CN108114737A - A kind of hydrocatalyst for saturating, its preparation method and application - Google Patents
A kind of hydrocatalyst for saturating, its preparation method and application Download PDFInfo
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- CN108114737A CN108114737A CN201611065773.3A CN201611065773A CN108114737A CN 108114737 A CN108114737 A CN 108114737A CN 201611065773 A CN201611065773 A CN 201611065773A CN 108114737 A CN108114737 A CN 108114737A
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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
- B01J29/10—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing iron group metals, noble metals or copper
- B01J29/14—Iron group metals or copper
- B01J29/146—Y-type faujasite
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- 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
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/44—Hydrogenation of the aromatic hydrocarbons
- C10G45/46—Hydrogenation of the aromatic hydrocarbons characterised by the catalyst used
- C10G45/54—Hydrogenation of the aromatic hydrocarbons characterised by the catalyst used containing crystalline alumino-silicates, e.g. molecular sieves
-
- 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
- C10G2300/10—Feedstock materials
- C10G2300/1037—Hydrocarbon fractions
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- 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
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/30—Physical properties of feedstocks or products
- C10G2300/307—Cetane number, cetane index
-
- 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
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/04—Diesel oil
Abstract
A kind of hydrocatalyst for saturating, its preparation method and application, catalyst carrier is made with modified NaY zeolite and modified alumina composite, non-noble metal hydrogenation component and noble metal hydrogenating component are supported successively, by the dry and high-temperature oxygen-enriched nitrogen drying of negative pressure middle temperature is dried, hypoxemia nitrogen, then with hydrogen partial pressure reduction treatment；Use the mixed gas of hydrogen and inert gas in hydrogen partial pressure reduction, the volume fraction of hydrogen is 1% ~ 99% in mixed gas, and reduction temperature is 400~550 DEG C, obtains the hydrocatalyst for saturating.The present invention is using low hydrogen concentration hydrogen partial pressure and is reduced at relatively high temperatures to containing noble metal metallic catalyst, reduce the speed of metal oxide reduction generation water, reduce the risk that the noble metal crystal grain caused by reducing medium water content is excessively high is assembled, using this catalyst to the diesel oil fraction hydrogenating saturation containing aromatic hydrocarbons, it is cracked in conjunction with type selecting, low fragrant diesel oil, diesel cetane-number increase rate 23.8 units higher than the prior art can be produced.
Description
Technical field
The present invention relates to a kind of hydrocatalyst for saturating, are related to a kind of saturated hydrogenation catalyst of arylhydrocarbon in diesel oil by it, belong to
In hydrogenation catalyst technical field.
Background technology
The key component of catalytic diesel oil is condensed-nuclei aromatics, and Cetane number is very low.With enhancing of the people to environmental consciousness,
Environmental protection institution also proposed diesel oil index harsher requirement, define the arene content of diesel oil and minimum hexadecane
Value.Therefore, market needs low fragrant high cetane number diesel oil.
CN1156752A discloses a kind of diesel modifying technique, be using poor ignition quality fuel as raw material, particularly with LCO raw materials,
Maintain certain N+ α NH3Under the conditions of value and hydro-conversion,（With FH-98 and 3963 catalyst combinations）Make feedstock oil by containing point
The hydrogenation conversion catalyst bed of son sieve makes choice cracking, improves Cetane number.The technology has more set commercial plants at home
It uses, there are problems to be：Its selective splitting is to an aromatic ring hydrocracking in condensed-nuclei aromatics, it is impossible to removing virtue
Hydrocarbon improves Cetane number and is also simply carried out in aromatic hydrocarbons, limited extent.
US5114562 describes the two-stage method work flow of a kind of intermediate oil hydrodesulfurization and aromatic hydrocarbons saturation.The party
Method carries out hydrodesulfurization, the product after desulfurization enters stripper, using hydrogen in the first reactor there are two independent reactor
Circulation of vital energy in the wrong direction stream stripping removing H2S and NH3.Then second reactor is entered back into, second reactor is using noble metal catalyst, behaviour
Make condition as high pressure low temperature, be substantially carried out the hydrogenation saturated reaction of aromatic hydrocarbons.The method is hydrogenation technique more mature at this stage
Process, commercial Application also compare more.The technology there are the problem of be to improve diesel cetane-number contribution it is little.
CN00123141.3 discloses a kind of hydrocatalyst for saturating arylhydrocarbon in diesel oil and preparation method thereof, it selects a kind of acidity
Suitable Y zeolites and aluminium oxide are carrier, support base metal nickel and noble metal, improve the sulfur resistive of catalyst, anti-nitrogen performance.
Its there are the problem of be：The thermal stability of aluminium oxide also has the space promoted, in addition, in catalyst application aspect, it is using biography
The restoring method of system --- low-temperature reduction method, therefore, the activity of catalyst also have the space promoted.
The content of the invention
It is limited to solve hydrogenation activity existing for diesel oil hydrogenation catalyst in the prior art, journey is improved to diesel cetane-number
The problem of limited is spent, the present invention intends providing a kind of hydrocatalyst for saturating, and diesel oil hydrogenation modification technology Cetane number is overcome to carry
The defects of high-amplitude is small, catalyst using the present invention carry out hydrogenation saturation to the condensed-nuclei aromatics in diesel oil, are carried for type selecting cracking
It for quality raw materials, then cracks and combines with type selecting, improve Cetane number, produce low fragrant diesel oil.
The technical purpose of first aspect present invention is to provide a kind of preparation method of hydrocatalyst for saturating, including following step
Suddenly：
The first step, NaY zeolite are modified：Soluble ammonium salting liquid is contacted with NaY zeolite, it is stirred to react 0.5 in 50~100 DEG C~
5 it is small when, filtering adds in ammonium salt solution and repeats above reaction, again until Na in NaY zeolite2O mass contents reach 2.0% with
Under；By ammonium salt solution, treated that zeolite is placed in hydro-thermal process stove carries out steam treatment, is warming up to 250~850 DEG C, heating
Be passed through nitrogen in the process, keep afterwards temperature carry out hydro-thermal process 0.5 it is small when more than, zeolite after steam treatment using containing
There is H+And NH4 +Two kinds of cationic buffer solution processing, obtain Modified NaY Zeolite；
Second step, it is alumina modified：Aluminium oxide is subjected to high-temperature water atmosphere acidification in 40 ~ 70 DEG C, obtains modified aluminas；
3rd step prepares catalyst carrier：By the first step prepare Modified NaY Zeolite, second step prepare modified aluminas with
Extrusion aid mixes, and through kneading, shaping, drying and the obtained catalyst carrier of roasting, the mass ratio of the NaY zeolite and aluminium oxide is
40~85：15~60；
4th step loads hydrogenation component：Catalyst carrier prepared by the 3rd step is supported into non-noble metal hydrogenation component and expensive successively
Metal hydrogenation component；
5th step does the catalyst of the 4th step by negative pressure middle temperature is dried, the dry and high-temperature oxygen-enriched nitrogen of hypoxemia nitrogen successively
It is dry, then with hydrogen partial pressure reduction treatment；The mixed gas of hydrogen and inert gas is used in the hydrogen partial pressure reduction, is mixed
The volume fraction for closing hydrogen in gas is 1% ~ 99%, and reduction temperature is 400~550 DEG C, obtains the hydrocatalyst for saturating.
In above-mentioned preparation method, soluble ammonium salt is selected from ammonium nitrate, ammonium sulfate, ammonium acetate and chlorine described in the first step
Change at least one of ammonium, ammonium salt concentration is 0.5 ~ 5mol/L, and ammonium salt solution is mixed by weight with zeolite as 0.1 ~ 10：1.
It in above-mentioned preparation method, is handled in the first step by ammonium salt solution, Na2O mass contents control preferably 1.0%
Hereinafter, it is more preferably less than 0.5%.
In above-mentioned preparation method, the temperature that hydro-thermal process is carried out in the first step is preferably 450 ~ 750 DEG C.
In above-mentioned preparation method, in the first step carry out hydro-thermal process when system in PH2O/ P is 0.2 ~ 0.9, is preferably
0.3 ~ 0.8, PNH3/ P is 0.1 ~ 0.8, is preferably 0.2 ~ 0.7, NH therein3It is the NH that the molecular sieve after being exchanged by ammonium carries4 +From
Son volatilization generation.When the time of hydro-thermal process is preferably 1 ~ 5 small.
In above-mentioned preparation method, H in buffer solution in the first step+It can be provided by acid, NH4 +It can be provided by ammonium salt；It is slow
The pH of solution is rushed as 4 ~ 6, preferably 4 ~ 5.
In above-mentioned preparation method, the Modified NaY Zeolite obtained in the first step has following characteristics：Aperture is more than 1.7
×10-10The pore volume of rice accounts for total pore volume more than 45%, and surface area is more than 750 ~ 900m2/g；SiO2/Al2O3Than 8 ~ 15；Structure cell is joined
2.423 ~ 2.545nm of number, crystallinity 95 ~ 110%, sodium weight content 0.05% ~ 0.25%, pyridine adsorption IR-TPD total acid contents 0.5 ~
1.5mmol/g, DTA structure destroy 920 ~ 1100 DEG C of peak temperature.
In above-mentioned preparation method, aluminium oxide described in second step is that aluminium oxide general in hydrogenation catalyst field is former
Material includes but are not limited to the HT oxidations of SB powder aluminium oxide, HP aluminium oxide or high temperature precipitations the method production of Ziegler methods production
Aluminium.
In above-mentioned preparation method, alumina modified temperature is preferably 50 ~ 60 DEG C in second step, and the modified time is
16 ~ 80 it is small when, preferably 24 ~ 72 it is small when, using dust technology when modified, concentration is 0.05 ~ 0.5M, is preferably 0.1 ~ 0.2M；Often
The dust technology dosage of 100g aluminium oxide is 100 ~ 300mL, is preferably 160 ~ 240mL.
In above-mentioned preparation method, extrusion aid is in sesbania powder, citric acid, oxalic acid and cellulose described in the 3rd step
At least one.
In above-mentioned preparation method, sheet, spherical, cylindrical bars or irregular bar are shaped to described in the 3rd step（Such as three leaves
Grass, bunge bedstraw herb etc.）, it is preferably cylindrical bars or irregular bar.
In above-mentioned preparation method, drying condition is described in the 3rd step：When drying 2 ~ 12 is small at 110 DEG C ± 10 DEG C.
The condition of the roasting is 450 ~ 750 DEG C of temperature, is preferably 500 ~ 650 DEG C, is preferably 2 ~ 8 small when roasting time is 2 ~ 24 small
When.
In above-mentioned preparation method, non-noble metal hydrogenation component described in the 4th step in Ni, W, Mo and Co extremely
Few one kind, the noble metal hydrogenating component are selected from least one of Ru, Rh, Pd, Os, Ir and Pt, are being catalyzed with metallic element
Mass content meter in agent, the loading of the non-noble metal hydrogenation component is 0.5% ~ 10.0%, the noble metal hydrogenating component
Loading be 0.1% ~ 2.0%.
In above-mentioned preparation method, using infusion process carrying metal component in the 4th step, by metallic components during dipping
Maceration extract and catalyst carrier with 1.5 ~ 3:1 volume ratio mixes, and when dipping 6 ~ 24 is small, and stirs simultaneously, pH controls 2 ~ 10,
Dry in the shade after dipping 8 ~ 24 it is small when, it is then dry at 80 ~ 120 DEG C, roasted at 550 ~ 590 DEG C.
In above-mentioned preparation method, negative pressure middle temperature is dried described in the 5th step is in 200~300 DEG C of temperature, preferably 230
~270 DEG C, when constant temperature 2~8 is small under the conditions of vacuum degree ＞ 66kPa, preferably 3 ~ 6 it is small when；
270~420 DEG C of the hypoxemia nitrogen drying temperature, Oxygen in Nitrogen content are 0.2 volume %-1.5 volume %, are preferably 0.5
The volume % of volume % ~ 1.
The high-temperature oxygen-enriched nitrogen drying condition is 400~480 DEG C of temperature, preferably 420~460 DEG C, Oxygen in Nitrogen content
For the volume % of 5 volume %~8, when constant temperature 2~8 is small, preferably 3 ~ 6 it is small when.
In above-mentioned preparation method, the actual conditions of the reduction of hydrogen partial pressure described in the 5th step is：Temperature is preferably 420
~ 550 DEG C, more preferably 480 ~ 510 DEG C；0.01 ~ 2.00Mpa of pressure；Mixed gas and catalyst by volume 100 ~ 1500：1,
Preferably 500 ~ 1200：1 is mixed, the recovery time for 1 ~ 96 it is small when, preferably 24 ~ 72 it is small when.
Further, hydrogen volume fraction is preferably 20% ~ 80% in the mixed gas, and more preferably 60% ~ 80%, it is described
Inert gas is selected from least one of helium, neon, argon and krypton.Hydrogen in the mixed gas can be selected by adsorbing and removing or
Person's hydrogenolysis falls C2 +Hydrocarbon reforms hydrogen, the hydrogen of refinery's pressure-variable adsorption separator production or the electrolysis hydrogen by molecular sieve dehydration.
The technical purpose of another aspect of the present invention is the hydrocatalyst for saturating for providing above method preparation.The present invention's
In catalyst, using modified NaY zeolite and modified aluminium oxide collectively as carrier.The oxygen that method by the present invention is modified
Change aluminium property more to stablize, rear surface product variation difference is heat-treated at 450~750 DEG C<23.By hydrogen partial pressure reduction treatment,
The speed of metal oxide reduction generation water can be reduced, the noble metal crystal grain caused by reducing medium water content is excessively high is reduced and gathers
Collection, so that the distribution of metallic element is more uniform in catalyst.
The technical purpose of third aspect present invention is that providing a kind of arylhydrocarbon in diesel oil is hydrogenated with saturation process, will contain aromatic hydrocarbons
Diesel oil distillate is contacted with above-mentioned hydrocatalyst for saturating.
It is hydrogenated in above-mentioned arylhydrocarbon in diesel oil in saturation process, the diesel oil distillate is the straight-run diesel oil that boiling range is 160 ~ 360 DEG C
The diesel oil distillate that boiling range is 160 ~ 360 DEG C in coking, catalytic cracking process production in fraction or PETROLEUM PROCESSING.Hydrogenation process
Operating condition reaction be：2 ~ 15MPa of pressure is preferably 3 ~ 10MPa；200 ~ 400 DEG C of reaction temperature, preferably 250 ~ 350 DEG C；Instead
0.5 ~ 5.0h of volume space velocity when answering liquid-1, preferably 1.0 ~ 3.0h-1, reaction hydrogen to oil volume ratio is 500 ~ 1800, preferably 800 ~ 1200.
It is hydrogenated in above-mentioned arylhydrocarbon in diesel oil in saturation process, it is desirable that the nitrogen content in feedstock oil<600 μ g/g, preferably<300μg/
G, more preferably<100μg/g.
Compared with prior art, the present invention has following features：
The hydrocatalyst for saturating of the present invention is to carry out sour modified, raising to accounting for the aluminium oxide of catalyst carrier total amount 30~50%
The thermal stability of modified aluminas specific surface area, that is, improve the thermal stability of the specific surface area of catalyst carrier, make catalysis
Agent hydrogenation activity is improved, and regenerability is improved；The present invention is using low hydrogen concentration hydrogen partial pressure and at relatively high temperatures
It is reduced to containing noble metal metallic catalyst, reduces the speed of metal oxide reduction generation water, reduce because of reducing medium
The risk of noble metal crystal grain aggregation caused by water content is excessively high, noble metal crystal grain assembles shadow when overcoming prior art high temperature reduction
Catalyst activity is rung, the insufficient shortcoming for influencing catalyst activity of metal oxide reduction, makes catalyst during low-temperature reduction
Hydrogenation saturated activity higher；High-activity hydrogenation saturation catalyst using the present invention satisfies to the diesel oil fraction hydrogenating containing aromatic hydrocarbons
With, it is cracked in conjunction with type selecting, low fragrant diesel oil can be produced, meanwhile, diesel cetane-number increase rate is higher than the prior art by 23.8
A unit.
Specific embodiment
Following non-limiting examples can make those of ordinary skill in the art be more fully understood the present invention, but not with
Any mode limits the present invention.
Embodiment 1
The preparation of hydrocatalyst for saturating C1：
The first step, NaY zeolite are modified：Industrial 100 grams of NaY zeolite is placed in every liter of (NH containing 150g4)2SO4It is water-soluble
It is stirred in liquid, when being warming up to 90 ~ 100 DEG C and small holding 1, filtering, after repeating aforesaid operations three times, washing.By what is handled above
Product is placed in tube furnace, and 500 DEG C are warming up to while being passed through nitrogen, stops logical nitrogen, keeps pressure in 0.1MPa, maintenance 2
Temperature fall after hour.The product obtained after hydro-thermal process is placed in 1 liter of CH containing 154g3COONH4With 100g CH3The water of COOH
It is handled in solution, then filters, washs, is dry to get Modified NaY Zeolite, physico-chemical property is shown in Table 1.
Second step, it is alumina modified：Take the SB powder aluminium oxide of German import（Al2O3Aluminium powder, contents on dry basis 75%）120g with
100mL concentration is that the nitric acid glue of 0.2M melts, and obtained glue is melted object in the heatproof container of a capping, puts hydro-thermal process into
In stove, 55 DEG C, when constant temperature 72 is small are heated to, modified aluminas G1 is made, heat stabilization test the results are shown in Table 2.
3rd step prepares catalyst carrier：The modification that Modified NaY Zeolite 222g prepared by the first step is taken to be prepared with second step
1 220g of alumina G mixing rolls, extrusion, when 110 DEG C of dryings 4 are small, when 550 DEG C of roastings 5 are small.
4th step：Load hydrogenation component：The catalyst carrier that 3rd step obtains with nickel nitrate solution is impregnated, obtains Ni weights
The carrier that content is 3.8% is measured, when 110 DEG C of dryings 4 are small, when 550 DEG C of roastings 5 are small；Pd (NH are used again4)NO3Solution dipping is above-mentioned to urge
Agent, it is the bimetallic high-activity hydrogenation saturation catalyst C1 that 0.8%, Ni weight contents are 3.8% to obtain Pt weight contents, property
Matter is listed in table 3.
5th step, by hydrocatalyst for saturating successively by negative pressure middle temperature is dried, the dry and high-temperature oxygen-enriched nitrogen of hypoxemia nitrogen
Gas is dried, and carries out hydrogen partial pressure reduction, and dry and reduction actual conditions is shown in Table 4 and table 5.
Embodiment 2
The preparation of hydrocatalyst for saturating C2：
As different from Example 1, when hydrothermal conditions are 84 small in second step, modified aluminas G2, thermostabilization is made
Property result of the test is shown in Table 2.Other steps are identical with embodiment 1, and bimetallic high-activity hydrogenation saturation catalyst C2, property is made
It is listed in table 3.
Embodiment 3
The preparation of hydrocatalyst for saturating C3：
As different from Example 1, when hydrothermal conditions are 96 small in second step, modified aluminas G3, thermostabilization is made
Property result of the test is shown in Table 2.Other steps are identical with embodiment 1, and bimetallic high-activity hydrogenation saturation catalyst C3, property is made
It is listed in table 3.
Comparative example 1
It changes the modified aluminas G1 in embodiment 1 into SB powder alumina raw materials without modification, Pt is changed into Pd, make
Standby catalyst DC, property are listed in table 3.It, which is reduced, uses traditional low-temperature reduction method, and actual conditions is shown in Table 5.
Comparative example 2
In embodiment 1 in catalyst process is prepared, the hydrogen partial pressure reduction not using the present invention when being reduced, but adopt
With the identical low-temperature reduction method of comparative example 1, corresponding catalyst DC1 is respectively obtained, property is listed in table 3, dry and reduction
Actual conditions is shown in Table 4 and table 5.
The physico-chemical property for the Modified NaY Zeolite that the first step obtains in 1. embodiment 1 of table
Thermal stability of alumina is tested：
By SB powder aluminium oxide and modified aluminas G1, G2 and G3 be respectively placed under different temperatures heat treatment 4 it is small when, then measure it
Specific surface area the results are shown in Table 2.
Specific surface area of 2. alumina support of table after different temperatures heat treatment
As can be seen from Table 2：By 450 ~ 750 DEG C of heat treatments, modified aluminas G1, G2 and G3 surface area variation difference are respectively
23rd, 22 and 22, and change difference 99 without the SB powder aluminium oxide surface area of modification, illustrate modified aluminas specific surface area
Thermal stability it is better than without the SB powder aluminium oxide of modification.The good aluminium oxide of thermal stability is to develop under the high temperature conditions
The high-activity hydrogenation saturation catalyst used is laid a good foundation.
3. catalyst C1 ~ C3 of table, the property of DC, DC1
4. catalyst C1 ~ C3 of table, the drying condition of DC, DC1
5. catalyst C1 ~ C3 of table, the reducing condition of DC, DC1
Embodiment 4
The performance evaluation of catalyst：
（1）Diesel oil fraction hydrogenating saturation experiments：
In 100 milliliters of single tube hydrogen once by being carried out on device.Feedstock oil is triumph 160~360 DEG C of fractions of catalytic diesel oil,
Character is shown in Table 6, and evaluation condition and result are listed in table 7,8 respectively.
6. raw material oil nature of table
7. catalyst C1 ~ C3 of table, DC, DC1 carry out the experiment condition of diesel oil hydrogenation
8. catalyst C1 ~ C3 of table, DC, DC1 carry out product hydrocarbon types and content after diesel oil hydrogenation
The evaluation result of table 8 show the oily arene content of catalyst reaction of the present invention generation be respectively 11.9m%, 12.1m% and
12.6m%, and the oily arene content of the reaction of comparative catalyst DC generation is 18.5m%, the oily arene content of reaction generation of DC1 is
16.6m% illustrates that the hydrogenation saturation performance of catalyst of the present invention is substantially better than comparative catalyst.
（2）The regenerability experiment of catalyst
The degradation condition of accelerating of catalyst C1 and DC are shown in Table 9, and regeneration test condition is shown in Table 10, is denoted as ZC1 after regeneration respectively
And ZDC, diesel oil hydrogenation experiment is carried out respectively, and test raw material oil nature is shown in Table 6, and regenerated catalyst carries out diesel oil hydrogenation experiment condition
11 and 12 are shown in Table respectively with the product hydrocarbon types after hydrogenation and content results.
Table 9. accelerates degradation condition
10. regeneration test condition of table
11. regenerated catalyst of table carries out the experiment condition after diesel oil hydrogenation
12. regenerated catalyst of table carries out the product hydrocarbon types and content after diesel oil hydrogenation
The evaluation result of table 11 shows：The oily arene content of regenerative agent reaction generation of catalyst C1 of the present invention is 12.6m%, with table 5
Fresh catalyst evaluation result it is suitable；And the oily arene content of regenerative agent reaction generation of the catalyst DC of comparative example 1 is
20.1m% differs 1.6 percentage points with 7 fresh catalyst evaluation result of table.Illustrate that the regenerability of catalyst of the present invention is apparent
Better than comparative catalyst.
（3）Catalyst application test
With（1）Middle catalyst C1 is raw material to triumph catalytic diesel oil hydrogenation saturation testing generation oil（It is denoted as 1#Raw material）It is urged with triumph
Change diesel oil is raw material（Referred to as 2#Raw material）, property is shown in Table 6, in 3963 catalyst（The catalyst and FH-98 catalyst combinations are
Through on mostly set commercial plants application success, property be shown in Table 13, the condition of comparative evaluation and the results are shown in Table 14.
13. 3963 catalyst property of table
Modification effect of the 14. different material oil of table on 3963 catalyst
Table 14 statistics indicate that, hydrogenation saturation is carried out to the triumph catalytic diesel oil after refined with catalyst of the present invention, is then used again
3693 catalyst carry out type selecting cracking, and aromatic hydrocarbons can be made to reduce by 53.9 percentage points, and Cetane number improves 35.1 units, with showing
There is technology（The combinations of FH-98 and 3963）Type selecting cracking is compared, high 23.8 units of diesel cetane-number increase rate, arene content
It is lower.
Claims (10)
1. a kind of preparation method of hydrocatalyst for saturating, comprises the following steps：
The first step, NaY zeolite are modified：Soluble ammonium salting liquid is contacted with NaY zeolite, it is stirred to react 0.5 in 50~100 DEG C~
5 it is small when, filtering adds in ammonium salt solution and repeats above reaction, again until Na in NaY zeolite2O mass contents reach 2.0% with
Under；By ammonium salt solution, treated that zeolite is placed in hydro-thermal process stove carries out steam treatment, is warming up to 250~850 DEG C, heating
Be passed through nitrogen in the process, keep afterwards temperature carry out hydro-thermal process 0.5 it is small when more than, zeolite after steam treatment using containing
There is H+And NH4 +Two kinds of cationic buffer solution processing, obtain Modified NaY Zeolite；
Second step, it is alumina modified：Aluminium oxide is subjected to high-temperature water atmosphere acidification in 40 ~ 70 DEG C, obtains modified aluminas；
3rd step prepares catalyst carrier：By the first step prepare Modified NaY Zeolite, second step prepare modified aluminas with
Extrusion aid mixes, and through kneading, shaping, drying and the obtained catalyst carrier of roasting, the mass ratio of the NaY zeolite and aluminium oxide is
40~85：15~60；
4th step loads hydrogenation component：Catalyst carrier prepared by the 3rd step is supported into non-noble metal hydrogenation component and expensive successively
Metal hydrogenation component；
5th step does the catalyst of the 4th step by negative pressure middle temperature is dried, the dry and high-temperature oxygen-enriched nitrogen of hypoxemia nitrogen successively
It is dry, then with hydrogen partial pressure reduction treatment；The mixed gas of hydrogen and inert gas is used in the hydrogen partial pressure reduction, is mixed
The volume fraction for closing hydrogen in gas is 1% ~ 99%, and reduction temperature is 400~550 DEG C, obtains the hydrocatalyst for saturating.
2. according to the method described in claim 1, it is characterized in that：Soluble ammonium salt is selected from ammonium nitrate, sulphur described in the first step
At least one of sour ammonium, ammonium acetate and ammonium chloride, ammonium salt concentration are 0.5 ~ 5mol/L, and ammonium salt solution mixes by weight with zeolite
Than for 0.1 ~ 10：1.
3. according to the method described in claim 1, it is characterized in that：In the first step carry out hydro-thermal process when system in PH2O/ P is
0.2 ~ 0.9, it is preferably 0.3 ~ 0.8, PNH3/ P is 0.1 ~ 0.8, is preferably 0.2 ~ 0.7.
4. according to the method described in claim 1, it is characterized in that：H in buffer solution in the first step+It is provided by acid, NH4 +By ammonium
Salt provides, and the pH of buffer solution is 4 ~ 6.
5. according to the method described in claim 1, it is characterized in that：It is dense using dust technology when alumina modified in second step
It spends for 0.05 ~ 0.5M, the dust technology dosage per 100g aluminium oxide is 100 ~ 300mL.
6. according to the method described in claim 1, it is characterized in that：Non-noble metal hydrogenation component described in 4th step be selected from Ni,
W, at least one of Mo and Co, the noble metal hydrogenating component are selected from least one of Ru, Rh, Pd, Os, Ir and Pt, with
The mass content meter of metallic element in the catalyst, the loading of the non-noble metal hydrogenation component is 0.5% ~ 10.0%, described
The loading of noble metal hydrogenating component is 0.1% ~ 2.0%.
7. according to the method described in claim 1, it is characterized in that：The actual conditions of the reduction of hydrogen partial pressure described in 5th step
For：Temperature is 420 ~ 550 DEG C, 0.01 ~ 2.00Mpa of pressure；Mixed gas and catalyst by volume 100 ~ 1500：1, mixing connects
It touches, when the recovery time is 1 ~ 96 small.
8. hydrocatalyst for saturating prepared by the method described in claim 1 ~ 7 any one.
9. arylhydrocarbon in diesel oil is hydrogenated with saturation process, the hydrogenation saturation described in the diesel oil distillate containing aromatic hydrocarbons and claim 8 is catalyzed
Agent contacts.
10. arylhydrocarbon in diesel oil according to claim 9 is hydrogenated with saturation process, it is characterised in that：The operating condition of hydrogenation process
It reacts and is：2 ~ 15MPa of pressure, 200 ~ 400 DEG C of reaction temperature, 0.5 ~ 5.0h of volume space velocity during reaction solution-1, react hydrogen to oil volume ratio
For 500 ~ 1800.
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