CN108246343A - A kind of heavy diesel, which is hydrocracked, prepares catalyst of naphtha and preparation method thereof - Google Patents
A kind of heavy diesel, which is hydrocracked, prepares catalyst of naphtha and preparation method thereof Download PDFInfo
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- CN108246343A CN108246343A CN201611236414.XA CN201611236414A CN108246343A CN 108246343 A CN108246343 A CN 108246343A CN 201611236414 A CN201611236414 A CN 201611236414A CN 108246343 A CN108246343 A CN 108246343A
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- catalyst
- molecular sieve
- hydrocracked
- heavy diesel
- naphtha
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
- B01J29/16—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J29/166—Y-type faujasite
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G47/00—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions
- C10G47/02—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used
- C10G47/10—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used with catalysts deposited on a carrier
- C10G47/12—Inorganic carriers
- C10G47/16—Crystalline alumino-silicate carriers
- C10G47/20—Crystalline alumino-silicate carriers the catalyst containing other metals or compounds thereof
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/70—Catalyst aspects
Abstract
The catalyst for preparing naphtha is hydrocracked the invention discloses a kind of heavy diesel, with catalyst butt quality percentages, including modified Y molecular sieve 40.0~70.0%, 10.0~28.0% and the VIIIth race of small porous aluminum oxide and/or group VIB metal oxides 20.0~37.0%.The catalyst has catalytic activity, naphtha yield high, and good reformer feed can be used as by producing heavy naphtha fraction virtue height of diving.
Description
Technical field
Metal salt and the dry-mixed one-time formed catalyst preparation mode of catalyst support material are used the present invention relates to a kind of.
Voluminous latent naphtha catalyst of high virtue and preparation method thereof is hydrocracked more particularly to a kind of heavy diesel.
Background technology
China's consumption diesel and gasoline ratio reached 2.27 from 2005:It keeps falling behind 1 peak, it is contemplated that the year two thousand twenty Consumption of China bavin
Vapour ratio would fall to about 1.1:1, the lower general who has surrendered's centering state oil refining apparatus structural adjustment for consuming diesel and gasoline ratio brings huge challenge.At present
Straight-run diesel oil accounts for about 65% in China's diesel pool, and straight-run diesel oil partial hydrogenation is converted to the latent naphtha of high virtue and high added value is navigated
Coal can improve refinery's economic benefit simultaneously significantly reducing diesel and gasoline ratio.Conventional straight-run diesel oil Hydrofining Technology can only reduce
Product sulphur, nitrogen content improve Cetane number, are unable to reach the purpose for diesel and gasoline ratio of optimizing product structure, reduce.It is excellent to improve refinery
Change product structure ability, the variation for adapting to market product demand, the hydrocracking catalyst developed uses heavy diesel as original
Material, under the premise of ensureing that high liquid is received, the high latent naphtha of virtue of fecund and high-quality aviation kerosine.
Hydrocracking catalyst has Hydrogenation and cracking performance as a kind of bifunctional catalyst.It generally selects non-
Your group vib and VII races metal are as hydrogenation component, and selecting molecular sieve and/or amorphous silicon aluminium, molecular sieve is as Cracking Component
The key component of cracking is played in such catalyst.The main active component of hydrocracking catalyst is Y type molecular sieve, and Y divides
The hydrothermal stability and acid resistance that son sieve silica alumina ratio will directly affect molecular sieve.Silica alumina ratio is improved, contributes to reduction acid site close
Degree improves acid strength, can improve cracking and the ratio between react with hydrogen transfer activity, reduces coke generation, and improvement product is distributed.This
Outside, there is the molecular sieve compared with high silica alumina ratio can bear to be hydrocracked more stringent reaction condition, extends the use of catalyst
Service life.Silica alumina ratio is higher, and heat-resisting, the resistance to steam and acid resistance of molecular sieve are better, and application field will also obtain further
It expands.
CN101618347A discloses a kind of hydrocracking catalyst containing modified Y molecular sieve and preparation method thereof, this changes
Property is mentioned using aluminium salt and inorganic acid combined treatment NH4NaY molecular sieve, then carry out ammonium fluosilicate dealumination complement silicon and hydro-thermal process.
The removing of part framework aluminum is be easy to cause when removing molecular sieve non-framework aluminum using inorganic acid, molecular sieve non-bone is removed using aluminium salt
Since aluminium salt pH value is relatively low during frame aluminium, it is difficult to remove the non-framework aluminum in micropore, and use inorganic acid and aluminium salt combination dealuminzation, both
It can ensure that a large amount of removing non-framework aluminums can reduce the destruction to framework aluminum again.But the isomery performance of Y molecular sieve is relatively low, institute
The cryogenic property for producing intermediate oil is poor.
US4762813 and US4860803 are proposed after aluminium oxide and molecular sieve mixed-forming, then calcination process under high temperature,
Then hydrogenation metal is impregnated, the purpose is to voluminous intermediate oil and solves the problems, such as unstable product quality.Y molecular sieve used
Super stabilizing processing is first passed through, brilliant packet constant is between 2.440~2.465nm, and depth steam treatment makes brilliant packet normal again after molding
Number is further reduced between 2.420~2.435nm so that molecular sieve super-hydrophobicization, carrier secondary pore increase, sour density drop
Low, intensity improves, so as to achieve the purpose that improve the highly selective of intermediate oil.With molecular sieve elder generation hydro-thermal process aftershaping again
Metal phase ratio is soaked, molecular sieve is molded hydro-thermal process again prior to aluminium oxide, sieve particle can be made more uniformly to contact vapor,
So as to be easier to ensure that quality between every batch materials.This method shortcoming is aluminium oxide and hydro-thermal process after molecular sieve mixed-forming
Energy consumption is higher.
US4672048 describes a kind of light oil type hydrogen cracking catalyst, and molecular sieve silica alumina ratio best 11 used~
15, preparation method is that common NaY molecular sieve obtains NH after ammonium exchanges4NaY molecular sieve, then to NH4NaY molecular sieve carries out fluorine
Ammonium silicate is modified, then is carried out hydro-thermal process and obtained USSSY molecular sieves.Method for preparing catalyst is, modified Y molecular sieve with by aperture
Aluminium oxide after drying and roasting soaks metal, is urged after drying and roasting again with binding agent kneading and compacting, carrier made of nitric acid
Agent finished product.Catalyst prepared by the technology has higher light oil selectivity and anti-nitrogen performance, but due to Y molecular sieve acid density
It is relatively low, cause catalyst activity relatively low, in addition impregnate an one-step baking more than upper metal on a catalyst support using metal salt solution
Program.
The patent of invention of Patent No. CN1059846C discloses a kind of light oil type hydrogen cracking catalyst, catalyst composition
For low-Na and high-Si Y-type molecular sieve 50~65wt% of content, aperture alumina content 10~26wt%, WO3Content 18~26%,
NiO contents 4~6%.Preparation method is extruded moulding after low-Na and high-Si Y-type molecular sieve is mixed with small porous aluminum oxide, molding
The high-temperature process under ammonia-water vapour atmosphere, carrier tungstenic after processing, the mixed solution dipping of nickel, dry, roasting are urged
Agent finished product.Catalyst prepared by the technology has higher lytic activity, but liquid receipts are relatively low.
Invention content
Catalyst and its preparation side for preparing naphtha are hydrocracked the purpose of the present invention is to provide a kind of heavy diesel
Method.
To achieve the above object, the present invention provides a kind of heavy diesel and is hydrocracked the catalyst for preparing naphtha, to urge
Agent butt quality percentages, including modified Y molecular sieve 40.0~70.0%, small porous aluminum oxide 10.0~28.0% and the VIIIth
Race and/or group VIB metal oxides 20.0~37.0%.
Further, with catalyst butt quality percentages, including modified Y molecular sieve 40%~70%, preferably 45%
~65%, small porous aluminum oxide 10~28%, preferably 10%~25%, WO316~28%, preferably 18%~25% and NiO 4~
9%, preferably 5~7%.
Further, the modified Y molecular sieve crystalline substance packet constant be 2.440~2.455nm, preferably 2.445~2.455nm,
Mole silica alumina ratio is 7~15, preferably 10~14, Na2O is less than or equal to 0.15wt%, and relative crystallinity is more than or equal to 80%.
Further, the specific surface area of catalyst is 200~450m2/ g, preferably 200~400m2/ g, Kong Rongwei 0.2~
0.5ml/g, preferably 0.2~0.4ml/g.
Further, the preparation method of the modified Y molecular sieve includes：The NH obtained after NaY molecular sieve ammonium is exchanged4Y
Molecular sieve consolidates mass ratio 5 according to liquid:1~15:1 mashing, after being warming up to 80~95 DEG C, by mass fraction 4~8% in 1~3 hour
Ammonium fluosilicate aqueous solution slowly instill in slurries, be added dropwise constant temperature stir 0.5~2 hour, filter, beaten at 40~50 DEG C
Pulp-water is washed 2~5 times, and gained sample is 3~5 hours dry at 110~130 DEG C, obtains ammonium fluosilicate modified Y molecular sieve.
Further, it is atmosphere 3rd side cut and/or first vacuum side stream that the catalyst, which is suitable for heavy diesel,.
Further, the naphtha boiling range that the catalyst preparation obtains is 65~175 DEG C.
To achieve the above object, the present invention also provides the systems that a kind of heavy diesel is hydrocracked the catalyst for preparing naphtha
Preparation Method includes the following steps：
Small porous aluminum oxide is all added in kneading machine, after 5~10min of kneading, adds in aqueous solution of nitric acid, mix by step 1
It pinches to paste shape, is preserved as first binding agent seal for use；
Step 2, the NH obtained after NaY molecular sieve ammonium is exchanged4Y molecular sieve consolidates mass ratio 5 according to liquid:1~15:1 dozen
Slurry, after being warming up to 80~95 DEG C, slowly instills the ammonium fluosilicate aqueous solution of mass fraction 4~8% in slurries in 1~3 hour,
Constant temperature is added dropwise to stir 0.5~2 hour, filters, mashing washing 2~5 times at 40~50 DEG C, gained sample is 110~130
It is 3~5 hours dry at DEG C, obtain ammonium fluosilicate modified Y molecular sieve；And
Step 3, after modified Y molecular sieve, 10~15min of binding agent kneading, by the VIIIth race and/or group VIB metal
Salt, the citric acid for accounting for finished catalyst quality 5%~8% once add in kneading machine, after 10~15min of kneading, are transferred to roller
15~25min is rolled, an extruded moulding, for 110~130 DEG C of freeze-day with constant temperature after 4~8 hours, 450~550 DEG C of roastings 3~6 are small
When, obtain finished catalyst.
Further, the VIIIth race and/or group VIB metal salt are nickel nitrate hexahydrate and/or ammonium tungstate.
The beneficial effects of the invention are as follows：Using the Y molecular sieve that ammonium fluosilicate is modified as crucial Cracking Component, NiO-WO3
As hydrogenation metal component, which there is simple preparation, naphtha yield height, lytic activity height and C5+ liquid to receive high spy
Point.
Specific embodiment
In order to which the present invention is further detailed, spy enumerates following embodiment, but the present invention is not limited in implementing
Example.
A kind of heavy diesel is hydrocracked the catalyst for preparing naphtha, with catalyst butt quality percentages, including
Modified Y molecular sieve 40.0~70.0%, 10.0~28.0% and the VIIIth race of small porous aluminum oxide and/or group VIB metallic element oxygen
Compound 20.0~37.0%.
Further, with catalyst butt quality percentages, including modified Y molecular sieve 40%~70%, preferably 45%
~65%, small porous aluminum oxide 10~28%, preferably 10%~25%, WO316~28%, preferably 18%~25% and NiO 4~
9%, preferably 5~7%.
Further, the modified Y molecular sieve crystalline substance packet constant be 2.440~2.455nm, preferably 2.445~2.455nm,
Mole silica alumina ratio is 7~15, preferably 10~14, Na2O is less than or equal to 0.15wt%, and relative crystallinity is more than or equal to 80%.
Further, the specific surface area of catalyst is 200~450m2/ g, preferably 200~400m2/ g, Kong Rongwei 0.2~
0.5ml/g, preferably 0.2~0.4ml/g.
Further, the preparation method of the modified Y molecular sieve includes：The NH obtained after NaY molecular sieve ammonium is exchanged4Y
Molecular sieve consolidates mass ratio 5 according to liquid:1~15:1 mashing, after being warming up to 80~95 DEG C, by mass fraction 4~8% in 1~3 hour
Ammonium fluosilicate aqueous solution slowly instill in slurries, be added dropwise constant temperature stir 0.5~2 hour, filter, beaten at 40~50 DEG C
Pulp-water is washed 2~5 times, and gained sample is 3~5 hours dry at 110~130 DEG C, obtains ammonium fluosilicate modified Y molecular sieve.
Further, it is atmosphere 3rd side cut and/or first vacuum side stream that the catalyst, which is suitable for heavy diesel,.
Further, the naphtha boiling range that the catalyst preparation obtains is 65~175 DEG C.
A kind of heavy diesel is hydrocracked the preparation method for the catalyst for preparing naphtha, includes the following steps：
Small porous aluminum oxide is all added in kneading machine, after 5~10min of kneading, adds in aqueous solution of nitric acid, mix by step 1
It pinches to paste shape, is preserved as first binding agent seal for use；
Step 2, the NH obtained after NaY molecular sieve ammonium is exchanged4Y molecular sieve consolidates mass ratio 5 according to liquid:1~15:1 dozen
Slurry, after being warming up to 80~95 DEG C, slowly instills the ammonium fluosilicate aqueous solution of mass fraction 4~8% in slurries in 1~3 hour,
Constant temperature is added dropwise to stir 0.5~2 hour, filters, mashing washing 3 times at 40~50 DEG C, gained sample is dry at 120 DEG C
4 hours, obtain ammonium fluosilicate modified Y molecular sieve；Step 3, after modified Y molecular sieve, 10~15min of binding agent kneading, by
VIII race and/or group VIB metal salt, the citric acid of finished product 5%~8% once add in kneading machine, after 10~15min of kneading, turn
Enter roller and roll 15~25min, an extruded moulding, 110~130 DEG C of freeze-day with constant temperature are after 4~8 hours, 450~550 DEG C of roastings
It burns 3~6 hours, obtains finished catalyst.
Further, the VIIIth race and/or group VIB metal salt are nickel nitrate hexahydrate and/or ammonium tungstate.
NaY molecular sieve used is common commercially available NaY molecular sieve in carrier of hydrocracking catalyst of the present invention, silica alumina ratio 5:1,
Na2O content 12.5%, brilliant packet constant 2.468nm, relative crystallinity 96%.
The specific preparation method of modified Y molecular sieve is as follows in hydrocracking catalyst of the present invention：
(1) NH after ammonium is exchanged4NaY molecular sieve is with deionized water according to 1:10 mass ratioes are beaten, and are warming up to 90 DEG C.
The instillation of various concentration ammonium fluosilicate solution is contained into NH in (2) 2 hours4In the slurries of NaY molecular sieve, constant temperature stirring
It 1 hour, filters, mashing washing 3 times at 40~50 DEG C, gained sample is 4 hours dry at 120 DEG C.Ammonium fluosilicate is obtained to change
Property Y molecular sieve.
Embodiment 1
By commercially available Nankai's catalyst plant production NaY molecular sieve (relative crystallinity 95%, lattice constant 2.468nm,
SiO2/A12O3Molar ratio is 5.0, Na2O content is 11.9wt%) it is mixed with the ammonium nitrate solution of a concentration of 2.0mol/L, liquid is solid
Weight ratio is 10, is warming up to 95 DEG C, carries out ion exchange under stiring 1.5 hours, filters off mother liquor, repeats washing 3 times, filters.
It repeats the above process 1 time, filters, washing obtains NH4Y molecular sieve.
Take 200g NH4Y molecular sieve adds in 1.0L deionized waters in four-hole bottle, and stirring is warming up to 80 DEG C.Prepare quality
Score is the ammonium fluosilicate aqueous solution 500g of 4.0%wt, at the uniform velocity being added in molecular sieve slurry in 1 hour, adds in fluosilicic acid altogether
Ammonium 20g continues to stir 0.5h.10 minutes are stood after stopping stirring, is filtered, mashing washing 2 times at 40 DEG C, gained sample exists
It is 5 hours dry at 110 DEG C, it obtains modified Y molecular sieve and is denoted as Y-1, property is listed in table 1.
Embodiment 2
Take 200g NH4Y molecular sieve (with embodiment 1) adds in 2.0L deionized waters in four-hole bottle, and stirring is warming up to 90
℃.The ammonium fluosilicate aqueous solution 500g that mass fraction is 6.0%wt is prepared, at the uniform velocity being added in molecular sieve slurry in 2 hours, altogether
Ammonium fluosilicate 30g is added in, continues to stir 1h.10 minutes are stood after stopping stirring, is filtered, mashing washing 3 times, gained at 45 DEG C
Sample is 4 hours dry at 120 DEG C, obtains modified Y molecular sieve and is denoted as Y-2, property is listed in table 1.
Embodiment 3
Take 200g NH4Y molecular sieve (with embodiment 1) adds in 3.0L deionized waters in four-hole bottle, and stirring is warming up to 95
℃.The ammonium fluosilicate aqueous solution 500g that mass fraction is 8.0%wt is prepared, at the uniform velocity being added in molecular sieve slurry in 3 hours, altogether
Add in ammonium fluosilicate 40g.10 minutes are stood after stopping stirring, is filtered, mashing washing 5 times at 50 DEG C, gained sample is at 130 DEG C
Lower drying 3 hours obtains modified Y molecular sieve and is denoted as Y-3, and property is listed in table 1.
Embodiment 4
276.5g salpeter solutions (65%) are taken, after being diluted with 2318.6g Purified Waters, are slowly added to equipped with 1404.5g apertures
(in the kneading machine for burning residual 71.2%), abundant kneading to paste shape is prepared into nitric acid content 18% to aluminium oxide, and butt 25% glues
Agent is tied, is sealed for use.
By 70.5 grams of modified Y molecular sieve Y-1 (butt 78wt%), 80 grams of binding agents (nitric acid mass fraction 18%, butts
It 25wt%) is put into roller after kneading 15min, adds in 19.46g nickel nitrate hexahydrates, 21.9g ammonium tungstates, 6g citric acids, after
It after continuous kneading 15min, is transferred in roller and is rolled into paste shape, extrusion squeezes out item drying 8 hours at 110 DEG C, then program
It is warming up to 450 DEG C to roast 6 hours, catalyst C-1, property is listed in table 2.
Embodiment 5
By 70.5 grams of modified Y molecular sieve Y-2 (butt 78wt%), 80 grams of binding agents (with embodiment 4, nitric acid quality point
Number 18%, butt 25wt%) be put into roller after kneading 15min, add in 19.46g nickel nitrate hexahydrates, 21.9g ammonium tungstates,
6g citric acids after continuing kneading 15min, are transferred in roller and are rolled into paste shape, extrusion, and it is small to squeeze out item drying 6 at 120 DEG C
When, then temperature programming to 500 DEG C roast 4 hours, catalyst C-2, property is listed in table 2.
Embodiment 6
By 70.5 grams of modified Y molecular sieve Y-3 (butt 78wt%), 80 grams of binding agents (with embodiment 4, nitric acid quality point
Number 18%, butt 25wt%) be put into roller after kneading 15min, add in 19.46g nickel nitrate hexahydrates, 21.9g ammonium tungstates,
6g citric acids after continuing kneading 15min, are transferred in roller and are rolled into paste shape, extrusion, and it is small to squeeze out item drying 4 at 130 DEG C
When, then temperature programming to 550 DEG C roast 3 hours, catalyst C-3, property is listed in table 2.
Embodiment 7
By 64.1 grams of modified Y molecular sieve Y-3 (butt 78wt%), 80 grams of binding agents (with embodiment 4, nitric acid quality point
Number 18%, butt 25wt%) be put into roller after kneading 15min, add in 19.46g nickel nitrate hexahydrates, 27.4g ammonium tungstates,
5g citric acids after continuing kneading 15min, are transferred in roller and are rolled into paste shape, extrusion, and it is small to squeeze out item drying 6 at 120 DEG C
When, then temperature programming to 500 DEG C roast 4 hours, catalyst C-4, property is listed in table 2.
Embodiment 8
By 83.3 grams of modified Y molecular sieve Y-3 (butt 78wt%), 40 grams of binding agents (with embodiment 4, nitric acid quality point
Number 18%, butt 25wt%) be put into roller after kneading 15min, add in 27.2g nickel nitrate hexahydrates, 19.7g ammonium tungstates,
8g citric acids after continuing kneading 15min, are transferred in roller and are rolled into paste shape, extrusion, and it is small to squeeze out item drying 6 at 120 DEG C
When, then temperature programming to 500 DEG C roast 4 hours, catalyst C-5, property is listed in table 2.
Embodiment 9
On 200ml plus hydrogen evaluating apparatus, C1~C5 catalyst is evaluated with vacuum 1st side cut miscella using normal 3.It is former
Material oil enters cracking zone after 1 anti-refining stage hydrofinishing, and raw material oil nature is as shown in table 3.Cracking zone process conditions are：Reaction
Pressure 8.0MPa, hydrogen to oil volume ratio 800:1, volume space velocity 1.5h-1.Evaluation result is shown in Table 4.
By table 1 as it can be seen that as ammonium fluosilicate concentration increases, Y molecular sieve dealumination complement silicon degree is continuously increased, and silica alumina ratio is from Y-
The 6.7 of 1 increase to the 11.5 of Y-3, and brilliant packet constant is also contracted to 2.448 by the 2.457 of Y-1.Show in the acidity on molecular sieve
Calculation amount is constantly reduced, and acid strength is continuously increased, and is conducive to the raising of catalyst activity and selectivity.
1 modified molecular screen property of table
As can be seen from Table 2, the specific surface area of catalyst C1~C5 is in 233.8~277.8m2Between/g, catalytic mechanical intensity
It is improved with the addition of citric acid.
2 catalyst property of table
3 raw material oil nature of table
In C1, C2, C3 catalyst it can be seen from 4 result of table, using Y-3 Zeolite synthesis C3 catalyst have compared with
Good cracking activity, it is higher using the C1 catalyst C5+ liquid receipts of Y-1 Zeolite synthesis, it is catalyzed using the C2 of Y-2 Zeolite synthesis
Agent, has suitable cracking activity and hydrogenation activity, and product virtue dives up to 51.Tri- kinds of catalyst of C3, C4, C5 are compared, can be seen
The C4 catalyst for going out Y-3 molecular sieve contents 50% has higher heavy naphtha yield and heavy naphtha selectivity, Er Qiechong
Naphtha virtue dive up to 54.6 can be used as good reforming material, while C5+ liquid receive it is higher, reach 93.5%.
Table 4 plus hydrogen evaluation result
Certainly, the present invention can also have other various embodiments, without deviating from the spirit and substance of the present invention, ripe
Various corresponding changes and deformation, but these corresponding changes and deformation can be made according to the present invention by knowing those skilled in the art
The protection domain of the claims in the present invention should all be belonged to.
Claims (14)
1. a kind of heavy diesel is hydrocracked the catalyst for preparing naphtha, which is characterized in that with catalyst butt quality percentage
Than meter, including modified Y molecular sieve 40.0~70.0%, 10.0~28.0% and the VIIIth race of small porous aluminum oxide and/or group VIB gold
Belong to element oxide 20.0~37.0%.
2. heavy diesel according to claim 1 is hydrocracked the catalyst for preparing naphtha, which is characterized in that with catalysis
Agent butt quality percentages, including modified Y molecular sieve 40%~70%, small porous aluminum oxide 10~28%, WO316~28%
With NiO 4~9%.
3. heavy diesel according to claim 1 is hydrocracked the catalyst for preparing naphtha, which is characterized in that described to change
Property Y molecular sieve crystalline substance packet constant be 2.440~2.455nm, mole silica alumina ratio is 7~15, Na2O is less than or equal to 0.15wt%, relatively
Crystallinity is more than or equal to 80%.
4. heavy diesel according to claim 1 is hydrocracked the catalyst for preparing naphtha, which is characterized in that described to urge
Agent specific surface area is 200~450m20.2~0.5ml/g of/g, Kong Rongwei.
5. heavy diesel according to claim 1 is hydrocracked the catalyst for preparing naphtha, which is characterized in that described to change
The preparation method of property Y molecular sieve includes：The NH obtained after NaY molecular sieve ammonium is exchanged4Y molecular sieve consolidates mass ratio 5 according to liquid:1
~15:1 mashing, after being warming up to 80~95 DEG C, slowly drips the ammonium fluosilicate aqueous solution of mass fraction 4~8% in 1~3 hour
Enter in slurries, constant temperature is added dropwise and stirs 0.5~2 hour, filters, mashing washing 2~5 times, gained sample at 40~50 DEG C
It is 3~5 hours dry at 110~130 DEG C, obtain ammonium fluosilicate modified Y molecular sieve.
6. heavy diesel according to claim 1 is hydrocracked the catalyst for preparing naphtha, which is characterized in that described to urge
It is atmosphere 3rd side cut and/or first vacuum side stream that agent, which is suitable for heavy diesel,.
7. heavy diesel according to claim 1 is hydrocracked the catalyst for preparing naphtha, which is characterized in that described to urge
The naphtha boiling range that agent is prepared is 65~175 DEG C.
8. heavy diesel according to any one of claims 1 to 7 is hydrocracked the preparation method for the catalyst for preparing naphtha,
It is characterized by comprising the following steps：
Small porous aluminum oxide is all added in kneading machine, after 5~10min of kneading, adds in aqueous solution of nitric acid, kneading is extremely by step 1
Paste shape preserves for use as first binding agent seal；
Step 2, the NH obtained after NaY molecular sieve ammonium is exchanged4Y molecular sieve consolidates mass ratio 5 according to liquid:1~15:1 mashing, heating
To after 80~95 DEG C, 4~8% ammonium fluosilicate aqueous solution of mass fraction is slowly instilled in slurries in 1~3 hour, is added dropwise
Constant temperature stirs 0.5~2 hour, filters, and mashing washing 2~5 times at 40~50 DEG C, gained sample is dry at 110~130 DEG C
3~5 hours, obtain ammonium fluosilicate modified Y molecular sieve；Step 3, after modified Y molecular sieve, 10~15min of binding agent kneading,
VIIIth race and/or group VIB metal salt, the citric acid for accounting for finished catalyst catalyst quality 5%~8% are once added in into kneading
Machine after 10~15min of kneading, is transferred to roller and rolls 15~25min, an extruded moulding, and 110~130 DEG C of freeze-day with constant temperature 4~
After 8 hours, 450~550 DEG C roast 3~6 hours, obtain finished catalyst.
9. heavy diesel according to claim 8 is hydrocracked the preparation method for the catalyst for preparing naphtha, feature
It is, the VIIIth race and/or group VIB metal salt are nickel nitrate hexahydrate and/or ammonium tungstate.
10. heavy diesel according to claim 8 is hydrocracked the preparation method for the catalyst for preparing naphtha, feature
It is, the catalyst being prepared is with catalyst butt quality percentages, including modified Y molecular sieve 40%~70%, aperture
Aluminium oxide 10~28%, WO316~28% and NiO 4~9%.
11. heavy diesel according to claim 8 is hydrocracked the preparation method for the catalyst for preparing naphtha, feature
It is, the modified Y molecular sieve crystalline substance packet constant is 2.440~2.455nm, and mole silica alumina ratio is 7~15, Na2O is less than or equal to
0.15wt%, relative crystallinity are more than or equal to 80%.
12. heavy diesel according to claim 8 is hydrocracked the preparation method for the catalyst for preparing naphtha, feature
It is, the specific surface area of catalyst is 200~450m20.2~0.5ml/g of/g, Kong Rongwei.
13. heavy diesel according to claim 8 is hydrocracked the preparation method for the catalyst for preparing naphtha, feature
It is, it is atmosphere 3rd side cut and/or first vacuum side stream that the catalyst, which is suitable for heavy diesel,.
14. heavy diesel according to claim 8 is hydrocracked the preparation method for the catalyst for preparing naphtha, feature
It is, the naphtha boiling range that the catalyst preparation obtains is 65~175 DEG C.
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