CN103059986A - Hydrocracking method for producing chemical materials - Google Patents
Hydrocracking method for producing chemical materials Download PDFInfo
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- CN103059986A CN103059986A CN2011103246230A CN201110324623A CN103059986A CN 103059986 A CN103059986 A CN 103059986A CN 2011103246230 A CN2011103246230 A CN 2011103246230A CN 201110324623 A CN201110324623 A CN 201110324623A CN 103059986 A CN103059986 A CN 103059986A
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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 there being acquisition cracking hydrocarbon ils in the situation of hydrogen, more particularly, is a kind of method for hydrogen cracking of producing industrial chemicals.
Background technology
Reformer is the important secondary processing device of refinery, for the production of the stop bracket gasoline blend component or for the production of the aromatic hydrocarbons basic material.Reformed gasoline has the octane value height, does not contain alkene, and the characteristics such as sulfur-bearing, nitrogen impurity are not the gasoline blend components of high-quality.Compare with American-European countries, the reformed gasoline component was on the low side during present domestic gasoline consisted of, and catalytically cracked gasoline component proportion is higher, caused that domestic goods gasoline sulfur and olefin(e) centent are high, aromaticity content is relatively low; The ratio that increases reformed gasoline in the gasoline pool is conducive to reduce sulphur and olefin(e) centent, satisfies the environmental regulation requirement of increasingly stringent.Benzene,toluene,xylene is the basic material of petrochemical industry, and reformer generates in the 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 are produced the dual-pressure of clean fuel, so that hydrogenation process becomes more and more widely processing means of application, but the cheap hydrogen that the reformer by-product is a large amount of, also expect and can obtain more hydrogen by enlarging the reformer scale, satisfies the hydrogen balance of full factory the refinery.
Virgin naphtha is the main source of reformer charging.For a long time, the crude oil in China yield of light oil is lower, and virgin naphtha is one of raw material of ethylene unit, and the 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 resulting heavy naphtha has the aromaticity content height, and sulphur, the characteristics that nitrogen impurity content is low can directly as the reformer charging of high-quality, remedy the deficiency of virgin naphtha.
Hydrocracking process is take 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 the flow process, for improving the heavy naphtha productive rate, can take to improve the method for transformation efficiency, heavy ends more is converted into light-end products, descend but also can cause heavy naphtha selectivity and virtue to be dived simultaneously, hydrogen gas consumption increases.
Increasing heavy naphtha also can be to whole intermediate oils freshening that circulates, the method can effectively increase the yield of heavy naphtha, but on the one hand, a large amount of intercycle distillates will inevitably increase volume space velocity greatly under the prerequisite that catalytic amount does not increase, 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, be not that whole intermediate oils are suitable recycle fraction, and the virtue that adopts recycle to extinction may reduce heavy naphtha fraction is dived and selectivity.
CN 101210198A discloses a kind of method of hydrotreating of producing fine-quality diesel oil and high-quality reformer feed, after diesel oil and/or light wax oil raw material and hydrogen mix successively with Hydrobon catalyst with the hydrocracking catalyst contact reacts and without separating the centre, resultant of reaction is through cooling, obtain light naphtha fraction after the separation, 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, wherein resulting reformer feed yield is greater than 20 % by weight.
USP4,172,815 disclose the single hop circulation method for hydrogen cracking of producing simultaneously rocket engine fuel and diesel oil, and the initial boiling point of raw material is greater than 500 °F (about 260 ℃).Its technical process is briefly described as follows: stock oil is through hydrocracking, temperature of reaction is lower than 900 °F (about 482 ℃), 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, the rocket engine fuel cut is all or part of to be mixed with tail oil, sends the cracking reaction district back to.The method can reach the purpose that the while maximum is produced rocket engine fuel and diesel oil under the hydrocracking condition that comparatively relaxes, 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, after being heavy raw oil and hydrogen mixes, its characteristics enter the one-stage hydrogenation treatment zone, one section effluent separates the hydrogen-rich gas that obtains 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, intermediate oil separately or be mixed into the secondary hydrogenation treatment zone with other inferior distillate oil and carry out cracking, two sections gas circulation that obtain are used.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 urged bavin and the heavy hydrogenated cracking stock mixes, at first carry out hydrocracking, the gained intermediate oil carries out the secondary hydrogenation cracking, obtains the tail oil of the latent heavy naphtha of high virtue and low BMCI value.
Summary of the invention
The objective of the invention is to provide on the basis of existing technology a kind of method for hydrogen cracking of producing industrial chemicals.
Method provided by the invention comprises:
(1) stock oil with enter hydrofining reactor and follow-up the first hydrocracking reactor after hydrogen mixes, under the effect of Hydrobon catalyst and hydrocracking catalyst I, react;
The reaction effluent of (2) first hydrocracking reactors and the second hydrocracking reactor is after cooling, separating, 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 cut through fractionation;
(3) diesel oil distillate of step (2) gained enters into the second hydrocracking reactor, continue reaction under the effect of hydrocracking catalyst II, the percent by volume that the diesel oil distillate that wherein enters 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 of measuring on the low metal, measures on the metal that is lower than hydrocracking catalyst I on the metal of hydrocracking catalyst II and measures.
Take hydrocracking catalyst II as whole, in oxide compound, amount is less than or equal to 22 % by weight on its metal.
The boiling range of the diesel oil distillate of step (2) gained is 175～320 ℃.
Adopt method provided by the invention can effectively increase production reformer feed, extract 10%～100%175～320 ℃ of diesel oil distillates out to the second hydrocracking reactor, it is carried out freshening, in the heavy naphtha that raises productivity and improves the quality, also can improve the selectivity of heavy naphtha.The naphthenic hydrocarbon of described diesel oil distillate and aromaticity content are high, carry out again hydrocracking, and the heavy naphtha virtue of acquisition is dived higher, and selectivity is better.In addition, the hydrocracking catalyst II that measures on the low metal of the second hydrocracking reactor filling, the Hydrogenation that itself and cracking performance are complementary is lower, from reaction process, be conducive to increase the aromaticity content in the heavy naphtha, thereby the virtue that improves heavy naphtha fraction is dived reduction hydrogen consumption; On the other hand, the reaction raw materials of the second hydrocracking reactor is 175～320 ℃ of diesel oil distillates, its nitrogen content is low, boiling range is relatively light, compare more difficult generation dehydrogenation pyrogenic reaction with the wax oil cut, adopt the hydrocracking catalyst II that measures on the low metal, can the long-term operation of device not exerted an influence.
Description of drawings
Accompanying drawing is production industrial chemicals method for hydrogen cracking schematic flow sheet provided by the invention.
Embodiment
In step (1), stock oil enters hydrofining reactor with (mixed gas of recycle hydrogen and new hydrogen), under the effect of Hydrobon catalyst, carry out hydrogenating desulfurization, hydrodenitrification, olefin saturated and the reaction of part aromatic saturation, reaction conditions is as follows: 250 ℃～450 ℃ of temperature of reaction, preferred 300 ℃～420 ℃, hydrogen dividing potential drop 5.0～18.0MPa, preferred 8.0～15.0MPa, volume space velocity 0.2～10.0h during liquid
-1, preferred 0.4～3.0h
-1, hydrogen to oil volume ratio 100～3000Nm
3/ m
3, preferred 600～2000Nm
3/ m
3
Entering the first hydrocracking reactor after whole cuts of hydrofining gained and part recycle hydrogen mix contacts with hydrocracking catalyst I and reacts, reaction conditions is as follows: 250～450 ℃ of temperature of reaction, preferred 300～420 ℃, hydrogen dividing potential drop 5.0～18.0MPa, preferred 8.0～15.0MPa, volume space velocity 0.2～10.0h during liquid
-1, preferred 0.4～3.0h
-1, hydrogen to oil volume ratio 50～3000Nm
3/ m
3, preferred 600～2000Nm
3/ m
3
In step (2), the reaction of the first hydrocracking reactor generates oil after cooling, enter successively high-pressure separator and light pressure separator and carry 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 boosts; The liquid phase stream of gained enters fractionating system, obtains light naphtha fraction, heavy naphtha fraction, diesel oil distillate (175～320 ℃) and tail oil cut after fractionation.
In step (3), be that 10%～100% diesel oil distillate (175～320 ℃) is circulated to the second hydrocracking reactor after boosting with percent by volume, in the presence of hydrogen, contact with hydrocracking catalyst II and carry out cracking reaction.Reaction conditions is: 250～450 ℃ of temperature of reaction, preferred 300～420 ℃, hydrogen dividing potential drop 5.0～18.0MPa, preferred 8.0～15.0MPa, volume space velocity 0.2～10.0h during liquid
-1, preferred 1～4.0h
-1, hydrogen to oil volume ratio 50～3000Nm
3/ m
3, preferred 600～2000Nm
3/ m
3The reaction generation oil of the second hydrocracking reactor enters follow-up high-pressure separator, light pressure separator and fractionating system to be separated and fractionation.The reaction that preferably obtains 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 and produces in the oil one or more, and its boiling range scope is 260～610 ℃.
Described Hydrobon catalyst, take catalyzer as benchmark, it consists of: nickel oxide 1～10 heavy %, molybdenum oxide and Tungsten oxide 99.999 sum are 10～50 heavy %, fluorine 1～10 heavy %, phosphorus oxide 0.5～8 heavy %, surplus is silica-alumina; Take carrier as benchmark, by weight, the content of the silicon oxide in the 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 and above reaction pressure, be lower than 10 μ g/g through nitrogen content in the treated oil after this catalyst treatment, satisfy the charging requirement of cracking zone catalyzer fully.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 the stock oil, the charging that is easy to occur cracking reaction is provided for cracking zone, can be so that the hydrocracking tail oil aromaticity content be extremely low, have low BMCI value, can be used as the raw material of the preparing ethylene by steam cracking of high-quality.
The hydrocracking catalyst I that loads in described the first hydrocracking reactor, contain a kind of carrier and the molybdenum and/or tungsten and nickel and/or the cobalt that load on this carrier, in oxide compound and take the catalyzer total amount as benchmark, the content of molybdenum and/or tungsten is 10～35 heavy %, content 1～15 heavy % of nickel and/or cobalt, this carrier is comprised of aluminum oxide and zeolite, and the weight ratio of aluminum oxide and zeolite is 90: 10～10: 90.
Described aluminum oxide is the aluminum oxide that is composited according to 75: 25～50: 50 weight ratio by little porous aluminum oxide and macroporous aluminium oxide, wherein, to be diameter account for the aluminum oxide of total pore volume more than 95% less than the pore volume of 80 dusts to little porous aluminum oxide, and macroporous aluminium oxide is that the pore volume of diameter 60-600 dust accounts for the aluminum oxide of total pore volume more than 70%.
The total acid content of described zeolite is 0.02 to less than 0.5 mmole/gram.The preferred hydrocracking catalyst I of the present invention performance is good, can transform nitrogen content and the higher raw material of aromaticity content under lower pressure.
The hydrocracking catalyst II that loads in described the second hydrocracking reactor, contain a kind of carrier and the molybdenum and/or tungsten and nickel and/or the cobalt that load on this carrier, in oxide compound and take the catalyzer total amount as benchmark, the content of molybdenum and/or tungsten is 10～21 heavy %, preferred 15～20 heavy %, content 1～6 heavy % of nickel and/or cobalt, preferred 2～4 heavy %, this carrier is comprised 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 of measuring on the low metal, measure on the metal that is lower than hydrocracking catalyst I on the metal of hydrocracking catalyst II and measure, namely the active metallic content of hydrocracking catalyst II load is lower than the active metallic content of hydrocracking catalyst I load.Take hydrocracking catalyst II as whole, in oxide compound, amount is less than or equal to 22 % by weight on its metal.
Described aluminum oxide is the aluminum oxide that is composited according to 75: 25～50: 50 weight ratio by little porous aluminum oxide and macroporous aluminium oxide, wherein, to be diameter account for the aluminum oxide of total pore volume more than 95% less than the pore volume of 80 dusts to little porous aluminum oxide, and macroporous aluminium oxide is that the pore volume of diameter 60-600 dust accounts for the aluminum oxide of total pore volume more than 70%.
The total acid content of described zeolite is 0.02 to less than 0.5 mmole/gram.The preferred hydrocracking catalyst II of the present invention excellent property be conducive to obtain the heavy naphtha fraction of Gao Fangqian, and selectivity is good.Heavy naphtha selectivity of the present invention refers to that cracking under certain depth of conversion generates the massfraction that heavy naphtha fraction yield in the oil accounts for whole naphtha fraction yields, and formulate is as follows:
Heavy naphtha selectivity=(heavy naphtha fraction yield/whole 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 Returning reacting system no longer after reaction, but with 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 ℃ of cut per pass conversion that formulate is as follows:
Accompanying drawing is the method for hydrogen cracking synoptic diagram of production industrial chemicals provided by the invention.Below in conjunction with accompanying drawing method provided by the present invention is described further, has omitted equipment component among the figure, such as pump, interchanger etc., but this is known to those of ordinary skills.
Method for hydrogen cracking technical process provided by the invention is described in detail as follows: from the stock oil of pipeline 1 with from the new hydrogen of pipeline 16 and mixed from the recycle hydrogen of pipeline 17 after enter hydrofining reactor 2, under the effect of Hydrobon catalyst, react, its reaction effluent with enter the first hydrocracking reactor 3 after part recycle hydrogen from pipeline 17 mixes, under the effect of hydrocracking catalyst I, react, 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 tops enters circulating hydrogen compressor 6, by pipeline 17 minutes three tunnel, enter respectively hydrofining reactor 2 and the first hydrocracking reactor 3 and the second hydrocracking reactor 15 through the circulating hydrogen compressor supercharging.The liquid phase thing of high-pressure separator 4 bottoms enters light pressure separator 5, carries out further gas-liquid separation at this; The liquid phase stream of light pressure separator 5 bottoms enters separation column 8.Enter the liquid phase stream of separation column 8 after fractionation, cut into the light naphtha fraction, heavy naphtha fraction, diesel oil distillate and the tail oil cut that obtain and extract out through pipeline 9,10,11 and 13 successively.Diesel oil distillate is after pipeline 11 is extracted out, and partly or entirely diesel oil distillate is pressurized to the second hydrocracking reactor 15 entrances through pipeline 12, and all the other diesel oil distillates go out device.Diesel oil distillate contacts 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 after make-up hydrogen compressor 7 pressurizations through pipeline 6.
Advantage of the present invention is:
1, adopt method provided by the invention, productive rate that can Effective Raise heavy naphtha, and improve the selectivity of heavy naphtha.Because behind the described diesel oil distillate process circulation freshening, further carry out cracking, thereby increased the productive rate of heavy naphtha; Owing to do not improve the severity of reaction, can keep high heavy naphtha selectivity.
2, compare with other middle runnings, 175～320 ℃ of diesel oil distillates that the present invention selects are because naphthenic hydrocarbon and aromaticity content are high, and the heavy naphtha virtue that this cut of freshening obtains is dived higher, and the heavy naphtha selectivity is good.
3, the second hydrocracking reactor has adopted the hydrocracking catalyst II that measures on the low metal, and the heavy naphtha that obtains virtue is dived high, and the hydrogen consumption is low.
The following examples will be further described method provided by the invention, but not thereby limiting the invention.
The trade names of used Hydrobon catalyst are RN-32V among the embodiment, and the trade names of the used hydrocracking catalyst I of the first hydrocracking reactor are RHC-3, are catalyzer Chang Ling branch office of China Petrochemical Corp. and produce.
Hydrocracking catalyst II consists of: in oxide compound, and take hydrocracking catalyst II total amount as benchmark, the content of molybdenum is 18 heavy %, the content 2 heavy % of nickel, and amount is 20% on total metal.Its carrier is: aluminum oxide 50 % by weight, zeolite (Y zeolite) 30 % by weight.
Used stock oil A is a kind of VGO among the embodiment, and its main character is as shown in table 1.
Embodiment 1
Adopt method provided by the invention, at reaction pressure 13.0MPa, 365 ℃ of hydrofining reactor temperature of reaction, air speed 1.0h
-1368 ℃ of the first hydrocracking reactor temperature of reaction, air speed 1.5h
-1368 ℃ of the second hydrocracking reactor temperature, air speed 1.5h
-1One anti-entrance criterion state hydrogen to oil volume ratio is under 1200 the reaction conditions, adopts raw material A (the second hydrocracking reactor catalyst system therefor is amount hydrocracking catalyst II on the low metal) to carry out the hydrocracking test.In the process of the test, the diesel oil distillate of 50% (accounting for whole 175～320 ℃ of diesel oil distillate volume numbers) is circulated to the second hydrocracking reactor entrance, test-results is as shown in table 2.
As can be seen from Table 2, be about at the first hydrocracking reactor＞350 ℃ transformation efficiency under 58% the condition, the productive rate of heavy naphtha fraction is 34.06% (accounting for the mass percent of liquid hydrocarbon product), and the productive rate of diesel oil distillate is 18.42%, and the tail oil productive rate is 42.03%; In addition, the selectivity of heavy naphtha is 86.1%.The heavy naphtha virtue that obtains is dived and has been reached 65.3%.
Comparative Examples 1
At reaction pressure 13.0MPa, 365 ℃ of hydrofining reactor temperature of reaction, air speed 1.0h
-1368 ℃ of hydrocracking reactor temperature of reaction, air speed 1.5h
-1, an anti-entrance criterion state hydrogen to oil volume ratio is under 1200 the reaction conditions.With conventional method for hydrogen cracking, adopt raw material A to carry out the hydrocracking test, test-results is as shown in table 4.
Can obtain from table 4, be about at＞350 ℃ of transformation efficiencys under 58% the condition, the productive rate of product heavy naphtha (65～175 ℃) cut only is 19.23% (accounting for the mass percent of liquid hydrocarbon), hang down about 15 percentage points than embodiment 1, the yield of diesel oil distillate (175～320 ℃) is 36.02%, and tail oil (＞320 ℃) cut productive rate is 41.10%; In addition, the selectivity of heavy naphtha only is 84.0%, hangs down about 2 percentage points than embodiment 1, and it is 61.5% that the virtue of heavy naphtha is dived, than embodiment 1 low 3.8%.The test-results explanation of embodiment 1 and Comparative Examples 1 once passing through to adopt method of the present invention under the identical condition of transformation efficiency, can effectively increase the productive rate of heavy naphtha, and the selectivity of heavy naphtha also improves a lot with fragrant diving.
Comparative Examples 2
Controlling the first hydrocracking reactor＞350 ℃ transformation efficiency is 58%, at reaction pressure 13.0MPa, 366 ℃ of hydrofining reactor temperature of reaction, air speed 1.0h
-1369 ℃ of the first hydrocracking reactor temperature of reaction, air speed 1.5h
-1369 ℃ of the second hydrocracking reactor temperature of reaction, air speed 1.5h
-1One anti-entrance criterion state hydrogen to oil volume ratio is under 1200 the reaction conditions, adopts raw material A (the second hydrocracking reactor filling hydrocracking catalyst II) to carry out the hydrocracking test.Be about at control heavy naphtha productive rate under 34% the condition, be that 175～370 ℃ part diesel oil distillate (the circulation diesel oil amount among internal circulating load and the embodiment 1 is basic identical) is recycled to the second hydrocracking reactor entrance with boiling range, product distributes and heavy naphtha product property data are listed in table 4.By table 2 and as seen from Table 4, embodiment 1 (175～320 ℃ of diesel oil distillates of freshening) compares with Comparative Examples 2 (175～370 ℃ of diesel oil distillates of freshening same amount), embodiment 1 obtains dive than Comparative Examples 2 high about 1 percentage point of heavy naphtha product virtue, and embodiment 1 heavy naphtha selectivity ratios Comparative Examples 2 height are about 0.6 percentage point in addition.
Embodiment 2
Adopt method provided by the invention, control the first hydrocracking reactor＞350 ℃ transformation efficiency 72%, at reaction pressure 13.0MPa, 365 ℃ of hydrofining reactor temperature of reaction, air speed 1.0h
-1374 ℃ of the first hydrocracking reactor temperature of reaction, air speed 1.5h
-1One anti-entrance criterion state hydrogen to oil volume ratio is under 1200 the reaction conditions, adopts raw material A (the second hydrocracking reactor filling hydrocracking catalyst II) to carry out the hydrocracking test.175～320 ℃ of diesel oil distillates of 50% are circulated to the second hydrocracking reactor entrance, and the temperature of reaction of the second hydrocracking reactor is 370 ℃, and product distributes and the quality product data of heavy naphtha are listed in table 2.By as seen from Table 2, under the condition of the first hydrocracking reactor＞350 ℃ transformation efficiency about 72%, the heavy naphtha productive rate that freshening obtains can reach 43.43%, and it is 64.5% that virtue is dived.Compare with embodiment 1, owing to increased substantially depth of conversion, under the identical condition of freshening diesel oil ratio, can increase the productive rate of heavy naphtha, but virtue is dived and can be descended to some extent.
Embodiment 3
Adopt method provided by the invention, it is about 59% to control the first hydrocracking reactor＞350 ℃ transformation efficiency, at 365 ℃ of reaction pressure 13.0MPa, hydrofining reactor temperature of reaction, air speed 1.0h
-1369 ℃ of the first hydrocracking reactor temperature of reaction, air speed 1.5h
-1One anti-entrance criterion state hydrogen to oil volume ratio is under 1200 the reaction conditions, adopts raw material A (the second hydrocracking reactor filling hydrocracking catalyst II) to carry out the hydrocracking test.100% 175～320 ℃ of diesel oil distillates that obtain are circulated to the second hydrocracking reactor entrance, and the temperature of reaction of the second hydrocracking reactor is 377 ℃, and product distributes and the quality product data of heavy naphtha are listed in table 3.By as seen from Table 3, under the condition of the first hydrocracking reactor＞350 ℃ transformation efficiency about 59%, the diesel oil distillate (175～320 ℃) that whole freshenings obtain, the heavy naphtha productive rate can reach 51.01%, the 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 ℃ transformation efficiency 68%, at reaction pressure 13.0MPa, 365 ℃ of hydrofining reactor temperature of reaction, air speed 1.0h
-1372 ℃ of the first hydrocracking reactor temperature of reaction, air speed 1.5h
-1One anti-entrance criterion state hydrogen to oil volume ratio is under 1200 the reaction conditions, adopts raw material A (the second hydrocracking reactor filling hydrocracking catalyst II) to carry out the hydrocracking test.100% 175～320 ℃ of diesel oil distillates that obtain are circulated to the second hydrocracking reactor entrance, and the temperature of reaction of the second hydrocracking reactor is 376 ℃, and product distributes and the quality product data of heavy naphtha are listed in table 3.By as seen from Table 3, under the condition of the first hydrocracking reactor＞350 ℃ transformation efficiency about 68%, diesel oil (175～320 ℃) cut that whole freshenings obtain, the heavy naphtha productive rate can reach 57.53%, and the scheelite selectivity is 85.4%, and it is 66.5% that virtue is dived.
Comparative Examples 3
Be the first hydrocracking catalyst I (RHC-3) at catalyzer that first, second hydrocracking reactor is filled out, it is about 69% to control the first hydrocracking reactor＞350 ℃ transformation efficiency, at reaction pressure 13.0MPa, 366 ℃ of hydrofining reactor temperature of reaction, air speed 1.0h
-1373 ℃ of the first hydrocracking reactor temperature of reaction, air speed 1.5h
-1One anti-entrance criterion state hydrogen to oil volume ratio is under 1200 the reaction conditions, adopts raw material A to carry out the hydrocracking test.175～320 ℃ of diesel oil distillates of 100% that test will obtain are circulated to the second hydrocracking reactor entrance, the temperature of reaction of the second hydrocracking reactor the second hydrocracking reactor is 376 ℃, and product distributes and the quality product data of heavy naphtha are listed in table 5.By as seen from Table 5, under the condition of the first hydrocracking reactor＞350 ℃ transformation efficiency about 69%, the diesel oil distillate (175～320 ℃) that whole freshenings obtain, the heavy naphtha productive rate is 57.88%, and the heavy naphtha selectivity is 85.3%, and it is 62.6% that virtue is dived.Owing to do not select the hydrocracking catalyst II that measures on the low metal in second hydrocracking reactor of this Comparative Examples, in the situation of whole freshening diesel oil (175～320 ℃) cuts, compare with embodiment 4, the virtue of the heavy naphtha of this Comparative Examples is dived and is descended obviously, 3.9 percentage points have been descended, in addition, the hydrogen consumption has increased about 0.1%.
Table 1 stock oil character
| The stock oil numbering | A |
| Density (20 ℃)/(g/cm 3) | 0.9197 |
| Carbon content/% | 85.89 |
| Hydrogen richness/% | 11.96 |
| Condensation point/℃ | 24 |
| Aniline point/℃ | 77.4 |
| Carbon residue/% | 0.07 |
| D-1160/ ℃ of boiling range ASTM | |
| IBP | 267 |
| 10％ | 376 |
| 50％ | 436 |
| 90％ | 474 |
| FBP | 517 |
Table 2 embodiment 1, embodiment 2 processing condition, product distribute and heavy naphtha character
Table 3 embodiment 3, embodiment 4 processing condition, product distribute and heavy naphtha character
Table 4 Comparative Examples 1, Comparative Examples 2 processing condition, product distribute and heavy naphtha character
Table 5 Comparative Examples 3 processing condition, product distribute and heavy naphtha character
Claims (13)
1. method for hydrogen cracking of producing industrial chemicals comprises:
(1) stock oil with enter hydrofining reactor and follow-up the first hydrocracking reactor after hydrogen mixes, under the effect of Hydrobon catalyst and hydrocracking catalyst I, react;
The reaction effluent of (2) first hydrocracking reactors and the second hydrocracking reactor is after cooling, separating, 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 cut through fractionation;
(3) diesel oil distillate of step (2) gained enters into the second hydrocracking reactor, continue reaction under the effect of hydrocracking catalyst II, the percent by volume that the diesel oil distillate that wherein enters 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 of measuring on the low metal, measures on the metal that is lower than hydrocracking catalyst I on the metal of hydrocracking catalyst II and measures.
2. in accordance with the method for claim 1, it is characterized in that take hydrocracking catalyst II as whole, in oxide compound, amount is less than or equal to 22 % by weight on its metal.
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 ℃.
4. in accordance with the method for claim 1, it is characterized in that,
The reaction conditions of hydrofining reactor: 250 ℃～450 ℃ of temperature of reaction, 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: 250～450 ℃ of temperature of reaction, 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: 250～450 ℃ of temperature of reaction, 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: 300 ℃～420 ℃ of temperature of reaction, the preferred 8.0～15.0MPa of hydrogen dividing potential drop, 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: 300～420 ℃ of temperature of reaction, 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: 300～420 ℃ of temperature of reaction, 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 is selected from decompressed wax oil, wax tailings, deasphalted oil, coal and produces in the oil one or more, its boiling range scope is 260～610 ℃.
7. in accordance with the method for claim 1, it is characterized in that described Hydrobon catalyst, take catalyzer as benchmark, it consists of: nickel oxide 1～10 heavy %, and molybdenum oxide and Tungsten oxide 99.999 sum are 10～50 heavy %, fluorine 1～10 heavy %, phosphorus oxide 0.5～8 heavy %, surplus is silica-alumina; Take carrier as benchmark, by weight, the content of the silicon oxide in the 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, contain a kind of carrier and the molybdenum and/or tungsten and nickel and/or the cobalt that load on this carrier, in oxide compound and take the catalyzer total amount as benchmark, the content of molybdenum and/or tungsten is 10～35 heavy %, content 1～15 heavy % of nickel and/or cobalt, this carrier is comprised 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 is 0.02 to less than 0.5 mmole/gram.
9. in accordance with the method for claim 8, it is characterized in that, described aluminum oxide is the aluminum oxide that is composited according to 75: 25～50: 50 weight ratio by little porous aluminum oxide and macroporous aluminium oxide, wherein, to be diameter account for the aluminum oxide of total pore volume more than 95% less than the pore volume of 80 dusts to little porous aluminum oxide, and macroporous aluminium oxide is that the pore volume of diameter 60-600 dust accounts for the aluminum oxide of total pore volume more than 70%.
10. according to claim 1 or 2 described methods, it is characterized in that, described hydrocracking catalyst II, contain a kind of carrier and the molybdenum and/or tungsten and nickel and/or the cobalt that load on this carrier, in oxide compound and take the catalyzer total amount as benchmark, the content of molybdenum and/or tungsten is 10～21 heavy %, content 1～6 heavy % of nickel and/or cobalt, this carrier is comprised of aluminum oxide, zeolite, the weight ratio of aluminum oxide and zeolite is 90: 10～10: 90, and the total acid content of described zeolite is 0.02 to less than 0.5 mmole/gram.
11. in accordance with the method for claim 10, it is characterized in that in oxide compound and take the catalyzer total amount as benchmark, the content of molybdenum and/or tungsten is 15～20 heavy %, content 2～4 heavy % of nickel and/or cobalt.
12. in accordance with the method for claim 10, it is characterized in that, described aluminum oxide is the aluminum oxide that is composited according to 75: 25～50: 50 weight ratio by little porous aluminum oxide and macroporous aluminium oxide, wherein, to be diameter account for the aluminum oxide of total pore volume more than 95% less than the pore volume of 80 dusts to little porous aluminum oxide, and macroporous aluminium oxide is that the pore volume of diameter 60-600 dust accounts for the aluminum oxide of total pore volume more than 70%.
13. in accordance with the method for claim 1, it is characterized in that the per pass conversion of controlling the first hydrocracking reactor is 50%～80%.
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