CN101684415B - Hydrocracking method for producing chemical materials to maximum with low cost - Google Patents
Hydrocracking method for producing chemical materials to maximum with low cost Download PDFInfo
- Publication number
- CN101684415B CN101684415B CN2008101668522A CN200810166852A CN101684415B CN 101684415 B CN101684415 B CN 101684415B CN 2008101668522 A CN2008101668522 A CN 2008101668522A CN 200810166852 A CN200810166852 A CN 200810166852A CN 101684415 B CN101684415 B CN 101684415B
- Authority
- CN
- China
- Prior art keywords
- hydrogen
- oil
- reaction
- reaction zone
- gas
- 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
Images
Abstract
The invention relates to a hydrocracking method for producing chemical materials to the maximum with low cost, comprising the following steps: mixing raw oil and hydrogen gas , entering a first reaction area, sequentially contacting with hydrofining catalyst and hydrocracking catalyst, reacting under the pressure of 6.0-16.0 MPa; carrying out oil-gas separation and fractionation on the reaction products thereof to obtain liquefied gas, light naphtha fractions, heavy naphtha fractions, middle fractions and tail oil fractions; mixing the middle fractions and the hydrogen gas and enteringa second reaction area, contacting with the hydrocracking catalyst under the pressure of 1.0-5.5 MPa to react; and carrying out oil-gas separation on the reaction products thereof and entering a fractionation system . By adopting the method, heavy raw materials such as vacuum gas oil, coking gas oil and the like are treated to obtain more than 98 weight percent chemical materials. In the invention, the middle fractions are wholly converted into the chemical materials in the low pressure condition, and low hydrogen consumption, low investment cost and low operation cost are realized.
Description
Technical field
The invention belongs to a kind of is the hydrocarbon ils cleavage method that obtains low boiler cut existing under the situation of hydrogen, more particularly, is a kind of method for hydrogen cracking of producing industrial chemicals.
Background technology
For a long time, because the crude oil in China light oil yield is low, the industrial chemicals source is not enough to become the important factor of restriction ethene, aromatic hydrocarbons production increase.The increasing degree of following China's ethene and aromatic hydrocarbons demand will be far above the rate of growth of vehicle fuel and crude runs; Economic expert's prediction; The crude oil in China working ability 2010 with the year two thousand twenty with reaching 300,000,000 tons and 3.9 hundred million tons respectively; Calculate if account for crude oil about 10% according to present industrial chemicals (mainly being virgin naphtha) yield, domestic oil refining enterprises will can provide 3,000 ten thousand tons of industrial chemicals and 3,900 ten thousand tons in 2010 respectively with the year two thousand twenty; And the demand of industrial chemicals was about 5,300 ten thousand tons in 2010, about 8400～9,000 ten thousand tons of the year two thousand twenty, and the industrial chemicals breach is with reaching 23,000,000 tons and 45,000,000 tons respectively when the time comes.
Hydrogen cracking is as oil refining and chemical industry bonded bridge technology; BO such as VGO etc. be can transform, liquefied gas, light naphthar and the tail oil that obtains as high-quality preparing ethylene by steam cracking raw material, heavy naphtha and the clean diesel product that is used as high-quality aromatics producing unit raw material produced.This technology is a better approach of raising the output industrial chemicals.
But existing hydrocracking technology more is to be used to produce fine automobile-used (or aircraft with) transport fuel, and the correlation technique that is directed to the more producing chemical industry raw material seldom thereby has limited the effect of hydrocracking technology aspect the raising the output industrial chemicals to a certain extent.Further excavate these technological potentiality, can reduce the rate of growth of the national economic development to a certain extent, alleviate the insufficient predicament of industrial chemicals that petrochemical enterprise in China faces crude oil demand.
US4197184 discloses a kind of " parallel-flow " multistage hydrocracking process, this technology can be used for maximum and produce diesel oil and rocket(engine)fuel.Its technical process can be described as: raw material gets into the refining reaction device, and the product that product after refining and cracking case come out is mixed into separation system, obtains the variant prodn distillate, and tail oil is recycled to hydrocracking reactor and carries out cracking at the bottom of the tower of separating.The entire reaction system has only a circulating hydrogen compressor, make-up hydrogen compressor system and a separation system.This patent adopts two sections recycle to extinction conversion process, and hydrofined oil is without hydrogen cracking, and directly arrive separation system, and NH3 concentration is low in the atmosphere of hydrocracking reaction, cut yield and the activity of bringing into play cracking catalyst in helping improving.The technical process and the patent of invention of this technology have similarity, but the purpose product has remarkable difference, and this technology produces diesel oil with maximum and rocket(engine)fuel is a target, and patent of invention then requires diesel oil and rocket(engine)fuel to reduce to 0.
The method for hydrogen cracking that discloses a kind of mass production of chemical materials of CN1854263A.This method technical process and the present invention are similar, also are middle runnings circulation cracking case is set, and raw materials such as decompressed wax oil all are converted into industrial chemicals such as ethylene raw and aromatic hydrocarbons raw materials for production.The middle runnings circulation cracking case of this method and preceding two reactor drum parallel operations, three reactor operating pressure grades are consistent, shared separation system of entire reaction system and hydrogen gas circulating system.
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 chemical materials to maximum with low cost.
Method provided by the invention comprises:
(1) raw oil and hydrogen are mixed into first reaction zone; Contact with hydrocracking catalyst with Hydrobon catalyst successively; Under the pressure of 6.0-16.0MPa, react, its resultant of reaction is after gas-oil separation, and the hydrogen-rich gas I of gained returns first reaction zone after the circulating hydrogen compressor compression; The liquid phase stream I of gained gets into fractionating system, obtains liquefied gas, light naphtha fraction, heavy naphtha fraction, middle runnings and tail oil cut through fractionation;
(2) step (1) middle runnings that obtains and the hydrogen that the compression from the make-up hydrogen compressor one-level exports is mixed into second reaction zone; Under the pressure of 1.0-5.5MPa, contact and react with hydrocracking catalyst; Its resultant of reaction is after gas-oil separation; The hydrogen-rich gas II of gained returns the make-up hydrogen compressor inlet, and the liquid phase stream II of gained mixes the back and gets into fractionating system with the liquid phase stream I of step (1).
Adopt the inventive method; Handle heavy feed stocks such as vacuum gas oil, coker gas oil and obtain the above industrial chemicals (liquefied gas, light naphtha fraction, heavy naphtha and tail oil cut) of 98 heavy %; Wherein liquefied gas, light naphthar and tail oil cut are as the raw material of preparing ethylene by steam cracking, and heavy naphtha fraction then can be produced aromatic hydrocarbons behind CR.Method of the present invention is converted into industrial chemicals with middle runnings entirely under the low pressure condition, the hydrogen consumption is low, and investment cost and process cost are low.
Description of drawings
Accompanying drawing is the method for hydrogen cracking schematic flow sheet of producing chemical materials to maximum with low cost provided by the present invention.
Embodiment
Method provided by the invention is such practical implementation:
(1) raw oil and hydrogen are mixed into first reaction zone; Contact with hydrocracking catalyst with Hydrobon catalyst successively, under the pressure of 6.0-16.0MPa, react, its resultant of reaction gets into HP separator I after gas-oil separation; The hydrogen-rich gas I of gained returns first reaction zone after the circulating hydrogen compressor compression; The liquid phase stream I of gained gets into fractionating system, and liquid advances light pressure separator and proceeds gas-oil separation, and the liquid that light pressure separator comes out gets into separation column and carries out product separation; Cat head obtains liquefied gas; Side line obtains light naphtha fraction, heavy naphtha fraction and middle runnings, is the tail oil cut at the bottom of the tower, wherein liquefied gas, light naphtha fraction, heavy naphtha fraction and the direct withdrawing device of tail oil cut.The hydrogen of step (1) is the hydrogen of circulating hydrogen compressor outlet and the mixture of the hydrogen of the make-up hydrogen compressor outlet of choosing wantonly.
Liquefied gas refers to carbon three, carbon four components; The boiling range of light naphthar is generally C5～65 ℃; Common 65～175 ℃ of heavy naphtha boiling range; The cutting temperature of tail oil cut and middle runnings is 300～350 ℃.
(2) step (1) middle runnings that obtains and the hydrogen that the compression from the make-up hydrogen compressor one-level exports is mixed into second reaction zone; Under the pressure of 1.0-5.5MPa, contact and react with hydrocracking catalyst; Its resultant of reaction gets into HP separator II and carries out gas-oil separation; The hydrogen-rich gas II of gained returns the make-up hydrogen compressor inlet; The liquid phase stream II of gained mixes back entering light pressure separator and proceeds gas-oil separation with the liquid phase stream I of step (1), the liquid that light pressure separator comes out gets into separation column and carries out product separation.
Described raw oil is selected from one or more in decompressed wax oil, wax tailings, the deasphalted oil.Heavy distillate contains impurity such as more S, N, and aromaticity content is higher, and 5% distillates o'clock about 300 ℃, and doing can be up to 560 ℃.
Other reaction conditions of described first reaction zone is: 330～430 ℃ of refining reaction temperature, cracking reaction temperature are 320～420 ℃, TV air speed 0.1～4.0h
-1, hydrogen to oil volume ratio 300～1500Nm
3/ m
3
Other reaction conditions of described second reaction zone is: 310～420 ℃ of temperature of reaction, volume space velocity 0.5～8.0h
-1, hydrogen to oil volume ratio 50～500Nm
3/ m
3
Described make-up hydrogen compressor adopts reciprocation compressor, establishes stage compression, and number of compression stages is 2～5 grades.Be preferably 3～4 grades.
Number of compression stages and compression ratio are important notions in the reciprocation compressor, and under the big situation of overall compression ratio, excessive discharge temperature when avoiding single-stage compression generally can be taked stage compression, inter-stage temperature reduction way, and compressed number of times is number of compression stages; Compression ratio then refers to the compressed degree of gas; Say The more the betterly on the series theory of compressor, but in fact the progression of compressor should be not too many, because the every increase one-level of progression, corresponding just parts such as cover cylinder air valves that increase make compressor arrangement complicated more.Compression ratio is big more, and the outlet exhaust temperature is just high more, and the power of consumption is big, and temperature out also may surpass lubricated oil flash, causes lubricating oil can be burnt till the carbon slag.Generally speaking, the every stage compression ratio of compressor is no more than 4, and exhaust temperature is no more than 150 ℃.
The hydrogen consumption refers to the amounts of hydrogen that every process unit weight raw oil is consumed.On the full scale plant, total hydrogen consumption comprises the little hydrogen of chemical hydrogen consumption, system leak loss and is dissolved in the oil and the little hydrogen of being taken out of.Pressure is low more, and aromatic hydrocarbons generation saturated reaction degree is low more, and the aromatic hydrocarbons saturated reaction is the reaction that consumes a large amount of hydrogen, and therefore chemical hydrogen consumption can reduce with pressure.
Described first reaction zone is provided with two reactors in series operations, loads Hydrobon catalyst and hydrocracking catalyst respectively; Or only use a reactor drum, combination loading Hydrobon catalyst and hydrocracking catalyst in the reactor drum.First reaction zone is set up hydrogen gas circulating system.
Described second reaction zone is provided with a reactor drum, the filling hydrocracking catalyst, and cracking middle runnings is used to circulate; Second reaction zone is operated under the low hydrogen dividing potential drop, directly utilizes the hydrogen of make-up hydrogen compressor one-level compression outlet, and hydrogen does not circulate.Owing to reduce the pressure rating requirement of second reaction zone, thereby reduce hydrogen consumption, reduction facility investment and process cost.
In the hydrocracking process, the activity of cracking reaction derives from the acidic zeolite center, and the organic nitrogen compound in the raw material is adsorbed on the acid sites easily, causes cracking activity to reduce, even loss of activity.Therefore, for guaranteeing the active stability of cracking catalyst, need make the nitrogen content of refining reaction device outlet oil be lower than certain controlling index.The denitrification activity of catalyst for refining is high more, and the reaction conditions of refining reaction device just relaxes more.In other words, adopt the catalyst for refining of high denitrification activity, the average reaction temperature that can reduce the refining reaction device perhaps reduces the consumption of catalyst for refining.
Described Hydrobon catalyst is a kind of metal load type catalyst; Carrier is unformed aluminum oxide; Metal component is VIB or VIII family base metal or their combination, and wherein the group vib metal is selected from Mo and/or W, and VIII family metal is selected from and comprises Co and/or Ni.The composition of preferred described Hydrobon catalyst is by weight: the carrying alumina body burden is 50%～80%; The vib metal oxide content is 15%-35%; VIII family metal oxide content is 2%-15%.
Described Hydrobon catalyst preparation method is: add an amount of sticker, zero(ppm) water etc., extruded moulding in the aluminum oxide; The salts solution of related reactive metal is mixed with a kind of specific complex liquid according to a certain percentage, and alumina supporter joins in this mixing solutions, the dipping certain hour, and the elimination surplus solution carries out drying, activation obtains finished catalyst then.
Preferred Hydrobon catalyst, denitrification activity is active higher by about 30% than the denitrification catalyst of present advanced level, and perhaps temperature of reaction can reduce by 5～10 ℃ when reaching identical denitrification percent.
For guaranteeing the long-term operation of full scale plant, the filling guard catalyst on Hydrobon catalyst top, protective material is VIB or VIII family non-precious metal catalyst or their combination that loads on unformed aluminum oxide or the silica-alumina supports.This type of protective material has bigger pore volume and specific surface area.The volume ratio of protective material and Hydrobon catalyst is 0:100-30:100, preferred 5:100-15:100.
The reaction that the cracking of hydro carbons in the raw oil, open loop and isomery equimolecular structure change is mainly carried out in cracking case.Through cracking reaction, obtain clean cargo and unconverted part.Utilize method for hydrogen cracking provided by the invention, clean cargo comprise gently, heavy naphtha fraction, and unconverted part is called hydrocracking tail oil.Light naphtha fraction can be used as gasoline blending component, also can be used as the raw material of preparing ethylene by steam cracking; Heavy naphtha fraction is rich in aromatic hydrocarbons, is the fine reformer feed; Tail oil is rich in stable hydrocarbon, and aromaticity content is very low, therefore has lower BMCI value, is the raw material of fine preparing ethylene by steam cracking.
Described first reaction zone and the used hydrocracking catalyst of second reaction zone are molecular sieve carried non-precious metal catalysts; Metal component is VIB or VIII family base metal or their combination; Wherein the group vib metal is selected from Mo and/or W; VIII family metal is selected from and comprises that Co and/or Ni, molecular sieve are the Y zeolite of modification.The composition of preferred described hydrocracking catalyst is by weight: the carrying alumina body burden is 20%-70%, molecular sieve content 10%～65%, and the vib metal oxide content is 10%-40%, VIII family metal oxide content is 1%-20%.
The composition of preferred hydrocracking catalyst is by weight: the carrying alumina body burden is 30%～60%; Molecular sieve content 10%～55%; The vib metal oxide content is 20%-35%; VIII family metal oxide content is 2%-10%.
But preferred hydrocracking catalyst more producing chemical industry raw material, and tail oil BMCI value is relatively low.Compare with current high-caliber similar hydrogen cracking agent, under equal depth of conversion, industrial chemicals (light, heavy naphtha+tail oil) yield can improve 3～5 percentage points; Tail oil BMCI value reduces by 1～2 unit simultaneously.
Advantage of the present invention is:
(1) the present invention adopts the Hydrobon catalyst of high denitrification activity, to reduce catalyst levels, can dwindle refining section catalyst loading volume simultaneously.The effusive reactant of refining section directly gets into first cracking zone and reacts; Cracking zone filling novel cracking catalytic; The characteristics of this cracking catalyst are under certain depth of conversion; Can obtain more industrial chemicals, comprise liquefied gas, light naphthar, heavy naphtha and tail oil, and the middle runnings yield be lower.
(2) the present invention is provided with independent low pressure middle runnings circulation cracking case, can under the low pressure condition, middle runnings be converted into industrial chemicals entirely, directly utilizes the hydrogen of make-up hydrogen compressor one-level compression outlet, and hydrogen does not circulate.Thereby the reduction hydrogen consumption, and reduce facility investment and process costs such as reactor drum, circulating oil pump, this reactor drum low hydrogen press strip spare is operated the benefit that improves product naphtha fraction virtue potential content in addition, improves the quality of aromatic hydrocarbons raw materials for production.Device keeps certain production handiness simultaneously, can produce the industrial chemicals and the industrial chemicals that supplies the aromatic hydrocarbons raw materials for production that obtain supplying ethylene raw flexibly.
Below in conjunction with accompanying drawing the method that provides of the present invention is further explained.
Accompanying drawing is the method for hydrogen cracking schematic flow sheet of producing chemical materials to maximum with low cost provided by the invention.Omitted the equipment of many necessity among the figure, like process furnace, pump, interchanger etc.
The technical process of method provided by the present invention is described below:
From the raw oil of pipeline 1 with mix from the recycle hydrogen of pipeline 8 and from the new hydrogen that concerns 28; Get into first reactor drum 2 then; Desulfurization, denitrogenation and aromatic hydrocarbons saturated reaction take place under the Hydrobon catalyst effect; Reaction back logistics directly gets into second reactor drum 3, and oil, gas continue under the hydrocracking catalyst effect, to react.Flow through pipeline 4 of second reactor drum, 3 resultant of reaction gets into HP separators 5 and carries out gas-oil separation.HP separator 5 top gas are after pipeline 6 gets into recycle compressor 7 superchargings; Loop back reactor drum through pipeline 8; HP separator 5 lower liquid go light pressure separator 10 further to carry out gas-oil separation through pipeline 9, and the gas of light pressure separator 10 is through pipeline 11 emptying, and light pressure separator 10 lower liquid are removed separation column 13 through pipeline 12; Cat head tells liquefied gas and light naphtha fraction is extracted out through pipeline 14 and pipeline 15 respectively; Top side line 16 is extracted heavy naphtha fraction out, and bottom side line 17 is extracted middle runnings out, and the tail oil cut at the bottom of the tower is extracted out through pipeline 18.
Mix with new hydrogen after supercharging from the middle runnings of pipeline 17 from the make-up hydrogen compressor 24 one-levels outlet of pipeline 25; Get into the 3rd reactor drum 18 then; Under the hydrocracking catalyst effect, carry out secondary reaction, flow through pipeline 19 of the 3rd reactor drum 18 resultant of reaction gets into HP separators 20 and carries out gas-oil separation.HP separator 20 top hydrogen-rich gases loop back make-up hydrogen compressor 24 inlets through pipeline 22, and HP separator 20 lower liquid are mixed with HP separator 4 lower liquid through pipeline 21, get into light pressure separator 5 together and carry out further gas-oil separation.
New hydrogen from pipeline 23 gets into make-up hydrogen compressor 24; The hydrogen of make-up hydrogen compressor 24 one-levels outlet is divided into two-way; One the tunnel through pipeline 25 entering the 3rd reactor drum 18; One tunnel secondary inlet through pipeline 26 entering make-up hydrogen compressors 24, the new hydrogen of secondary outlet gets into three grades of inlets through pipeline 27, and the new hydrogen of 24 3 grades of outlets of make-up hydrogen compressor is extracted out through pipeline 28.
Following embodiment will further explain method provided by the invention, but therefore not limit the present invention.
The content of additional embodiment catalyzer
VGO is a raw material with the high nitrogen heavy of high-sulfur; Feedstock property is as shown in table 1, and raw oil and hydrogen are mixed into first reaction zone, successively with Hydrobon catalyst and hydrocracking catalyst contact reacts; Its resultant of reaction is after gas-oil separation; The hydrogen-rich gas I of gained returns first reaction zone after the circulating hydrogen compressor compression, the liquid phase stream I of gained gets into fractionating system, obtains liquefied gas, light naphtha fraction, heavy naphtha fraction, middle runnings and tail oil cut through fractionation; The middle runnings that obtains is mixed into second reaction zone with the hydrogen that the compression from the make-up hydrogen compressor one-level exports; Contact with hydrocracking catalyst and to react; Its resultant of reaction is after gas-oil separation; The hydrogen-rich gas II of gained returns the make-up hydrogen compressor inlet, and the liquid phase stream II of gained mixes the back and gets into fractionating system with the liquid phase stream I of step (1).Reaction conditions is listed in table 2, and product distributes and character is listed in table 4 and table 6.
Can find out that from table 4 yield of the middle runnings in the finished product of the inventive method is 0, and maximum production obtains liquefied gas, light naphthar, heavy naphtha and tail oil product, total recovery reaches 98.62 heavy %.
Comparative Examples
Adopt the raw oil identical with embodiment 1; And two reaction zones are set equally; But the pressure rating of two reaction zones is consistent; The gas that promptly gets into the oil circulation cracking case of middle runnings exports from circulating hydrogen compressor, and the gas of the oil circulation cracking case of entering middle runnings of embodiment 1 is then from the lower make-up hydrogen compressor one-level compression outlet of pressure rating.Reaction conditions is listed in table 2, and product distributes and character is listed in table 3 and table 5.
Data can be found out from table: compare with Comparative Examples, the hydrogen of embodiment 1 consumption is low, and chemical hydrogen consumption reduces to 2.45% from 2.55%, and total hydrogen consumption reduces to 2.68% from 2.80%; In addition, it is 57% that the heavy naphtha of embodiment 1 gained virtue is dived, and the heavy naphtha virtue that is higher than the Comparative Examples gained dives 54%.
Table 1 raw oil character
| Project | Data |
| Density (15 ℃/15 ℃), g/cm 3 | 0.9273 |
| Sulphur content, heavy % | 2.794 |
| Nitrogen content, μ g/g | 1200 |
| Hydrogen richness, heavy % | 11.9 |
| Alkali nitrogen, μ g/g | 230.2 |
| Boiling range (ASTM-D1160), ℃ | |
| Over point 550709095 final boiling point | 368372441484536545550 |
Table 2 reaction conditions
| Processing condition: | | Embodiment | 1 |
| First reaction zone inlet hydrogen dividing potential drop, MPa second reaction zone inlet hydrogen dividing potential drop, MPa | 12.012.0 | 12.03.0 | |
| Volume space velocity, h -1 | |||
| The refining section of first reaction zone | 1.05 | 1.05 | |
| The first reaction zone cracking zone | 1.65 | 1.65 | |
| Second reaction zone | 2.0 | 2.0 | |
| The bed medial temperature, ℃ | |||
| One is anti- | 372 | 372 | |
| Two is anti- | 378 | 378 | |
| Three is anti- | 355 | 355 | |
| First reaction zone inlet hydrogen-oil ratio, Nm 3/m 3 | 750 | 750 | |
| Second reaction zone inlet hydrogen-oil ratio, Nm 3/m 3 | 200 | 200 |
Table 3 Comparative Examples product distributed data
| Project | First reaction zone | Second reaction zone | Full device |
| Chemistry hydrogen consumption, heavy % | 2.25 | 1.52 | 2.55 |
| Total hydrogen consumption, heavy % | 2.48 | 1.67 | 2.80 |
| Product distributes: heavy %H2S/NH3 | 2.97/0.15 | 0.00/0.00 | 2.97/0.15 |
| C1/C2 | 0.08/0.39 | 0.22/0.90 | 0.12/0.57 |
| C3/C4 | 1.37/3.36 | 3.05/7.21 | 1.97/4.76 |
| C5～light naphthar | 4.89 | 15.54 | 7.92 |
| Heavy naphtha | 28.25 | 74.60 | 42.80 |
| Diesel oil | 19.50 | 0.00 | 0.00 |
| Tail oil | 41.29 | 0.00 | 41.29 |
Table 4 embodiment 1 product distributed data
| Project | First reaction zone | Second reaction zone | Full device |
| Chemistry hydrogen consumption, heavy % | 2.25 | 1.01 | 2.45 |
| Total hydrogen consumption, heavy % | 2.48 | 1.05 | 2.68 |
| Product distributes: heavy %H2S/NH3 | 2.97/0.15 | 0.00/0.00 | 2.97/0.15 |
| C1/C2 | 0.08/0.39 | 0.23/0.92 | 0.12/0.57 |
| C3/C4 | 1.37/3.36 | 3.08/7.25 | 1.97/4.77 |
| C5～light naphthar | 4.89 | 15.21 | 7.86 |
| Heavy naphtha | 28.25 | 74.32 | 42.74 |
| Middle runnings | 19.50 | 0.00 | 0.00 |
| Tail oil | 41.29 | 0.00 | 41.29 |
Table 5 Comparative Examples product main character
| Product | Light naphthar | Heavy naphtha | Tail oil |
| Gold-plating journey scope, ℃ | <65 | 65～165 | >300 |
| Density (20 ℃), g/cm3 | 0.645 | 0.747 | 0.835 |
| Total sulfur, ppm | <0.5 | <0.5 | <20 |
| Total nitrogen, ppm | <0.5 | <0.5 | <5 |
| Condensation point, ℃ | / | / | 38 |
| Aromaticity content, heavy % | / | / | <2 |
| Polycyclic aromatic hydrocarbon content, heavy % | / | / | <1 |
| RON/MON | 83/81 | / | / |
| Arene underwater content, heavy % | / | 54 | / |
| Cetane value | / | / | / |
| The BMCI value | / | / | <12 |
Table 6 embodiment 1 product main character
| Product | Light naphthar | Heavy naphtha | Tail oil |
| The boiling range scope, ℃ | <65 | 65～165 | >300 |
| Density (20 ℃), g/cm3 | 0.645 | 0.751 | 0.835 |
| Total sulfur, μ g/g | <0.5 | <0.5 | <20 |
| Total nitrogen, μ g/g | <0.5 | <0.5 | <5 |
| Condensation point, ℃ | 38 | ||
| Aromaticity content, heavy % | <2 | ||
| Polycyclic aromatic hydrocarbon content, heavy % | <1 | ||
| RON/MON | 83/81 | ||
| Arene underwater content, heavy % | 57 | ||
| Cetane value | |||
| The BMCI value | <12 |
Embodiment 2
To be raw material, carry out the hydrogen cracking test according to catalyzer provided by the present invention and technical process than heavier, that character the is relatively poor relatively VGO of embodiment 1.Test-results is listed in table 7～table 10.
Data can be found out from table: adopting the poorer VGO raw material of the method processing quality that provides of the present invention, under an anti-inlet hydrogen dividing potential drop 13.4MPa, three instead enters the mouth the condition of hydrogen dividing potential drop 3.5MPa, can the middle runnings yield be reduced to minimumly, is 0; And maximum production obtains liquefied gas, light naphthar, heavy naphtha and tail oil product, and total recovery reaches 98.7 heavy %.
Table 7 embodiment 2 raw oil character
| Project | |
| Density (15 ℃/15 ℃), g/cm3 | 0.9323 |
| Sulphur content, heavy % | 2.990 |
| Nitrogen content, μ g/g | 1300 |
| Hydrogen richness, heavy % | |
| Alkali nitrogen, μ g/g | |
| Metal, μ g/g | <2 |
| Bituminous matter, μ g/g | <200 |
| Carbon residue, heavy % | <0.5 |
| Boiling range (ASTM-D1160), ℃ | |
| Over |
368376412461502556580 |
Table 8 embodiment 2 reaction conditionss
| Processing condition: | |
| First reaction zone inlet hydrogen dividing potential drop, MPa second reaction zone inlet hydrogen dividing potential drop, MPa | 13.43.5 |
| Volume space velocity, h -1 | |
| The refining section of first reaction zone | 1.0 |
| The first reaction zone cracking zone | 1.50 |
| Second reaction zone | 3.0 |
| The bed medial temperature, ℃ | |
| One is anti- | 376 |
| Two is anti- | 376 |
| Three is anti- | 360 |
| First reaction zone inlet hydrogen-oil ratio, Nm 3/m 3 | 750 |
| Second reaction zone inlet hydrogen-oil ratio, Nm 3/m 3 | 300 |
Table 9 embodiment 2 material balance datas
| Project | First reaction zone | Second reaction zone | Full device |
| Total hydrogen consumption, heavy % | 2.60 | 1.08 | 2.81 |
| Product distributes: heavy %H 2S/NH 3 | 3.18/0.16 | 0.00/0.00 | 3.18/0.16 |
| C1/C2 | 0.10/0.42 | 0.24/0.95 | 0.14/0.60 |
| C3/C4 | 1.66/4.09 | 3.36/7.89 | 2.28/5.55 |
| C5～light naphthar | 5.61 | 15.18 | 8.42 |
| Heavy naphtha | 30.78 | 73.46 | 44.39 |
| Middle runnings | 18.53 | 0.00 | 0.00 |
| Tail oil | 38.07 | 0.00 | 38.07 |
Table 10 embodiment 2 product main character
| Product | Light naphthar | Heavy naphtha | Tail oil |
| The boiling range scope, ℃ | <65 | 65～165 | >300 |
| Density (20 ℃), g/cm3 | 0.644 | 0.750 | 0.839 |
| Total sulfur, μ g/g | <0.5 | <0.5 | <20 |
| Total nitrogen, μ g/g | <0.5 | <0.5 | <5 |
| Condensation point, ℃ | / | / | 38 |
| Aromaticity content, heavy % | / | / | <2 |
| Polycyclic aromatic hydrocarbon content, heavy % | / | / | <1 |
| RON/MON | 83/81 | / | / |
| Arene underwater content, heavy % | / | 56 | / |
| Cetane value | / | / | / |
| The BMCI value | / | / | <11 |
Claims (9)
1. the method for hydrogen cracking of a producing chemical materials to maximum with low cost comprises:
(1) raw oil and hydrogen are mixed into first reaction zone; Contact with hydrocracking catalyst with Hydrobon catalyst successively; Under the pressure of 6.0-16.0MPa, react, its resultant of reaction is after gas-oil separation, and the hydrogen-rich gas I of gained returns first reaction zone after the circulating hydrogen compressor compression; The liquid phase stream I of gained gets into fractionating system, obtains liquefied gas, light naphtha fraction, heavy naphtha fraction, middle runnings and tail oil cut through fractionation;
(2) step (1) middle runnings that obtains and the hydrogen that the compression from the make-up hydrogen compressor one-level exports is mixed into second reaction zone; Under the pressure of 1.0-5.5MPa, contact and react with hydrocracking catalyst; Its resultant of reaction is after gas-oil separation; The hydrogen-rich gas II of gained returns the make-up hydrogen compressor inlet, and the liquid phase stream II of gained mixes the back and gets into fractionating system with the liquid phase stream I of step (1).
2. according to the described method of claim 1, it is characterized in that described raw oil is selected from one or more in decompressed wax oil, wax tailings, the deasphalted oil.
3. according to the described method of claim 1, it is characterized in that other reaction conditions of described first reaction zone is: 330～430 ℃ of refining reaction temperature, cracking reaction temperature are 320～420 ℃, TV air speed 0.1～4.0h
-1, hydrogen to oil volume ratio 300～1500Nm
3/ m
3
4. according to the described method of claim 1, it is characterized in that other reaction conditions of described second reaction zone is: 310～420 ℃ of temperature of reaction, volume space velocity 0.5～8.0h
-1, hydrogen to oil volume ratio 50～500Nm
3/ m
3
5. according to the described method of claim 1, it is characterized in that described make-up hydrogen compressor adopts reciprocation compressor, establish stage compression, number of compression stages is 2～5 grades.
6. according to the described method of claim 1; It is characterized in that described Hydrobon catalyst is a kind of metal load type catalyst; Carrier is unformed aluminum oxide; Metal component is VIB or VIII family base metal or their combination, and wherein the group vib metal is selected from Mo and/or W, and VIII family metal is selected from and comprises Co and/or Ni.
7. according to claim 1 or 6 described methods, the composition that it is characterized in that described Hydrobon catalyst by weight: the carrying alumina body burden is 50%～80%; The vib metal oxide content is 15%-35%; VIII family metal oxide content is 2%-15%.
8. according to the described method of claim 1; It is characterized in that described first reaction zone and the used hydrocracking catalyst of second reaction zone are molecular sieve carried non-precious metal catalysts; Metal component is VIB or VIII family base metal or their combination; Wherein the group vib metal is selected from Mo and/or W, and VIII family metal is selected from and comprises that Co and/or Ni, molecular sieve are the Y zeolite of modification.
9. according to claim 1 or 8 described methods; The composition that it is characterized in that the hydrocracking catalyst that described first reaction zone and second reaction zone are used is by weight: the carrying alumina body burden is 20%-70%; Molecular sieve content 10%～65%; The vib metal oxide content is 10%-40%, and VIII family metal oxide content is 1%-20%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008101668522A CN101684415B (en) | 2008-09-27 | 2008-09-27 | Hydrocracking method for producing chemical materials to maximum with low cost |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008101668522A CN101684415B (en) | 2008-09-27 | 2008-09-27 | Hydrocracking method for producing chemical materials to maximum with low cost |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101684415A CN101684415A (en) | 2010-03-31 |
| CN101684415B true CN101684415B (en) | 2012-07-25 |
Family
ID=42047791
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2008101668522A Active CN101684415B (en) | 2008-09-27 | 2008-09-27 | Hydrocracking method for producing chemical materials to maximum with low cost |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101684415B (en) |
Families Citing this family (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103897732A (en) * | 2014-03-18 | 2014-07-02 | 何巨堂 | High-nitrogen and high-aromatic hydrocarbon hydrogenation modification process and thermal cracking process combining method |
| CN105085134B (en) * | 2014-05-14 | 2017-08-11 | 中国石油化工股份有限公司 | The method that aroamtic hydrocarbon raw material is directly produced by heavy aromatics inferior |
| CN109988647B (en) * | 2017-12-29 | 2021-07-09 | 中国石油化工股份有限公司 | Flexible single-stage two-agent hydrocracking process |
| CN109988636B (en) * | 2017-12-29 | 2021-07-09 | 中国石油化工股份有限公司 | Flexible single stage hydrocracking process |
| CN109988628B (en) * | 2017-12-29 | 2021-07-09 | 中国石油化工股份有限公司 | Flexible single-stage hydrocracking process |
| CN109988618B (en) * | 2017-12-29 | 2021-05-04 | 中国石油化工股份有限公司 | Flexible single-stage two-agent hydrocracking process |
| CN109988640B (en) * | 2017-12-29 | 2021-07-09 | 中国石油化工股份有限公司 | Flexible hydrocracking process |
| CN109988621B (en) * | 2017-12-29 | 2021-07-09 | 中国石油化工股份有限公司 | Flexible hydrocracking process |
| CN109988607B (en) * | 2017-12-29 | 2021-08-06 | 中国石油化工股份有限公司 | Flexible two-stage hydrocracking process |
| TWI756504B (en) * | 2017-12-29 | 2022-03-01 | 大陸商中國石油化工科技開發有限公司 | A kind of wax oil hydrocracking method and system |
| US20200102510A1 (en) * | 2018-09-29 | 2020-04-02 | Uop Llc | Process for maximizing production of heavy naphtha from a hydrocarbon stream |
| US10829703B2 (en) * | 2018-09-29 | 2020-11-10 | Uop Llc | Process for producing a naphtha stream |
| CN112322349B (en) | 2019-08-05 | 2021-11-30 | 中国石油化工股份有限公司 | Full conversion method and device for producing light aromatic hydrocarbon from catalytic diesel oil |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4197184A (en) * | 1978-08-11 | 1980-04-08 | Uop Inc. | Hydrorefining and hydrocracking of heavy charge stock |
| US6843906B1 (en) * | 2000-09-08 | 2005-01-18 | Uop Llc | Integrated hydrotreating process for the dual production of FCC treated feed and an ultra low sulfur diesel stream |
| CN1854263A (en) * | 2005-04-29 | 2006-11-01 | 中国石油化工股份有限公司 | Hydrogenation cracking method of mass production of chemical materials |
-
2008
- 2008-09-27 CN CN2008101668522A patent/CN101684415B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4197184A (en) * | 1978-08-11 | 1980-04-08 | Uop Inc. | Hydrorefining and hydrocracking of heavy charge stock |
| US6843906B1 (en) * | 2000-09-08 | 2005-01-18 | Uop Llc | Integrated hydrotreating process for the dual production of FCC treated feed and an ultra low sulfur diesel stream |
| CN1854263A (en) * | 2005-04-29 | 2006-11-01 | 中国石油化工股份有限公司 | Hydrogenation cracking method of mass production of chemical materials |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101684415A (en) | 2010-03-31 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101684415B (en) | Hydrocracking method for producing chemical materials to maximum with low cost | |
| CN101210198B (en) | Hydrogenation method for producing high grade diesel oil and high grade reforming raw material | |
| CN100434496C (en) | Two-way combined process of wax-oil hydrogenation treatment and catalytic cracking | |
| CN112143522B (en) | Hydrogenation method and system for production chemical material | |
| CN102031140B (en) | Combination method of gasification and coke processing from inferior heavy oil | |
| EP3266854B1 (en) | Diesel oil and jet fuel production system and method utilizing fischer-tropsch synthetic oil | |
| CN102399586A (en) | A mid-pressure hydrocracking method for producing jet fuel | |
| CN100389179C (en) | Hydrogenation cracking method of mass production of chemical materials | |
| CN104004541B (en) | A kind of preparation method of coal-based high arene underwater content stock oil | |
| CN100487087C (en) | Hydrogenation cracking method to produce more raw material for making ethylene | |
| CN101210195B (en) | Hydrocracking method for more producing chemical industry light oil from poor heavy raw material | |
| CN103773486B (en) | A kind of combined method of voluminous high-value product | |
| CN103525461B (en) | A kind of method for hydrogen cracking | |
| CN105713662A (en) | Hydrotreating and catalytic cracking combined process | |
| CN112143521B (en) | Hydrogenation method and system for producing catalytic reforming raw material | |
| CN105586084B (en) | Catalytic hydrogenation method for inferior wax oil | |
| CN102344826B (en) | Combined hydrogenation method for producing catalytic raw material and high-quality diesel oil | |
| CN109777481B (en) | Combined processing method for refinery gas | |
| CN100419044C (en) | Production of large-specific-weight aircraft liquid petroleum oil at maximum from coal liquefied oil | |
| CN1128859C (en) | Converting and combining method for hydrogenation of hydrocarbon | |
| CN108865253A (en) | The method of coal Direct Hydrogenation liquefaction richness production aromatic hydrocarbons | |
| CN109777488B (en) | Refinery gas combined processing technology | |
| CN102807898B (en) | Hydrocracking method for increasing production of high-quality middle distillates | |
| CN109988625B (en) | Hydrofining and hydrocracking combined process | |
| CN109777499B (en) | Refinery gas combined processing technology |
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 | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20230315 Address after: 100029, No. 6, Xin Xin Street East, Beijing, Chaoyang District Patentee after: CHINA PETROLEUM & CHEMICAL Corp. Patentee after: Sinopec Petrochemical Research Institute Co.,Ltd. Address before: 100029, No. 6, Xin Xin Street East, Beijing, Chaoyang District Patentee before: CHINA PETROLEUM & CHEMICAL Corp. Patentee before: RESEARCH INSTITUTE OF PETROLEUM PROCESSING, SINOPEC |
|
| TR01 | Transfer of patent right |