Prepare the method for hydrogen cracking of high-octane naphtha
Technical field
The present invention relates to a kind of method for hydrogen cracking preparing high-octane naphtha.
Background technology
Along with the fast development of national economy, the demand of people to light-weight fuel oil grows with each passing day, and along with the progress of society, environment is day by day harsh to the requirement of fuel oil.The quality and quantity of oil time processing all can not meet people's needs, and the light Fuel by the secondary operations of oil heavy distillate being converted into high-quality not only make use of limited petroleum resources fully, and alleviates the market demand of light ends oil.Hydrocracking technology is strong to adaptability to raw material, production decision is flexible, product quality is high, it is one of Main Means of oil secondary operations, the light naphtha fraction super-low sulfur that it is produced, low alkene and low aromatic hydrocarbons, be the blend component of high-quality clean gasoline, but its octane number of light naphthar that hydrocracking is at present produced is lower, usual <78 (RON).The aromatic hydrocarbons, alkene and the isohydrocarbon content that improve in gasoline component are favourable to the octane number improving naphtha, but because the content of requirement to Benzene In Gasoline of environmental protection has strict restriction, and require also more and more stricter to olefin(e) centent, therefore optimal method is improved the composition of gasoline component, and naphtha octane number is improved.
Hydrocracking technology relates generally to technology and catalyst technology, hydrocracking process flow process mainly comprises single-stage hydrocracking, one-stage serial hydrocracking and two-stage reforming, and often kind of flow process can also be divided into that one way is passed through, component loops and complete alternation three kinds of modes of operation.Hydrocracking catalyst can be divided into light oil type (it is main for producing naphtha), middle oil type (production kerosene and diesel oil are main) and heavy oil type (it is main for producing lube base oil) according to the difference of object product.
For to produce in the hydrocracking technology of naphtha for main purpose product, owing to needing the hydrocracking compared with the degree of depth, hydrocracking catalyst generally adopts light oil type hydrogen cracking catalyst, light oil type hydrogen cracking catalyst nitrogen resistance is poor, and technology adopts one-stage serial technique or two-stage process usually.The acidity of light oil type hydrogen cracking catalyst is strong, hydrogenation activity can adjust according to the requirement used, acid carrier used is that in zeolitic acid, calculation is many, acid strength is high, so obvious by the impact of the particularly organic nitrogen of nitrogen in raw material, therefore in one-stage serial technological process, in General Requirements hydrotreatment section effluent organic nitrogen content lower than 10 μ g/g to ensure that catalyst can long-term operation.
US4738766 discloses a kind of method of producing high-knock rating gasoline, catalytic cracking is combined with hydrocracking, hydrocracking is carried out with the light component of catalytic cracking recycle oil (end point of distillation is lower than 345 DEG C) raw material, single hop or two-stage process flow process is adopted to produce high-knock rating gasoline, the diesel oil distillate Returning catalyticing cracking device that hydrocracking obtains processes, and the technological process of this technology and mode of operation are also unwell to production object product.Because when single-stage hydrocracking is for the production of gasoline, need harsh operating condition, be worth low gas yield higher, the service life of catalyst also can be affected.
USP5,409,596 disclose a kind of catalysis conversion method improving hydrogasoline octane number, and the method is the gasoline fraction after making hydrofinishing and the catalyst exposure containing mesopore zeolite, is 150 ~ 482 DEG C, liquid hourly space velocity (LHSV) 0.5 ~ 10hr in reaction temperature
-1, reaction pressure be the volume ratio of 0.35 ~ 10.4MPa, hydrogen and hydro carbons is under the condition of 0 ~ 900, carry out n-alkane cracking reaction, thus the octane number of gasoline fraction be improved.
CN201010522133.7 discloses the method that high-knock rating gasoline is produced in the fraction oil of petroleum hydrocracking inferior of a kind of use, and the method comprises: 1. inferior distillate oil (boiling range 165 ~ 365 DEG C) being heated to 320 ~ 420 DEG C with hydrogen is to mix at 100: 1 ~ 1500: 1 by hydrogen to oil volume ratio; 2. by Hydrobon catalyst bed, (volume space velocity is 0.5 ~ 4hr to incoming mixture
-1, reaction pressure is 5 ~ 20MPa), remove the sulphur in incoming mixture, nitrogen impurity, and make two rings in incoming mixture or tricyclic compound fractional saturation, obtain refined oil; 3. refined oil is by by hydrocracking catalyst bed, (reaction temperature is 350 ~ 450 DEG C, and reaction pressure is 5 ~ 20MPa, and volume space velocity is 0.5 ~ 2.0hr
-1, hydrogen to oil volume ratio is 100: 1 ~ 1500: 1), make two rings with side chain in refined oil or tricyclic compound cracking, obtain being rich in the product of mononuclear aromatics as high-knock rating gasoline blend component.
Above technology is all for raw material produces high-octane gasoline or high-knock rating gasoline blend component by hydrofinishing and hydrocracking technology with the petrol and diesel oil cut of poor quality.
Summary of the invention
The object of this invention is to provide a kind of method for hydrogen cracking preparing high-octane naphtha, is a kind of one-stage serial hydrocracking technique, in the process taking heavy distillate as raw material production naphtha, obtain high-octane light naphthar.
The invention provides a kind of catalyst containing SAPO-11 molecular sieve, this catalyst is made up of SAPO-11 molecular sieve, hydrogenation active metals and inorganic oxide;
In described catalyst, the mass ratio of described SAPO-11 molecular sieve, hydrogenation active metals and inorganic oxide is 15 ~ 60:5 ~ 30:10 ~ 50;
Wherein, the quality of described hydrogenation active metals is in the quality of its oxide.
Above-mentioned contains in the catalyst of SAPO-11 molecular sieve, and the mass ratio of described SAPO-11 molecular sieve, hydrogenation active metals and inorganic oxide specifically can be 40 ~ 55:18 ~ 20:25 ~ 40,42:19.6:38.4 or 52.5:19.6:27.9.
Above-mentioned containing in the catalyst of SAPO-11 molecular sieve, described SAPO-11 molecular sieve has following physicochemical property:
Pore volume is 0.15 ~ 0.25ml/g, and as 0.18ml/g, specific area is 180 ~ 250m
2/ g, as 223m
2/ g; Described SAPO-11 molecular sieve has the ten-ring ellipse duct of three-dimensional, non-crossing, and aperture is 0.39 × 0.64nm, with Y zeolite facies than SAPO-11 molecular sieve by pore structure and weakly acidic restriction, the weak but isomery excellent performance of lytic activity.
Above-mentioned containing in the catalyst of SAPO-11 molecular sieve, described hydrogenation active metals can be group VIB metal and/or group VIII metal in the periodic table of chemical element;
Described group VIB metal can be molybdenum and/or tungsten, and described group VIII metal can be cobalt and/or nickel;
In described catalyst, the mass percentage of described group VIB metal can be 3.0% ~ 20.0%, specifically can be 9.0% ~ 15.0%, 9.8% or 14.6%, the mass percentage of described group VIII metal can be 2.0% ~ 10.0%, specifically can be 5.0% ~ 10.0%, 5.0% or 9.8%, all in the quality of its oxide.
Above-mentioned containing in the catalyst of SAPO-11 molecular sieve, described inorganic oxide can be at least one in aluminium oxide, silica and amorphous aluminum silicide;
SiO in described amorphous aluminum silicide
2mass percentage can be 35% ~ 65%, as 50%, the pore volume of described amorphous aluminum silicide can be 0.8 ~ 1.0ml/g, and as 0.85ml/g, specific area can be 350 ~ 500m
2/ g, as 370m
2/ g, can be prepared by coprecipitation.
Present invention also offers the preparation method of the above-mentioned catalyst containing SAPO-11 molecular sieve, comprise the steps:
Described SAPO-11 molecular sieve, described hydrogenation active metals, described inorganic oxide and adhesive being carried out mix, roll with extruded, then successively through leaving standstill aging, dry and roasting, namely obtaining the described catalyst containing SAPO-11 molecular sieve.
In above-mentioned preparation method, described adhesive can be made up of at least one in little porous aluminum oxide and inorganic acid and organic acid;
Described aperture aluminium oxide pore volume can be 0.3 ~ 0.5ml/g, and as 0.46ml/g, specific area can be 200 ~ 400m
2/ g, as 280m
2/ g, described inorganic acid can be hydrochloric acid or nitric acid etc., and described organic acid can be acetic acid or ethanedioic acid etc.;
Described leaving standstill agingly can be carried out under air humidity is the condition of 50 ~ 95%, as in air humidity be 80% or 95% condition under carry out, described standing aging temperature is 50 ~ 120 DEG C, specifically can be 70 DEG C ~ 75 DEG C, 70 DEG C or 75 DEG C, time is 4 ~ 24 hours, specifically can be 8 hours ~ 10 hours, 8 hours or 10 hours;
The temperature of described drying can be 100 ~ 130 DEG C, and specifically can be 110 DEG C or 120 DEG C, the time can be 4 ~ 16 hours, specifically can be 5 hours or 6 hours;
The temperature of described roasting can be 400 ~ 550 DEG C, specifically can be 500 DEG C, and the time can be 2 ~ 8 hours, specifically can be 4 hours.
A kind of method for hydrogen cracking preparing high-octane naphtha provided by the invention, comprises the steps:
(1) in the first reactor, heavy distillate carries out hydrofining reaction under the catalysis of Hydrobon catalyst;
(2) product of described hydrofining reaction enters in the second reactor, and on the upper strata of described second reactor, the product of described hydrofining reaction carries out hydrocracking reaction under the catalysis of hydrocracking catalyst; The product of described hydrocracking reaction enters the lower floor of described second reactor, under the catalysis of the described catalyst containing SAPO-11 molecular sieve, carry out isomerization reaction;
(3) namely the product being separated described isomerization reaction obtains high-octane naphtha.
In above-mentioned preparation method, the boiling range of described heavy distillate can be 280 ~ 580 DEG C;
Described heavy distillate can be at least one in gas oil, vacuum distillate, deasphalted oil, catalytic cracking recycle oil, shale oil and coal tar.
In above-mentioned preparation method, described Hydrobon catalyst can select the conventional Hydrobon catalyst that can process heavy distillate or suitable commercial catalyst, also can be prepared by this area general knowledge, as 3996 of CNPC's Fushun Petrochemical Company production;
Described hydrocracking catalyst is light oil type hydrogen cracking catalyst, can select the commercial catalyst be suitable for, and also can prepare by this area general knowledge, as the FC-24 industrial catalyst that CNPC's Fushun Petrochemical Company is produced.
In above-mentioned preparation method, the filling dosage that described hydrocracking catalyst is loaded on the upper strata of described second reactor is 50 ~ 95%, is volume parts, as 80 ~ 90%, 80% or 90%;
The filling dosage of the described catalyst containing SAPO-11 molecular sieve of lower floor's filling of described second reactor is 5 ~ 50%, is volume parts, as 10 ~ 20%, 10% or 20%.
In above-mentioned preparation method, in step (1), the temperature of described hydrofining reaction can be 320 ~ 430 DEG C, and hydrogen to oil volume ratio is 500 ~ 2000:1, and during liquid, volume space velocity is 0.4 ~ 4.0h
-1; And/or,
In step (2), the temperature of described hydrocracking reaction is 350 ~ 430 DEG C, and hydrogen to oil volume ratio is 500 ~ 2000:1, and during liquid, volume space velocity is 0.4 ~ 4.0h
-1, pressure is 3.0 ~ 18.0MPa;
In step (2), temperature and the Cracking catalyst bed of described cracking and isomerization reaction are all 350 ~ 430 DEG C mutually, and pressure can be 3.0 ~ 18.0MPa.
The method taking heavy distillate as raw material hydrocracking and produce naphtha provided by the invention, adopt one-stage serial technological process, first reactor dress Hydrobon catalyst, the second reactor top dress hydrocracking catalyst, bottom dress is containing the catalyst of SAPO-11 molecular sieve.Heavy distillate contacts macromolecular cleavage with Cracking catalyst and becomes Small molecular, and many rings and condensed-nuclei aromatics open loop become mononuclear aromatics; Product is through the beds containing SAPO-11 zeolite of isomery excellent performance, and the side chain generation isomerization reaction of chain hydrocarbon and cyclic hydrocarbon, generates the isohydrocarbon that octane number is high.Therefore the present invention has the following advantages: strong to adaptability to raw material, and process is simple, and do not need to transform existing apparatus, good product quality, the octane number of light naphthar is high.
Detailed description of the invention
The experimental technique used in following embodiment if no special instructions, is conventional method.
Material used in following embodiment, reagent etc., if no special instructions, all can obtain from commercial channels.
In following embodiment 2-3 and comparative example 1, Hydrobon catalyst used is 3996 Hydrobon catalysts that CNPC's Fushun Petrochemical Company is produced,
In following embodiment 2-3 and comparative example 1, hydrocracking catalyst used is the FC-24 catalyst that CNPC's Fushun Petrochemical Company is produced.
Embodiment 1, preparation contain the catalyst CA of SAPO-11 molecular sieve
By SAPO-11 molecular sieve, (pore volume is 0.18ml/g, and specific area is 223m
2/ g) 200 grams, MoO
337.5 grams, Ni (NO
3)
26H
2o 145 grams, amorphous aluminum silicide (SiO
2content 50wt%, pore volume 0.85ml/g, specific area 370m
2/ g, butt 75wt%) 35 grams, macroporous aluminium oxide (pore volume 1.0ml/g, specific area 400m
2/ g, butt 75wt%) 80 grams, (butt 30wt%, the mol ratio of nitric acid and little porous aluminum oxide is 0.3 to adhesive, and the pore volume of little porous aluminum oxide is 0.46ml/g, and specific area is 280m
2/ g) 66.5 grams be placed in roller kneading, roll, be pressed into paste, extruded moulding, catalyst after shaping is placed in that air humidity is 90%, temperature is carry out standing aging 8 hours under the condition of 75 DEG C, and at 110 DEG C dry 6 hours, temperature programming rises to 500 DEG C in 4 hours, constant temperature calcining 4 hours, the obtained catalyst A containing SAPO-11 molecular sieve.
The present embodiment prepares in catalyst, SAPO-11 molecular sieve, MoO
3, NiO, amorphous aluminum silicide and aluminium oxide mass percentage be respectively 52.5%, 9.8%, 9.8%, 6.9% and 21.0%.
The pore volume that the present embodiment prepares catalyst is 0.225ml/g, and specific area is 247m
2/ g.
Embodiment 2, preparation contain the catalyst CB of SAPO-11 molecular sieve
By SAPO-11 molecular sieve, (pore volume is 0.20ml/g, and specific area is 212m
2/ g) 160 grams, MoO
337.5 grams, Ni (NO
3)
26H
2o 145 grams, amorphous aluminum silicide (SiO
2content 50wt%, pore volume 0.85ml/g, specific area 370m
2/ g, butt 75wt%) 35 grams, macroporous aluminium oxide (pore volume 1.0ml/g, specific area 400m
2/ g, butt 75wt%) 133 grams, (butt 30wt%, the mol ratio of nitric acid and little porous aluminum oxide is 0.3 to adhesive, and the pore volume of little porous aluminum oxide is 0.46ml/g, and specific area is 280m
2/ g) 66.5 grams be placed in roller kneading, roll, be pressed into paste, extruded moulding, catalyst after shaping is placed in that air humidity is 80%, temperature is carry out standing aging 10 hours under the condition of 70 DEG C, and at 120 DEG C dry 5 hours, temperature programming rises to 500 DEG C in 4 hours, constant temperature calcining 4 hours, the obtained catalyst B containing SAPO-11 molecular sieve.
The present embodiment prepares in catalyst, SAPO-11 molecular sieve, MoO
3, NiO, amorphous aluminum silicide and aluminium oxide mass percentage be respectively 42.0%, 9.8%, 9.8%, 6.9% and 31.5%.
The pore volume that the present embodiment prepares catalyst is 0.232ml/g, and specific area is 241m
2/ g.
Embodiment 3, preparation contain the catalyst CC of SAPO-11 molecular sieve
By SAPO-11 molecular sieve, (pore volume is 0.20ml/g, and specific area is 212m
2/ g) 160 grams, MoO
355.6 grams, Ni (NO
3)
26H
2o 74 grams, amorphous aluminum silicide (SiO
2content 50wt%, pore volume 0.85ml/g, specific area 370m
2/ g, butt 75wt%) 35 grams, macroporous aluminium oxide (pore volume 1.0ml/g, specific area 400m
2/ g, butt 75wt%) 133 grams, (butt 30wt%, the mol ratio of nitric acid and little porous aluminum oxide is 0.3 to adhesive, and the pore volume of little porous aluminum oxide is 0.46ml/g, and specific area is 280m
2/ g) 66.5 grams be placed in roller kneading, roll, be pressed into paste, extruded moulding, catalyst after shaping is placed in that air humidity is 80%, temperature is carry out standing aging 10 hours under the condition of 70 DEG C, and at 120 DEG C dry 5 hours, temperature programming rises to 500 DEG C in 4 hours, constant temperature calcining 4 hours, the obtained catalyst B containing SAPO-11 molecular sieve.
The present embodiment prepares in catalyst, SAPO-11 molecular sieve, MoO
3, NiO, amorphous aluminum silicide and aluminium oxide mass percentage be respectively 42.0%, 14.6%, 5.0%, 6.9% and 31.5%.
The pore volume that the present embodiment prepares catalyst is 0.228ml/g, and specific area is 239m
2/ g.
Embodiment 4, hydrocracking prepare high-octane naphtha
Adopt feedstock oil to be Iranian VGO, the main character of feedstock oil is as shown in table 1.
At the first reactor charge Hydrobon catalyst 3996; At the second reactor top filling light oil type hydrogen cracking catalyst FC-24, prepared by bottom filling embodiment 1 contains SAPO-11 zeolite catalyst CA, the volume ratio of CA catalyst and FC-24 catalyst is 1:9, and the filling dosage that the filling dosage of FC-24 catalyst is 90m, CA catalyst is 10ml.The temperature of hydrofining reaction is 371 DEG C, and hydrogen to oil volume ratio is 1500:1, and during liquid, volume space velocity is 1.0h
-1; Feedstock oil is effluent oil nitrogenous control <10 μ g/g after an anti-refining stage is refining, and then enter in the second reactor, hydrogen to oil volume ratio 1500:1, the reaction pressure of the second reactor is 14.7MPa, and remaining process conditions is as shown in table 2; In the second reactor, obtain high-octane naphtha through hydrocracking reaction and cracking and isomerization reaction, its octane number is as shown in table 2.
Embodiment 5, hydrocracking prepare high-octane naphtha
Adopt feedstock oil to be Iranian VGO, the main character of feedstock oil is as shown in table 1.
At the first reactor charge Hydrobon catalyst 3996; At the second reactor top filling light oil type hydrogen cracking catalyst FC-24, prepared by bottom filling embodiment 1 contains SAPO-11 zeolite catalyst CA, the volume ratio of CA catalyst and FC-24 catalyst is 2:8, and the filling dosage that the filling dosage of FC-24 catalyst is 80ml, CA catalyst is 20ml.First reactor charge Hydrobon catalyst 3996; Second reactor top filling light oil type hydrogen cracking catalyst FC-24, bottom filling is containing SAPO-11 zeolite catalyst CA, the volume ratio of CA catalyst and FC-24 catalyst is 2:8, feedstock oil is effluent oil nitrogenous control <10 μ g/g after an anti-refining stage is refining, hydrogen to oil volume ratio 1500:1, the reaction pressure of the first reactor and the second reactor is 14.7MPa, and remaining process conditions and invention effect are in table 2.
Comparative example 1,
Adopt normal one-stage serial hydrocracking technique, feedstock oil is Iranian VGO, and the main character of feedstock oil is in table 1.
First reactor charge Hydrobon catalyst 3996; Second reactor all loads light oil type hydrogen cracking catalyst FC-24, feedstock oil is effluent oil nitrogenous control <10 μ g/g after an anti-refining stage is refining, hydrogen to oil volume ratio 1500:1, the reaction pressure of the second reactor is 14.7MPa, remaining process conditions and reaction result as shown in table 2.
As can be seen from the test data of table 2, under the prerequisite that working condition is substantially suitable, method provided by the invention can make the octane number of light naphthar raising 4 ~ 5 units (not reduce hydrocracking catalyst performance under the condition that reactivity is suitable with light naphthar yield, improve the octane number of light naphthar, reach technique effect of the present invention).
The Iranian VGO main character of table 1
Project |
Analysis result |
Density (20 DEG C), g/cm3 |
0.9027 |
Sulphur, μ g/g |
10100 |
Nitrogen, μ g/g |
1200 |
Boiling range, DEG C |
|
IPB/10%/30%/50%/70%/90%/95%/EPB |
328/388/422/447/473/506/520/532 |
The experimental condition of table 2 embodiment 2-3 and comparative example 1 and product characteristics