CN104667984B - A kind of catalyst for hydro-upgrading carrier and preparation method thereof - Google Patents
A kind of catalyst for hydro-upgrading carrier and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of catalyst for hydro-upgrading carrier and preparation method.The catalyst carrier includes beta-molecular sieve and aluminum oxide, wherein the property of beta-molecular sieve used is as follows：Specific surface area is 400m2/g~800m2/ g, total pore volume is 0.4ml/g ~ 0.55mL/g, SiO2/Al2O3Mol ratio is 30 ~ 60, and relative crystallinity is 120% ~ 140%, and meleic acid amount is 0.55 ~ 1.0mmol/g, and non-framework aluminum accounts for less than 1%, NH of total aluminium3The acid amount for the middle strong acid that TPD methods are measured accounts for 70% ~ 85%, Na of total acid content2O≤0.15wt%.Preparation method includes：Beta-molecular sieve and aluminum oxide kneading and compacting are prepared into carrier.Catalyst carrier of the present invention be by silica alumina ratio is suitable, bigger serface, acid suitable, pore structure rationally and the low beta-molecular sieve of non-framework aluminum content is as Cracking Component, the catalyst being made from it is especially suitable as during the hydro-upgrading of bad diesel oil processed, diesel product yield height and good product quality.
Description
Technical field
The present invention relates to a kind of catalyst for hydro-upgrading carrier and preparation method thereof, particularly a kind of poor ignition quality fuel hydrogenation changes
Matter catalyst carrier and preparation method thereof.
Background technology
Due to the advantage in Diesel engine performance and its widely use, so the demand to diesel oil is very vigorous always.
In addition, to protect ecological environment for the survival of mankind, the quality to diesel product it is also proposed higher requirement.《Fire in the world
Fuel oil meter model》From II class standards, just the indexs such as the sulphur and arene content in diesel oil, Cetane number, density, T95 are proposed more
Plus strict requirements.
The diesel oil produced at present mainly has straight-run diesel oil and secondary processing diesel oil.Produce the main path of secondary processing diesel oil
There is catalytic cracking, be hydrocracked and delayed coking.Due to the raising of clean fuel standards, catalytic diesel oil inferior is caused（Especially
Heavy MIP diesel oil）Index request can not have been met with coker gas oil, it is necessary to which further hydro-upgrading can dispatch from the factory.How to use
Alap investment and operating cost, the friendly fuel oil for vehicles of production environment, it has also become oil refining enterprise's problem urgently to be resolved hurrily.
For cleaning diesel production, prior art mainly includes the technologies such as hydrofinishing and MHUG.Hydrogenation essence
System can effectively reduce the sulfur content of modification diesel oil, but limited to improving Cetane number and reduction T95 temperature capabilities.Medium pressure hydrogenation changes
Matter is to utilize suitably to crack diesel oil under conditions of middle pressure, the naphtha and wide cut diesel fuel of generating portion, and middle pressure at present
Cracking Component employed in diesel modifying catalyst is mainly modified Y type molecular sieve, because Y type molecular sieve has ten binary
The supercage structure of ring so that the dry gas amount amount of existing diesel modifying catalyst is big, the yield of diesel product is low, Cetane number is improved
The shortcomings of amplitude is small, T95 points reclaim high small, condensation point and big density.Such as, CN1184843A and CN101463271A.
CN1184843A discloses a kind of catalyst for hydrocracking diesel oil, and the composition of the catalyst is 40 ~ 80wt% of aluminum oxide, unformed
0 ~ 20wt% of sial, 5 ~ 30wt% of molecular sieve, described molecular sieve is 0.4 ~ 0.52mL/g of pore volume, 750 ~ 900m of specific surface area2/ g,
2.420 ~ 2.500nm of lattice constant, silica alumina ratio is 7 ~ 15 Y type molecular sieve.
CN101463271A discloses a kind of catalyst for hydro-upgrading of inferior diesel and preparation method thereof, mainly using oxygen
SiClx-aluminum oxide, the predecessor of aluminum oxide and/or aluminum oxide and Y type molecular sieve mixing, shaping and roasting, afterwards in shaping species
Introduce the hydrogenation metal of effective dose.Above-mentioned catalyst has higher desulfurization and denitrification activity, but the yield of diesel product is low, bavin
The Cetane number of oil improve amplitude is small, high condensation point and the shortcomings of big density.
The key component for being applied to play cracking in modifying catalyst at present is generally Y type molecular sieve and beta-molecular sieve.Relatively
In Y type molecular sieve, beta-molecular sieve has three-dimensional twelve-ring pore structure, but no supercage structure as Y type molecular sieve, its
Double 6 yuan of rings unit bug hole structures of two 4 yuan of rings and four 5 yuan of rings are mainly characterized by, belong to cubic system, main channel diameter exists
0.56-0.75nm.There is beta-molecular sieve topological structure and stereoscopic three-dimensional duct feature to cause it in cracking reaction to chain hydrocarbon
Selectivity fracture has effect well, and with very strong isomery performance, can be used for as cracking component in Low Freezing Point
Between oil distillate, be industrially widely used.
The various and complexity of beta-molecular sieve silicon-aluminum structure.The skeleton structure of beta-molecular sieve is more multiple compared to Y type molecular sieve
Miscellaneous, two linear channels are mutually orthogonal and perpendicular to [001] direction in three cross one another pore canal systems, and pore size is
The nm of 0.57 nm × 0.75, the 3rd twelve-ring pore canal system, parallel to [001] direction, is non-linear channels, pore size
For the nm of 0.56 nm × 0.65；The complete beta-molecular sieve framework silicon-aluminum structure of crystallization is there is also diversity, and framework silicon-aluminum structure is four
Coordination structure and this structure account for the main body of sial existence form total in molecular sieve, also exist a small amount of six in molecular sieve in addition
The non-framework aluminum of coordination；In follow-up different modifying process different changes occur for these various sial existing ways and content
Change, so that different catalytic performances will be produced.
A kind of method of modifying of beta-molecular sieve is disclosed in CN101450318A.This method is by sodium form beta-molecular sieve and ammonium salt
Exchange, then the solution with phosphorus-containing compound solution and containing transistion metal compound carries out dipping modification, obtained β to molecular sieve
Molecular sieve has the relative crystallinity of higher specific surface area and Geng Gao, further can generate low-carbon alkene by shape slective cracking.
EP95304, EP488867, US4554065 disclose beta-molecular sieve method of modifying, are mainly removed using three sections of alternating temperatures
Remove template（De- ammonium process）, then by certain density acid（Inorganic acid）Processing, acid treatment process can be by molecular sieve
The abjection of part framework aluminum, obtained modified beta molecular sieve has higher silica alumina ratio.The standby modified molecules sifter device of these patent systems
There is poor acid to be distributed and calculate density, prepared catalyst has poor purpose product selectivity and general product matter
Amount.
CN1362362A discloses a kind of method of modifying of beta-molecular sieve.This method process is as follows：（1）Complete β points of crystallization
Son sieve directly carries out ammonium salt exchange；（2）Beta-molecular sieve after ammonium salt is exchanged is filtered, washed, being dried and is calcined；（3）Roasting is de-
Beta-molecular sieve after ammonium carries out acid treatment, filtering, and the acid used is generally inorganic acid, can be nitric acid, hydrochloric acid or sulfuric acid etc.；
（4）The complete beta-molecular sieve of acid treatment carries out pressurized thermal water processing.In this method, acid treatment first is carried out to β zeolites, then carried out again
Hydro-thermal process, is to use mineral acid treatment during acid treatment, due to using inorganic acid concentration higher, in this course
The skeleton structure of moieties sieve will be destroyed, molecular sieve crystallinity declines, and the non-skeleton structure for forming bulk stays in molecular sieve
In duct, it is difficult to be removed, the acid distribution of influence modified molecular screen and acid strength, in addition, also having carried out high temperature after acid treatment
Hydro-thermal process, can also form a certain amount of non-framework aluminum in molecular sieve, and these non-framework aluminum structures will block molecular sieve pore passage,
And the acid site in part mask molecule sieve skeleton structure, this will directly affect the pore structure and Acidity of molecular sieve, molecule
The acid distribution and the change of Acidity of sieve will directly affect the performance of thus molecular sieve as the catalyst of Cracking Component, especially
The yield and product property of influence modification diesel oil.
The content of the invention
In order to overcome weak point of the prior art, the invention provides a kind of catalyst for hydro-upgrading carrier and its system
Preparation Method.The catalyst for hydro-upgrading carrier uses a kind of suitable silica alumina ratio, bigger serface, acid suitable, pore structure reasonable
Low beta-molecular sieve is as main modification Cracking Component with non-framework aluminum content, and the catalyst prepared by carrier of the present invention has bavin
The features such as oil product high income and good product quality.
Catalyst for hydro-upgrading carrier of the present invention, comprising beta-molecular sieve and aluminum oxide, wherein described beta-molecular sieve, its property
It is as follows：Specific surface area is 400m2/g~800m2/ g, preferably 500 ~ 750m2/ g, total pore volume is 0.4ml/g ~ 0.55mL/g,
SiO2/Al2O3Mol ratio be 30 ~ 60, preferably 35 ~ 55, relative crystallinity be 120% ~ 140%, meleic acid amount be 0.55 ~
1.0mmol/g, non-framework aluminum accounts for less than 1%, NH of total aluminium3The middle strong acid that-TPD methods are measured acid amount account for total acid content 70% ~
85%, preferably 75% ~ 85%, Na2O≤0.15wt%, is preferably≤0.10wt%.
In the beta-molecular sieve of the present invention, total aluminium refers to the summation of the aluminium in aluminium and non-framework aluminum in molecular sieve middle skeleton aluminium.
Non-framework aluminum refers to the aluminium existed in molecular sieve with hexa-coordinate structure type.Framework aluminum refers in molecular sieve with four-coordination structure shape
The aluminium that formula is present.
Described catalyst for hydro-upgrading carrier, on the basis of the weight of carrier, the content of beta-molecular sieve is 5% ~ 40%, oxygen
The content for changing aluminium is 60% ~ 95%.
The specific surface area of catalyst for hydro-upgrading carrier of the present invention is 300 ~ 500m2/ g, pore volume is 0.5 ~ 1.0mL/g.
The preparation method of diesel oil hydrogenation modification catalyst carrier of the present invention, including：
By beta-molecular sieve and aluminum oxide mechanical mixture, shaping, then dry and be calcined, catalyst carrier is made；It is wherein described
Beta-molecular sieve use following method and step：
（1）The former powder of beta-molecular sieve is handled under the conditions of normal pressure, dynamic water vapour, treatment temperature is 500 ~ 650
DEG C, processing time is 5 ~ 10 hours；
（2）With highly basic weak solution process step（1）The beta-molecular sieve of gained, then filters, washes and dries, obtain beta molecule
Sieve.
Step（1）Beta-molecular sieve original powder is synthesized using hydrothermal crystallization method, its SiO2/Al2O3Mol ratio 20.0 ~ 25.0,
Na2O content is less than 0.2wt%.
Step（1）Beta-molecular sieve original powder can typically be steamed in normal pressure, the processing of dynamic water vapour condition using the water of flowing
Vapour is carried out, using 100wt% water vapours.Water vapour passes through beta-molecular sieve by every kilogram of 20 ~ 100L/h of beta-molecular sieve.
Step（2）In, in the highly basic weak solution, the concentration of diluted alkaline（With OH-Meter）0.01 ~ 0.2mol/L, preferably 0.02 ~
0.15mol/L.The highly basic weak solution can be added to the water using highly basic to be formulated, and highly basic can be lithium hydroxide, hydrogen-oxygen
Change the one or more in sodium, potassium hydroxide.Highly basic weak solution and the weight of beta-molecular sieve ratio are 5:1~20:1.Described processing
Condition：40 ~ 120 DEG C of temperature, preferably 70 ~ 100 DEG C, the time is 1.0 ~ 8.0 hours, preferably 2.0 ~ 4.0 hours.Described washing
Condition：50 ~ 90 DEG C of washing temperature, preferably 60 ~ 80, washing time 0.5 ~ 1.0 hour, until cleaning solution pH value close to neutrality is
Only, then dried 3 ~ 6 hours under conditions of 100 ~ 120 DEG C.
The inventive method is first using normal pressure, Dynamic Hydrothermal processing molecular screen primary powder, in the effect of dynamic high temperature water vapour
Under can realize that molecular sieve takes off ammonium（Template removal）Framework aluminum activation energy is reduced with selectivity, and is avoided to framework of molecular sieve knot
The destruction of structure, and the homogeneity of framework of molecular sieve structure is kept, it is engaged with follow-up highly basic weak solution modifying process, Neng Gouyou
Effect ground uniformly deviates from non-framework aluminum, forms unimpeded pore structure, and make a small amount of OH-Adsorb the skeleton structure in molecular sieve
On, be conducive to improving the acid strength and sour density of molecular sieve, be conducive to improving the isomery performance of catalyst.Relative to existing method
The method of middle use acid treatment and rear hydro-thermal process carries out the modification of molecular sieve, due to there is substantial amounts of H in strong acid acidization+
In the presence of that can be non-selectivity abjection to the framework aluminum in molecular sieve and non-framework aluminum structure, part non-framework aluminum knot can be both deviate from
Structure, can also deviate from part skeleton constructed of aluminium, framework of molecular sieve silicon-aluminum structure and acidic zeolite matter be had a strong impact on, in addition, in acid
High-temperature water heat treatment is carried out after change again, non-framework aluminum structure can be also produced again in this modification procedure, further influence
The Acidity of molecular sieve, a large amount of non-framework aluminum structures are present in the hole of Severe blockage molecular sieve in the duct of modified molecular sieve
Acid site in structure, but also meeting masked portion framework of molecular sieve, largely effects on the performance of modified molecular sieve, and then influence
To Cracking catalyst purpose product selectivity and product property.
The beta-molecular sieve that the present invention is selected has suitable cracking to make to long chain alkane and aromatic hydrocarbons, the long side chain n- alkyl of cycloalkane
With with very strong isomerization, enable catalyst for hydro-upgrading prepared therefrom while high diesel yield is kept, larger amplitude
The condensation point of degree reduction diesel oil distillate, reaches the effect of volume increase low-coagulation diesel oil.
When being used for poor ignition quality fuel modification as the catalyst prepared by catalyst for hydro-upgrading carrier of the present invention, particularly in
Press strip part（4~12MPa）With processing poor ignition quality fuel（Heavy MIP diesel oil and coker gas oil）With very high catalytic activity and diesel oil
Yield, and the condensation point reduction amplitude of diesel oil distillate is big, improves the Cetane number of modification diesel oil by a relatively large margin, diesel product it is close
Degree is effectively reduced, and can be met refinery's increase operating flexibility, increase device disposal ability, further be increased high-quality production diesel oil
Need.
Embodiment
Aluminum oxide can use oxygen used in conventional hydro modifying catalyst in catalyst for hydro-upgrading carrier of the present invention
Change aluminium, such as macroporous aluminium oxide and ∕ or small porous aluminum oxide.0.7 ~ 1.0mL/g of pore volume of macroporous aluminium oxide used, specific surface area
200~500m2/g.The pore volume of small porous aluminum oxide used is 0.3 ~ 0.5mL/g, and specific surface area is 200 ~ 400m2/g。
Conventional shaping assistant such as peptization acid, extrusion aid can also be added in catalyst carrier preparation process of the present invention
Deng.
Beta-molecular sieve in catalyst for hydro-upgrading carrier of the present invention, specific preparation method is as follows：
（1）The former powder of beta-molecular sieve is handled under the conditions of normal pressure, dynamic water vapour, treatment temperature is 500 ~ 650
DEG C, processing time is 5 ~ 10 hours；
The former powder of beta-molecular sieve that the present invention is synthesized using hydrothermal crystallizing.The chemical SiO of the former powder of used beta-molecular sieve2/Al2O3
Mol ratio 20.0 ~ 25.0, Na2O content is less than 0.2wt%, relative crystallinity more than 95%；
The hydrothermal conditions used in the present invention are that water vapour is 100wt% water vapours, and water vapour is by every kilogram of beta molecule
20 ~ 100L/h of sieve passes through beta-molecular sieve.In order that molecular sieve processing is evenly, preferably molecular sieve is placed in rotary container, water
Steam is passed into from one end of container and gone out again from the other end of container after molecular sieve.Pressure in container keeps normal pressure shape
State, treatment temperature is maintained at 500 ~ 650 DEG C, and processing time is 5 ~ 10 hours；
In the inventive method, beta-molecular sieve original powder is placed in container such as tube furnace, and using temperature programming, heating rate is
50 ~ 150 DEG C/h, when being preferably raised to 250 ~ 450 DEG C, further preferably start to introduce water vapour at 250 ~ 400 DEG C, then
500 ~ 650 DEG C are warming up to while water vapour is introduced, and is handled 5 ~ 10 hours at this temperature；
（2）With highly basic weak solution process step（3）The beta-molecular sieve of gained, then filters, washes and dries；
Highly basic weak solution, wherein highly basic weak solution concentration are added in return-flow system and closed container（With OH-
Meter）0.01 ~ 0.2mol/L, preferably 0.02 ~ 0.15mol/L, stir and are warming up to 40 ~ 120 DEG C, preferably 70 ~ 100 DEG C, then
It is 5 by highly basic weak solution and the weight of molecular sieve ratio:1~20:1, add step（3）The molecular sieve of acquisition, constant temperature stirring 1.0 ~
8.0 hours, preferably 2.0 ~ 4.0 hours, filtering, washing were washed untill cleaning solution pH value is close to neutrality, and 100 ~ 120
Dried 3 ~ 6 hours under conditions of DEG C, obtain the beta-molecular sieve of the present invention.Wherein highly basic weak solution can be lithium hydroxide, hydroxide
One or more aqueous solution in sodium, potassium hydroxide.
Detailed process prepared by catalyst for hydro-upgrading carrier of the present invention is：
Modified beta molecular sieve, aluminum oxide and adhesive are mixed, then extruded moulding is dried and is calcined, and is prepared into load
Body, described drying can be carried out 3 ~ 6 hours at a temperature of 80 DEG C to 150 DEG C, roasting be 500 DEG C ~ 600 DEG C be calcined 2.5 ~
6 hours.
, can be using load side conventional in the prior art when modifying catalyst carrier of the present invention is used to prepare modifying catalyst
Method, preferably infusion process, can be saturation leaching, excessive leaching or complexing leaching.
The following examples are used to the present invention is described in more detail, but the scope of the present invention is not limited solely to these embodiments
Scope.In the present invention, wt% is mass fraction.
Analysis method of the present invention：Specific surface area and pore volume use low temperature liquid nitrogen physisorphtion, silica alumina ratio useization
Method, meleic acid amount uses Pyridine adsorption IR spectra method, and the acid amount and total acid content of middle strong acid are by NH3- TPD methods are determined（It is logical
Cross NH3- TPD methods are determined：150 ~ 250 DEG C of corresponding acid are weak acid, and 250 ~ 400 DEG C of corresponding acid are middle strong acid, 400 ~ 500 DEG C
Corresponding acid is strong acid；Weak acid, middle strong acid and strong acid are sour measuring and are total acid content）, sodium content uses plasma emission spectrometry,
Relative crystallinity is determined using XRD method.
In the present invention, using nuclear magnetic resonance spectroscopy（NMR methods）Measure27Al MAS NMR spectras, so as to obtain framework aluminum
And the ratio of non-framework aluminum, in terms of aluminium atom.Nuclear magnetic resonance spectroscopy（NMR methods）It is to use Bruker AVANCE III 500
Type nuclear magnetic resonance spectrometer, wherein software use Topspin 2.0.Surveying27During Al MAS NMR spectras, accepted standard material is
Alchlor, resonant frequency is 133MHz, experiment condition：4-6 microsecond pulse widths, 60-120 seconds relaxation delays.Gained27Al
In MAS NMR spectras, the corresponding chemical shift of framework aluminum be 40 ~ 65ppm, the corresponding chemical shift of non-framework aluminum be -10 ~
10ppm。
Embodiment 1
Take the former powder about 3500g, its chemical sial SiO of beta-molecular sieve2/Al2O3（Mol ratio）Than for 22.68, sodium oxide content
For 0.18wt%.Beta-molecular sieve is fitted into tube furnace, using the method for temperature programming（Heating rate is 100 DEG C/h）, in pipe
Formula furnace temperature starts to introduce 100wt% water vapour when being raised to 300 DEG C, and water vapour passes through beta molecule by every kilogram of beta-molecular sieve 40L/h
Sieve, by diamond heating to 550 DEG C, constant temperature time is 8 hours.Gained molecular sieve numbering is BH-1, and property is shown in Table 1.
Embodiment 2
Take the former powder about 3500g of beta-molecular sieve, be the same as Example 1.Molecular sieve is fitted into tube furnace, using the side of temperature programming
Method（Heating rate is 100 DEG C/h）, start to introduce 100wt% water vapour, water vapour when tubular type furnace temperature is raised to 300 DEG C
By every kilogram of beta-molecular sieve 70L/h by beta-molecular sieve, by diamond heating to 620 DEG C, constant temperature time is 8 hours.Gained molecule
It is BH-2 to sieve numbering, and property is shown in Table 1.
Embodiment 3
50g BH-1 molecular sieves are weighed to be put into reflux and concentration 0.04mol/ can be added with closed flask
L NaOH aqueous solution 400ml, the NaOH aqueous solution and the weight ratio of BH-1 molecular sieves are 8：1, constant temperature stirring 2.0 is small at 95 DEG C
When, filtering, and filter cake is washed with hot deionized water, stop washing close to after 7 with the pH value of cleaning solution.Filter cake in an oven 120
DEG C dry 5 hours, obtain the beta molecular sieve of the present invention, its numbering BJ-1, molecular sieve property is shown in Table 1.
Embodiment 4
50g BH-1 molecular sieves are weighed to be put into reflux and concentration 0.1mol/L can be added with closed flask
NaOH aqueous solution 700ml, the NaOH aqueous solution and the weight ratio of BH-1 molecular sieves are 14：1, constant temperature is stirred 2.5 hours at 90 DEG C,
Filtering, and filter cake is washed with hot deionized water, stop washing close to after 7 with the pH value of cleaning solution.Filter cake is done for 120 DEG C in an oven
Dry 5 hours.The beta molecular sieve of the present invention is obtained, its numbering BJ-2, molecular sieve property is shown in Table 1.
Embodiment 5
50g BH-2 molecular sieves are weighed to be put into reflux and concentration 0.15mol/ can be added with closed flask
L KOH aqueous solution 1000ml, the KOH aqueous solution and the weight ratio of BH-2 molecular sieves are 20：1, constant temperature stirring 2.0 is small at 80 DEG C
When, filtering, and filter cake is washed with hot deionized water, stop washing close to after 7 with the pH value of cleaning solution.Filter cake in an oven 120
DEG C dry 5 hours, obtain the beta molecular sieve of the present invention, its numbering BJ-3, molecular sieve property is shown in Table 1.
Embodiment 6
50g BH-2 molecular sieves are weighed to be put into reflux and concentration 0.06mol/ can be added with closed flask
(NaOH+KOH, the two molar ratio is 1 to L：1) aqueous solution 300ml, NaOH and the KOH aqueous solution and the weight ratio of BH-2 molecular sieves
For 6：1, constant temperature is stirred 3.0 hours at 90 DEG C, and filtering and washs filter cake with hot deionized water, with the pH value of cleaning solution close to 7
Stop washing afterwards.Filter cake 120 DEG C of dryings 5 hours in an oven, obtain the beta molecular sieve of the present invention, its numbering BJ-4, molecular sieve
Property is shown in Table 1.
Comparative example 1
Modified molecular screen is prepared using the method in CN01106042.5.Gained molecular sieve is BD-1, and property is shown in Table 1, tool
Body process is as follows：
（1）Molecular screen primary powder 300g in Example 1, with 2.0M ammonium nitrate solutions using liquid-solid ratio as 10:1 is handed over
Change, be warming up to 90 ~ 95 DEG C, constant temperature is stirred 2 hours, is then cooled to 50 ~ 60 DEG C of filterings, wet cake carries out second of exchange again,
Condition is with for the first time.
（2）The beta-molecular sieve exchanged through ammonium salt twice, washing reaches 6 to pH, is then placed in drying box, 110 DEG C of dryings 6
Hour；
（3）Dried beta-molecular sieve, which was put into muffle furnace in 1 hour, is warming up to 250 DEG C, and constant temperature 2 hours is then proceeded to
It was warming up to 400 DEG C in 1 hour, then constant temperature 4 hours, 540 DEG C are finally warming up to, constant temperature 10 hours, material all burns white, carbon residue
≤0.2%；
（4）High-temperature roasting take off ammonium beta-molecular sieve it is size-reduced, sieving, weigh 400g, add 0.4M HCl 4000ml, stirring
80 DEG C are warming up to, constant temperature is stirred 2 hours, cold filtration washing.
（5）Beta-molecular sieve filtration washing through acid treatment, is then dried 6 hours, butt is 85% at 110 DEG C.
（6）The sample of above-mentioned drying is placed in closed hydro-thermal process stove, 0.4 is uniformly sprayed（Kg water/kg drying samples）
Water purification, it is then closed, heating, control pressure 300KPa, 600 DEG C of temperature, programming rate be 500 DEG C/h, constant temperature and pressure roasting
Burn 3 hours, then Temperature fall, that is, obtain comparative example modified molecular screen.
Comparative example 2
（1）Take commercial synthesis SiO2/Al2O3 24.35, Na2Slurries during O 3.75wt% Na beta-molecular sieves after crystallization
1000ml, 300g containing solid phase（In terms of butt）, 2M ammonium chloride solution 2000mL are added, stirs, be warming up to 95 DEG C, constant temperature stirring 2
Hour, 60 DEG C of filterings are then cooled to, wet cake carries out second of exchange again, and condition is with for the first time；
（2）The beta-molecular sieve exchanged through ammonium salt twice, washing reaches 6 to pH, is then placed in drying box, 110 DEG C of dryings 6
Hour；
（3）Dried beta-molecular sieve, which was put into muffle furnace in 1 hour, is warming up to 250 DEG C, and constant temperature 2 hours is then proceeded to
It was warming up to 400 DEG C in 1 hour, then constant temperature 4 hours, 540 DEG C are finally warming up to, constant temperature 10 hours, material all burns white, carbon residue
≤0.2%；
（4）Beta-molecular sieve is put into reflux and can add concentration 0.04mol/L NaOH water with closed flask
Solution 400ml, the NaOH aqueous solution and the solvent and solute weight ratio of molecular sieve are 8：1, constant temperature is stirred 2.0 hours at 95 DEG C, filtering, and
Filter cake is washed with hot deionized water, stops washing close to after 7 with the pH value of cleaning solution.120 DEG C of dryings 5 are small in an oven for filter cake
When, beta-molecular sieve is obtained, its numbering BD-2, molecular sieve property is shown in Table 1.
Comparative example 3
Using the former powder be the same as Example 1 of beta-molecular sieve.Above-mentioned molecular sieve 1000g is taken, is fitted into closed hydro-thermal process stove, is used
The method of temperature programming（Heating rate is 100 DEG C/h）, 620 DEG C of hydro-thermal process temperature, hydro-thermal process pressure is 0.2MPa.
Alkali process is being carried out using raw material, is using concentration to be handled for 0.04mol/L NaOH solution, the liquid of NaOH solution and molecular sieve is consolidated
Weight ratio is 8：1, treatment temperature is 95 DEG C, and processing time is 2.0 hours, and after constant temperature terminates, slurries are filtered, and gone with heat from
Sub- water washing filter cake, stops washing with the pH value of cleaning solution close to after 7.120 DEG C of dryings 5 hours, obtain beta molecule in an oven
Sieve, numbering is BD-3, and physico-chemical property is listed in table 1.
The property of molecular sieve obtained by the embodiment of table 1 and comparative example
Continued 1
Embodiment 7
By 33.3 grams of BJ-1 molecular sieves（Butt 90wt%）, 200.0 grams of macroporous aluminium oxides（Pore volume 1.0mL/g, specific surface area
400m2/ g, butt 70wt%）, 133.3 grams of adhesives（The mol ratio of butt 30wt%, nitric acid and small porous aluminum oxide is 0.4）It is put into
Mixed grind in roller, adds water, and is rolled into paste, extrusion, extrusion bar is dried 4 hours at 110 DEG C, then small in 550 DEG C of roastings 4
When, carrier GS-1 is obtained, property is shown in Table 2.
Embodiment 8
By 44.4 grams of BJ-1 molecular sieves（Butt 90wt%）, 171.4 grams of macroporous aluminium oxides（Pore volume 1.0mL/g, specific surface area
400m2/ g, butt 70wt%）, 133.3 grams of adhesives（The mol ratio of butt 30wt%, nitric acid and small porous aluminum oxide is 0.4）It is put into
Mixed grind in roller, adds water, and is rolled into paste, extrusion, extrusion bar is dried 4 hours at 110 DEG C, then small in 550 DEG C of roastings 4
When, carrier GS-2 is obtained, property is shown in Table 2.
The maceration extract room temperature immersion of carrier tungstenic and nickel 2 hours, 120 DEG C of dryings 4 hours, 500 DEG C of roastings 4 of temperature programming
Hour, catalyst FC-2 is obtained, carrier and corresponding catalyst property are shown in Table 2.
Embodiment 9
By 66.6 grams of BJ-3 molecular sieves（Butt 90wt%）, 142.9 grams of macroporous aluminium oxides（Pore volume 1.0mL/g, specific surface area
400m2/ g, butt 70wt%）, 133.3 grams of adhesives（The mol ratio of butt 30wt%, nitric acid and small porous aluminum oxide is 0.4）It is put into
Mixed grind in roller, adds water, and is rolled into paste, extrusion, extrusion bar is dried 4 hours at 110 DEG C, then small in 550 DEG C of roastings 4
When, carrier GS-3 is obtained, property is shown in Table 2.
Embodiment 10
By 77.8 grams of BJ-3 molecular sieves（Butt 90wt%）, 128.6 grams of macroporous aluminium oxides（Pore volume 1.0mL/g, specific surface area
400m2/ g, butt 70wt%）, 133.3 grams of adhesives（The mol ratio of butt 30wt%, nitric acid and small porous aluminum oxide is 0.4）It is put into
Mixed grind in roller, adds water, and is rolled into paste, extrusion, extrusion bar is dried 4 hours at 110 DEG C, then small in 550 DEG C of roastings 4
When, carrier GS-4 is obtained, property is shown in Table 2.
Comparative example 4
By 44.4 grams of BD-1 molecular sieves（Butt 90wt%）, 171.4 grams of macroporous aluminium oxides（Pore volume 1.0mL/g, specific surface area
400m2/ g, butt 70wt%）, 133.3 grams of adhesives（The mol ratio of butt 30wt%, nitric acid and small porous aluminum oxide is 0.4）It is put into
Mixed grind in roller, adds water, and is rolled into paste, extrusion, extrusion bar is dried 4 hours at 110 DEG C, then small in 550 DEG C of roastings 4
When, carrier DGS-1 is obtained, property is shown in Table 2.
The maceration extract room temperature immersion of carrier tungstenic and nickel 2 hours, 120 DEG C of dryings 4 hours, 500 DEG C of roastings 4 of temperature programming
Hour, catalyst FCD-1 is obtained, carrier and corresponding catalyst property are shown in Table 2.
Comparative example 5
By 66.6 grams of BD-3 molecular sieves（Butt 90wt%）, 142.9 grams of macroporous aluminium oxides（Pore volume 1.0mL/g, specific surface area
400m2/ g, butt 70wt%）, 133.3 grams of adhesives（The mol ratio of butt 30wt%, nitric acid and small porous aluminum oxide is 0.4）It is put into
Mixed grind in roller, adds water, and is rolled into paste, extrusion, extrusion bar is dried 4 hours at 110 DEG C, then small in 550 DEG C of roastings 4
When, carrier DGS-2 is obtained, property is shown in Table 2.
The maceration extract room temperature immersion of carrier tungstenic and nickel 2 hours, 120 DEG C of dryings 4 hours, 500 DEG C of roastings 4 of temperature programming
Hour, catalyst FCD-2 is obtained, carrier and corresponding catalyst property are shown in Table 2.
Embodiment 11
This embodiment describes the catalyst activity evaluation result prepared by carrier of the present invention.In fixed bed hydrogenation experiment
Evaluated on device, appreciation condition is：React stagnation pressure 10.0MPa, hydrogen to oil volume ratio 700：1, volume space velocity 2.0h during liquid-1,
Using catalytic diesel oil as feedstock oil, raw material oil nature is listed in table 3.By catalyst FC-2, FCD-1 and FCD-2 in identical work
Evaluated under the conditions of skill, obtained evaluation result is listed in table 4.
Carrier prepared catalyst of the present invention is under identical process conditions it can be seen from evaluation result, diesel yield
Reference catalyst is superior to product quality.
The physico-chemical property of the catalyst carrier of table 2 and catalyst
| Embodiment 7 | Embodiment 8 | Embodiment 9 | Embodiment 10 | Comparative example 4 | Comparative example 5 | |
| Carrier is constituted and property | ||||||
| Numbering | GS-1 | GS-2 | GS-3 | GS-4 | DGS-1 | DGS-2 |
| Beta-molecular sieve, wt% | 15 | 20 | 30 | 35 | 20 | 30 |
| Aluminum oxide, wt% | Surplus | Surplus | Surplus | Surplus | Surplus | Surplus |
| Specific surface area, m2/g | 435 | 403 | 447 | 453 | 356 | 408 |
| Pore volume, mL/g | 0.69 | 0.64 | 0.56 | 0.55 | 0.51 | 0.47 |
| Catalyst is constituted and property | ||||||
| Numbering | FC-2 | FCD-1 | FCD-2 | |||
| WO3, wt% | 24.5 | 24.7 | 22.1 | |||
| NiO, wt% | 5.9 | 6.1 | 5.8 |
The raw material oil nature of table 3
| Feedstock oil | MIP catalytic diesel oils |
| Density (20 DEG C), g/cm3 | 0.9537 |
| Boiling range/DEG C | |
| IBP/10% | 200/234 |
| 30%/50% | 256/277 |
| 70%/90% | 305/348 |
| 95%/EBP | 363/367 |
| Condensation point, DEG C | 5 |
| Sulphur, μ g/g | 8568 |
| Nitrogen, μ g/g | 1150 |
| Cetane number | <20.0 |
| C, wt% | 88.49 |
| H, wt% | 11.04 |
Table 4 FC-2, FCD-1 and FCD-1 catalyst performance comparative evaluation's result
| Catalyst | FC-2 | FCD-1 | FCD-2 |
| Feedstock oil | MIP catalytic diesel oils | MIP catalytic diesel oils | MIP catalytic diesel oils |
| Volume space velocity during liquid, h-1 | 2.0 | 2.0 | 2.0 |
| React stagnation pressure, MPa | 10.0 | 10.0 | 10.0 |
| Hydrogen to oil volume ratio | 700:1 | 700:1 | 700:1 |
| Reaction temperature, DEG C | 365 | 373 | 371 |
| Product yield and property | |||
| Naphtha | |||
| Yield, wt% | 2.0 | 3.6 | 3.5 |
| Virtue is latent, wt% | 58.6 | 51.3 | 50.4 |
| Diesel oil | |||
| Yield, wt% | 96.8 | 93.2 | 92.1 |
| Density (20 DEG C)/g.cm-3 | 0.8353 | 0.8375 | 0.8377 |
| T95, DEG C | 345 | 353 | 354 |
| Condensation point, DEG C | -25 | -14 | -12 |
| Cetane number | 39.8 | 31.6 | 32.1 |
| Sulphur, μ g/g | 6 | 15 | 17 |
| Liquid is received, wt% | 98.8 | 96.8 | 95.6 |
Claims (19)
1. a kind of catalyst for hydro-upgrading carrier, comprising beta-molecular sieve and aluminum oxide, the property of the beta-molecular sieve is as follows：Compare surface
Product is 400m2/g~800m2/ g, total pore volume is 0.4ml/g ~ 0.55mL/g, SiO2/Al2O3Mol ratio is 30 ~ 60, relative crystallinity
For 120% ~ 140%, meleic acid amount is 0.55 ~ 1.0mmol/g, and non-framework aluminum accounts for less than 1%, NH of total aluminium3- TPD methods are measured
The acid amount of middle strong acid accounts for 70% ~ 85%, Na of total acid content2O≤0.15wt%。
2. according to the catalyst carrier described in claim 1, it is characterised in that the specific surface area of the beta-molecular sieve is 500 ~
750m2/ g, total pore volume is 0.4ml/g ~ 0.55mL/g.
3. according to the catalyst carrier described in claim 1, it is characterised in that the SiO of the beta-molecular sieve2/Al2O3Mol ratio is
35~55。
4. according to the catalyst carrier described in claim 1, it is characterised in that in the beta-molecular sieve, NH3- TPD methods are measured
The acid amount of middle strong acid accounts for the 75% ~ 85% of total acid content.
5. according to the catalyst carrier described in claim 1, it is characterised in that：Described catalyst for hydro-upgrading carrier, to carry
On the basis of the weight of body, the content of beta-molecular sieve is 5% ~ 40%, and the content of aluminum oxide is 60% ~ 95%.
6. according to the catalyst carrier described in claim 1, it is characterised in that：The specific surface area of described catalyst carrier is
300~500m2/ g, pore volume is 0.5 ~ 1.0mL/g.
7. the preparation method of any described catalyst carrier of claim 1 ~ 6, including：Beta-molecular sieve, aluminum oxide machinery is mixed
Close, then shaping is dried and be calcined, catalyst carrier is made；The wherein preparation method of beta-molecular sieve, including：
（1）The former powder of beta-molecular sieve is handled under the conditions of normal pressure, dynamic water vapour, treatment temperature is 500 ~ 650 DEG C, place
The reason time is 5 ~ 10 hours；
（2）With highly basic weak solution process step（1）The beta-molecular sieve of gained, then filters, washes and dries, obtain beta-molecular sieve,
Wherein, in the highly basic weak solution, the concentration of diluted alkaline is with OH-Count 0.01 ~ 0.2mol/L.
8. in accordance with the method for claim 7, it is characterised in that step（1）Beta-molecular sieve original mealiness matter is as follows：SiO2/Al2O3
Mol ratio 20.0 ~ 25.0, Na2O content is less than 0.2wt%.
9. in accordance with the method for claim 7, it is characterised in that step（1）Using the 100wt% steam treatments of flowing.
10. according to the method described in claim 7 or 9, it is characterised in that step（1）In, water vapour is by every kilogram of beta-molecular sieve 20
~ 100L/h passes through beta-molecular sieve.
11. according to the method described in claim 7 or 9, it is characterised in that step（1）In, step（1）In, beta-molecular sieve original powder is put
In container, using temperature programming, heating rate is 50 ~ 150 DEG C/h, when rising to 250 ~ 450 DEG C, starts to introduce water vapour,
Then 500 ~ 650 DEG C are warming up to while water vapour is introduced, and is handled 5 ~ 10 hours at this temperature.
12. in accordance with the method for claim 7, it is characterised in that the highly basic is lithium hydroxide, sodium hydroxide, potassium hydroxide
In one or more.
13. according to the method described in claim 7 or 12, it is characterised in that step（2）In, in the highly basic weak solution, diluted alkaline
Concentration with OH-Count 0.02 ~ 0.15mol/L.
14. in accordance with the method for claim 7, it is characterised in that the weight ratio of the highly basic weak solution and beta-molecular sieve is 5:1
~20:1。
15. in accordance with the method for claim 7, it is characterised in that step（2）Described treatment conditions：40 ~ 120 DEG C of temperature,
Time is 1.0 ~ 8.0 hours.
16. in accordance with the method for claim 7, it is characterised in that step（2）Described treatment conditions：70 ~ 100 DEG C of temperature,
Time is 2.0 ~ 4.0 hours.
17. in accordance with the method for claim 7, it is characterised in that step（2）Described drying is the condition at 100 ~ 120 DEG C
Lower drying 3 ~ 6 hours.
18. in accordance with the method for claim 7, it is characterised in that：The drying and roasting of carrier are as follows：At 100 DEG C ~ 150 DEG C
Dry 1 ~ 12 hour, be then calcined 2.5 ~ 6.0 hours at 450 DEG C ~ 550 DEG C.
19. in accordance with the method for claim 7, it is characterised in that：Described aluminum oxide is using macroporous aluminium oxide He ∕ or aperture
Aluminum oxide, the 0.7 ~ 1.0mL/g of pore volume, 200 ~ 500m of specific surface area of macroporous aluminium oxide used2/ g, small porous aluminum oxide used
Pore volume be 0.3 ~ 0.5mL/g, specific surface area be 200 ~ 400m2/g。
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| CN106669796B (en) * | 2015-11-10 | 2019-05-21 | 中国石油化工股份有限公司 | A kind of preparation method of catalyst for hydro-upgrading |
| CN106669797B (en) * | 2015-11-10 | 2019-06-11 | 中国石油化工股份有限公司 | A kind of preparation method of catalyst for hydro-upgrading |
| CN106669859B (en) * | 2015-11-10 | 2019-05-21 | 中国石油化工股份有限公司 | A kind of method of modifying of catalyst for hydro-upgrading carrier |
| CN106669848B (en) * | 2015-11-10 | 2019-06-11 | 中国石油化工股份有限公司 | A kind of method of modified catalyst for hydro-upgrading carrier |
| CN107344121B (en) * | 2016-05-05 | 2019-10-15 | 中国石油化工股份有限公司 | A kind of catalyst for hydro-upgrading carrier and preparation method thereof |
| CN108283942B (en) * | 2017-01-10 | 2021-07-30 | 中国石油化工股份有限公司 | Modified alpha-alumina carrier and preparation method thereof, silver catalyst and application |
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