
| CN105567273B (en) * | 2014-10-17 | 2018-04-13 | 中国石油化工股份有限公司 | The weighted BMO spaces method of coal tar and the hydrotreating method of coal tar |
| CN106520195B (en) * | 2015-09-11 | 2018-05-18 | 中国石油化工股份有限公司 | A kind of method for hydrogen cracking for improving boat coal quality |
| CN105694966B (en) * | 2016-03-25 | 2017-08-22 | 中国海洋石油总公司 | A kind of method that naphtha and clean gasoline are produced by catalytic cracking diesel oil |
| CN108003933B (en) * | 2016-10-31 | 2020-05-19 | 中国石油化工股份有限公司 | Hydrocracking method for producing chemical raw materials from diesel oil fraction |
| CN110257102B (en) * | 2019-07-17 | 2021-12-07 | 胜帮科技股份有限公司 | Production system and method for preparing light aromatic hydrocarbon by staged hydro-pyrolysis of raw material rich in polycyclic aromatic hydrocarbon |
| CN116064139A (en) * | 2021-10-30 | 2023-05-05 | 中国石油化工股份有限公司 | Combined hydrogenation process and system for maximally producing chemical raw materials |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1488731A (en) * | 2002-10-10 | 2004-04-14 | 中国石油化工股份有限公司 | Hydrocracking method for increasing quality of refined diesel oil |
| US7094332B1 (en) * | 2003-05-06 | 2006-08-22 | Uop Llc | Integrated process for the production of ultra low sulfur diesel and low sulfur fuel oil |
| CN101117594A (en) * | 2006-07-31 | 2008-02-06 | 中国石油化工股份有限公司 | Hydrogenation method for producing clean diesel oil |
| CN101173190A (en) * | 2007-10-22 | 2008-05-07 | 中国石油集团工程设计有限责任公司抚顺分公司 | Feito synthetic oil processing line |
| CN101210198A (en) * | 2006-12-27 | 2008-07-02 | 中国石油化工股份有限公司 | Hydrogenation method for producing high grade diesel oil and high grade reforming raw material |
| CN101280221A (en) * | 2007-04-04 | 2008-10-08 | 中国石油化工股份有限公司 | Hydrogenation conversion method for poor ignition quality fuel distillate |
-
2011
- 2011-10-24 CN CN201110324623.0A patent/CN103059986B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1488731A (en) * | 2002-10-10 | 2004-04-14 | 中国石油化工股份有限公司 | Hydrocracking method for increasing quality of refined diesel oil |
| US7094332B1 (en) * | 2003-05-06 | 2006-08-22 | Uop Llc | Integrated process for the production of ultra low sulfur diesel and low sulfur fuel oil |
| CN101117594A (en) * | 2006-07-31 | 2008-02-06 | 中国石油化工股份有限公司 | Hydrogenation method for producing clean diesel oil |
| CN101210198A (en) * | 2006-12-27 | 2008-07-02 | 中国石油化工股份有限公司 | Hydrogenation method for producing high grade diesel oil and high grade reforming raw material |
| CN101280221A (en) * | 2007-04-04 | 2008-10-08 | 中国石油化工股份有限公司 | Hydrogenation conversion method for poor ignition quality fuel distillate |
| CN101173190A (en) * | 2007-10-22 | 2008-05-07 | 中国石油集团工程设计有限责任公司抚顺分公司 | Feito synthetic oil processing line |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103059986A (en) | 2013-04-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103059972B (en) | Combined hydrogenation method of producing chemical materials | |
| CN103013559B (en) | Hydrocracking method for selective increasing of aviation kerosene yield | |
| CN103059986B (en) | Hydrocracking method for producing chemical materials | |
| CN102399586B (en) | A mid-pressure hydrocracking method for producing jet fuel | |
| CN102453535B (en) | Hydrocracking method for reforming material yield increase | |
| CN112143522A (en) | Hydrogenation method and system for production chemical material | |
| CN101684417A (en) | Optimized hydrogenation-catalytic cracking combination process | |
| CN102344828B (en) | Processing method of inferior residual oil | |
| CN103102944A (en) | Combined process of hydrotreatment and light fraction-conversion for residual oil | |
| CN101747936B (en) | Hydrogenation method for producing high-quality low-sulfur diesel fraction | |
| CN103102980A (en) | Combined process for in-depth conversion of residual oil | |
| CN104593068A (en) | A method of producing gasoline with a high octane number from residual oil | |
| CN103102982A (en) | Combined process for conversion of residual oil | |
| CN103305273B (en) | A kind of catalysis conversion method reducing coke and dry gas yied | |
| CN103059934A (en) | Hydrogenation, modification and pour point depression method by consideration of product quality of diesel oil | |
| CN103305272B (en) | Catalytic conversion method for reducing yield of cokes | |
| CN101892078A (en) | Preparation method of coal-based naphtha with high potential aromatic content for catalytic reforming, product and application thereof | |
| CN100419044C (en) | Production of large-specific-weight aircraft liquid petroleum oil at maximum from coal liquefied oil | |
| CN100510022C (en) | Low-hydrogenloss hydrogenation of high-output qulified diesel oil | |
| CN105618111A (en) | Preparation of catalyst catalyzing diesel hydro-conversion, and hydrogenation process | |
| CN106520197B (en) | A kind of method for hydrogen cracking that boat coal is produced by inferior feedstock oil | |
| CN109988631A (en) | A kind of method of the catalyst grade with technology production gasoline and base oil | |
| CN103102981A (en) | Treating method for heavy raw material | |
| CN103059993B (en) | Catalytic conversion method of petroleum hydrocarbon | |
| CN102911730B (en) | Catalytic conversion method for high sulfur wax oil |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |