CN104667984A - A catalyst carrier for hydrogenation modification and a preparing method thereof - Google Patents
A catalyst carrier for hydrogenation modification and a preparing method thereof Download PDFInfo
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Abstract
A catalyst carrier for hydrogenation modification and a preparing method thereof are disclosed. The catalyst carrier comprises a beta molecular sieve and aluminum oxide, wherein properties of the beta molecular sieve are as follows: the specific surface area is 400-800 m2/g, the total pore volume is 0.4-0.55 mL/g, the SiO2/Al2O3 mole ratio is 30-60, the relative crystallinity is 120-140%, the infrared acid content is 0.55-1.0 mmol/g, the non-framework aluminum accounts for less than 1% of the total aluminum, the amount of medium-strong acids which is measured by a NH3-TPD method accounts for 70-85% of the total acid amount, and the percent of Na2O is not more than 0.15 wt%. The preparing method includes mixing the beta molecular sieve and the aluminum oxide, kneading and forming to prepare the carrier. The beta molecular sieve which is proper in silicon aluminum ratio, large in specific surface area, proper in acidity, reasonable in pore structure and low in content of non-framework aluminum is adopted as a cracking component of the catalyst carrier. A catalyst prepared from the carrier is particularly suitable for hydrogenation modification processes of diesel oil with low quality, and diesel oil products are high in yield and good in 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 catalyst for hydro-upgrading of inferior diesel carrier and preparation method thereof.
Background technology
Due to the advantage in Diesel engine performance and widely use, so always very vigorous to the demand of diesel oil.In addition, be the ecological environment that the protection mankind depend on for existence, higher requirement be it is also proposed to the quality of diesel product." world's fuel oil specification ", from II class standard, just proposes stricter requirement to indexs such as the sulphur in diesel oil and arene content, Cetane number, density, T95.
The diesel oil of current production mainly contains straight-run diesel oil and secondary processing diesel oil.The main path producing secondary processing diesel oil has catalytic cracking, hydrocracking and delayed coking.Due to the raising of clean fuel standards, cause catalytic diesel oil inferior (especially heavy MIP diesel oil) and coker gas oil can not meet index request, need further hydro-upgrading to dispatch from the factory.How to use alap investment and operating cost, the fuel oil for vehicles of production environment close friend, become the problem that oil refining enterprise is urgently to be resolved hurrily.
Produce for clean diesel, prior art mainly comprises the technology such as hydrofinishing and MHUG.Hydrofinishing effectively can reduce the sulfur content of upgrading diesel oil, but limited to improving Cetane number and reducing T95 temperature capability.MHUG utilizes suitable for diesel oil cracking under the condition of middle pressure, the naphtha of generating portion and wide cut diesel fuel, and at present in the Y zeolite of the Cracking Component that adopts in pressure diesel modifying catalyst mainly modification, because Y zeolite has the supercage structure of twelve-ring, the shortcoming such as such that the amplitude that the dry gas amount amount of existing diesel modifying catalyst is large, the yield of diesel product is low, Cetane number improves is little, the recovery of T95 point is little, condensation point is high and density is large.Such as, CN1184843A and CN101463271A.CN1184843A discloses a kind of catalyst for hydrocracking diesel oil, this catalyst consist of aluminium oxide 40 ~ 80wt%, amorphous silicon aluminium 0 ~ 20wt%, molecular sieve 5 ~ 30wt%, described molecular sieve is pore volume 0.4 ~ 0.52mL/g, specific area 750 ~ 900m
2/ g, lattice constant 2.420 ~ 2.500nm, silica alumina ratio is the Y zeolite of 7 ~ 15.
CN101463271A discloses a kind of catalyst for hydro-upgrading of inferior diesel and preparation method thereof, mainly adopt the predecessor of silica-alumina, aluminium oxide and/or aluminium oxide and Y zeolite mixing, shaping and roasting, introduce the hydrogenation metal of effective dose afterwards at shaping species.Above-mentioned catalyst has higher desulfurization and denitrification activity, but the shortcoming such as the amplitude that the yield of diesel product is low, the Cetane number of diesel oil improves is little, condensation point is high and density is large.
Be applied in modifying catalyst the key component playing cracking at present and mostly be Y zeolite and beta-molecular sieve.Relative to Y zeolite, beta-molecular sieve has three-dimensional twelve-ring pore structure, but does not have the supercage structure as Y zeolite, and its main feature is two 6 ring unit bug hole structures of two 4 rings and four 5 rings, belong to cubic system, main channel diameter is at 0.56-0.75nm.Have topological structure and the stereoscopic three-dimensional duct feature of beta-molecular sieve make it in cracking reaction, have good effect to the fracture of chain hydrocarbon-selective, and there is very strong isomery performance, can be used for Low Freezing Point middle oil fraction as cracking component, be industrially widely used.
Various and the complexity of beta-molecular sieve silicon-aluminum structure.The skeleton structure of beta-molecular sieve is more complicated compared to Y zeolite, in three cross one another pore canal system, two linear channels are mutually orthogonal and perpendicular to [001] direction, pore size is 0.57 nm × 0.75 nm, 3rd twelve-ring pore canal system is parallel to [001] direction, be non-linear channels, pore size is 0.56 nm × 0.65 nm; Also there is diversity in crystallization completely beta-molecular sieve framework silicon-aluminum structure, framework silicon-aluminum structure is four-coordination structure and this structure accounts for the main body of sial existence form total in molecular sieve, also there is the non-framework aluminum of a small amount of hexa-coordinate in addition in molecular sieve; There is different changes in these various sial existing waies and content, thus will produce different catalytic performances in follow-up different modifying process.
A kind of method of modifying of beta-molecular sieve is disclosed in CN101450318A.The method is exchanged sodium form beta-molecular sieve and ammonium salt, with phosphorus-containing compound solution and the solution containing transistion metal compound, dipping modification is carried out to molecular sieve again, the beta-molecular sieve obtained has higher specific area and the relative crystallinity of Geng Gao, can generate low-carbon alkene by shape slective cracking further.
EP95304, EP488867, US4554065 disclose beta-molecular sieve method of modifying, mainly adopt three sections of alternating temperature removing templates (de-ammonium process), then process through certain density acid (inorganic acid), part framework aluminum in molecular sieve can be deviate from by acid treatment process, and the modified beta molecular sieve obtained has higher silica alumina ratio.The standby modified molecular screen of these patent systems has poor acid distribution and calculates density, and prepared catalyst has poor object product selectivity and general product quality.
CN1362362A discloses a kind of method of modifying of beta-molecular sieve.The method process is as follows: (1) crystallization completely beta-molecular sieve directly carries out ammonium salt exchange; (2) ammonium salt exchange after beta-molecular sieve carry out filtering, wash, dry and roasting; (3) beta-molecular sieve after roasting takes off ammonium carries out acid treatment, filtration, and the acid adopted is generally inorganic acid, can be nitric acid, hydrochloric acid or sulfuric acid etc.; (4) beta-molecular sieve that acid treatment is complete carries out pressurized thermal water process.In the method, first acid treatment is carried out to β zeolite, and then carry out hydrothermal treatment consists, adopt mineral acid treatment in acid treatment process, owing to adopting inorganic acid concentration higher, the skeleton structure of moieties sieve will be destroyed in this course, molecular sieve crystallinity declines, the non-skeleton structure forming bulk is stayed in molecular sieve pore passage, be difficult to be removed, affect acid distribution and the acid strength of modified molecular screen, in addition, also high-temperature water heat treatment has been carried out after acid treatment, also a certain amount of non-framework aluminum can be formed in molecular sieve, these non-framework aluminum structures will block molecular sieve pore passage, and the acid site on part mask molecule sieve skeleton shelf structure, this will directly affect pore structure and the Acidity of molecular sieve, the acid distribution of molecular sieve and the change of Acidity using directly affect thus molecular sieve as the performance of the catalyst of Cracking Component, especially output and the product property of upgrading diesel oil is affected.
Summary 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 preparation method thereof.This catalyst for hydro-upgrading carrier adopts that a kind of silica alumina ratio is suitable for, bigger serface, acid suitable, pore structure rationally and the low beta-molecular sieve of non-framework aluminum content as main upgrading Cracking Component, the catalyst prepared by carrier of the present invention has the features such as the high and good product quality of diesel product yield.
Catalyst for hydro-upgrading carrier of the present invention, comprises beta-molecular sieve and aluminium oxide, wherein said beta-molecular sieve, and its character is as follows: specific area is 400m
2/ g ~ 800m
2/ g, is preferably 500 ~ 750m
2/ g, total pore volume is 0.4ml/g ~ 0.55mL/g, SiO
2/ Al
2o
3mol ratio is 30 ~ 60, and be preferably 35 ~ 55, 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 aluminium
3the acid amount of the middle strong acid that-TPD method records accounts for 70% ~ 85% of total acid content, is preferably 75% ~ 85%, Na
2o≤0.15wt%, is preferably≤0.10wt%.
In beta-molecular sieve of the present invention, total aluminium refers to the summation of the aluminium in molecular sieve in framework aluminum and the aluminium in non-framework aluminum.Non-framework aluminum refers in molecular sieve with the aluminium that hexa-coordinate version exists.Framework aluminum refers in molecular sieve with the aluminium that four-coordination version exists.
Described catalyst for hydro-upgrading carrier, with the weight of carrier for benchmark, the content of beta-molecular sieve is 5% ~ 40%, and the content of aluminium oxide is 60% ~ 95%.
The specific area of catalyst for hydro-upgrading carrier of the present invention is 300 ~ 500m
2/ g, pore volume is 0.5 ~ 1.0mL/g.
The preparation method of diesel oil hydrogenation modification catalyst carrier of the present invention, comprising:
By beta-molecular sieve and aluminium oxide mechanical mixture, shaping, then dry and roasting, makes catalyst carrier; Wherein said beta-molecular sieve adopts following method step:
(1) processed under normal pressure, dynamic water vapour condition by former for beta-molecular sieve powder, treatment temperature is 500 ~ 650 DEG C, and the processing time is 5 ~ 10 hours;
(2) with the beta-molecular sieve of highly basic weak solution treatment step (1) gained, then filter, wash and drying, obtain beta-molecular sieve.
The former powder of step (1) beta-molecular sieve adopts hydrothermal crystallization method synthesis, its SiO
2/ Al
2o
3mol ratio 20.0 ~ 25.0, Na
2o content is for being less than 0.2wt%.
The former powder of step (1) beta-molecular sieve, in normal pressure, dynamic water vapour condition process, generally can adopt the water vapour of flowing to carry out, adopt 100wt% water vapour.Water vapour passes through beta-molecular sieve by every kilogram of beta-molecular sieve 20 ~ 100L/h.
In step (2), in described highly basic weak solution, rare paper mill wastewater is (with OH
-meter) 0.01 ~ 0.2mol/L, preferably 0.02 ~ 0.15mol/L.It is formulated that described highly basic weak solution can adopt highly basic to be added to the water, and highly basic can be one or more in lithium hydroxide, NaOH, potassium hydroxide.The weight ratio of highly basic weak solution and beta-molecular sieve is 5:1 ~ 20:1.Described treatment conditions: temperature 40 ~ 120 DEG C, be preferably 70 ~ 100 DEG C, the time is 1.0 ~ 8.0 hours, preferably 2.0 ~ 4.0 hours.Described washing conditions: washing temperature 50 ~ 90 DEG C, preferably 60 ~ 80, washing time 0.5 ~ 1.0 hour, until cleaning solution pH value is close to neutrality, then under the condition of 100 ~ 120 DEG C dry 3 ~ 6 hours.
First the inventive method adopts normal pressure, Dynamic Hydrothermal process molecular screen primary powder, molecular sieve can be realized take off ammonium (Template removal) and selective reduction framework aluminum activation energy under the effect of dynamic high temperature water vapour, and avoid framework of molecular sieve structural damage, and keep the homogeneity of framework of molecular sieve structure, match with follow-up highly basic weak solution modifying process, effectively non-framework aluminum evenly can be deviate from, form unimpeded pore structure, and make a small amount of OH
-be adsorbed in the skeleton structure of molecular sieve, be conducive to improving the acid strength of molecular sieve and sour density, be conducive to the isomery performance improving catalyst.Relative to the modification adopting the method for acid treatment and rear hydrothermal treatment consists to carry out molecular sieve in existing method, owing to there being a large amount of H in strong acid acidization
+existence can be that non-selectivity is deviate to the framework aluminum in molecular sieve and non-framework aluminum structure, both part non-framework aluminum structure can have been deviate from, also part framework aluminum structure can be deviate from, have a strong impact on framework of molecular sieve silicon-aluminum structure and acidic zeolite matter, in addition, high-temperature water heat treatment is carried out again after acidifying, also non-framework aluminum structure can again be produced in this modification procedure, the further Acidity affecting molecular sieve, a large amount of non-framework aluminum structure is present in the pore structure of Severe blockage molecular sieve in the duct of modified molecular sieve, but also the acid site in meeting masked portion framework of molecular sieve, greatly affect the performance of modified molecular sieve, and then have influence on Cracking catalyst object product selectivity and product property.
The long side chain n-alkyl of the beta-molecular sieve that the present invention selects to long chain alkane and aromatic hydrocarbons, cycloalkane has suitable splitting action and very strong isomerization, make catalyst for hydro-upgrading prepared therefrom can maintenance high diesel yield while, reduce the condensation point of diesel oil distillate by a relatively large margin, reach the effect of volume increase low-coagulation diesel oil.
When catalyst prepared by catalyst for hydro-upgrading carrier of the present invention is used for poor ignition quality fuel upgrading, particularly middle press strip part (4 ~ 12MPa) and process poor ignition quality fuel (heavy MIP diesel oil and coker gas oil), there is very high catalytic activity and diesel yield, and the condensation point reduction amplitude of diesel oil distillate is large, improve the Cetane number of upgrading diesel oil by a relatively large margin, the density of diesel product is effectively reduced, and can meet refinery and increase operating flexibility, increases device disposal ability, increases the needs that high-quality produces diesel oil further.
Detailed description of the invention
In catalyst for hydro-upgrading carrier of the present invention, aluminium oxide can adopt aluminium oxide used in conventional hydro modifying catalyst, as macroporous aluminium oxide and ∕ or little porous aluminum oxide.Pore volume 0.7 ~ the 1.0mL/g of macroporous aluminium oxide used, specific area 200 ~ 500m
2/ g.The pore volume of little porous aluminum oxide used is 0.3 ~ 0.5mL/g, and specific area is 200 ~ 400m
2/ g.
The such as peptization acid of conventional shaping assistant can also be added, extrusion aid etc. in catalyst support preparation process of the present invention.
Beta-molecular sieve in catalyst for hydro-upgrading carrier of the present invention, concrete preparation method is as follows:
(1) processed under normal pressure, dynamic water vapour condition by former for beta-molecular sieve powder, treatment temperature is 500 ~ 650 DEG C, and the processing time is 5 ~ 10 hours;
The former powder of the beta-molecular sieve that the present invention adopts hydrothermal crystallizing to synthesize.Adopt the chemical SiO of the former powder of beta-molecular sieve
2/ Al
2o
3mol ratio 20.0 ~ 25.0, Na
2o content for being less than 0.2wt%, relative crystallinity more than 95%;
The hydrothermal conditions adopted in the present invention is water vapour is 100wt% water vapour, and water vapour passes through beta-molecular sieve by every kilogram of beta-molecular sieve 20 ~ 100L/h.In order to make molecular sieve process evenly, preferably molecular sieve is placed in rotary container, the other end of water vapour again from container after passing into molecular sieve from one end of container is gone out.Pressure in container keeps atmospheric pressure state, and treatment temperature remains on 500 ~ 650 DEG C, and the processing time is 5 ~ 10 hours;
In the inventive method, the former powder of beta-molecular sieve is placed in container such as tube furnace, adopt temperature programming, heating rate is 50 ~ 150 DEG C/h, when preferably rising to 250 ~ 450 DEG C, preferably further start to introduce water vapour 250 ~ 400 DEG C time, then while introducing water vapour, be warming up to 500 ~ 650 DEG C, and process 5 ~ 10 hours at this temperature;
(2) with the beta-molecular sieve of highly basic weak solution treatment step (3) gained, then filter, wash and drying;
Adding highly basic weak solution with return-flow system in airtight container, wherein highly basic weak solution concentration is (with OH
-meter) 0.01 ~ 0.2mol/L, preferably 0.02 ~ 0.15mol/L, stirs and is warmed up to 40 ~ 120 DEG C, is preferably 70 ~ 100 DEG C, then be 5:1 ~ 20:1 by the weight ratio of highly basic weak solution and molecular sieve, add the molecular sieve that step (3) obtains, constant temperature stirs 1.0 ~ 8.0 hours, preferably 2.0 ~ 4.0 hours, filter, wash, washing, until cleaning solution pH value is close to neutrality, and under the condition of 100 ~ 120 DEG C dry 3 ~ 6 hours, obtains beta-molecular sieve of the present invention.Wherein highly basic weak solution can be one or more the aqueous solution in lithium hydroxide, NaOH, potassium hydroxide.
Detailed process prepared by catalyst for hydro-upgrading carrier of the present invention is:
Modified beta molecular sieve, aluminium oxide and adhesive are mixed, extruded moulding, then carries out drying and roasting, is prepared into carrier, and described drying can carry out 3 ~ 6 hours at the temperature of 80 DEG C to 150 DEG C, and roasting is 500 DEG C ~ 600 DEG C roastings 2.5 ~ 6 hours.
When modifying catalyst carrier of the present invention is for the preparation of modifying catalyst, can adopt carrying method conventional in prior art, preferred infusion process, can be saturated leaching, excessive leaching or complexing leaching.
The following examples are used for illustrating in greater detail the present invention, but scope of the present invention is not only limited to the scope of these embodiments.In the present invention, wt% is mass fraction.
Analytical method of the present invention: specific area and pore volume adopt low temperature liquid nitrogen physisorphtion, and silica alumina ratio adopts chemical method, and meleic acid amount adopts Pyridine adsorption IR spectra method, and the acid amount of middle strong acid and total acid content are by NH
3-TPD method measures (passes through NH
3-TPD method measures: 150 ~ 250 DEG C of corresponding acid are weak acid, and 250 ~ 400 DEG C of corresponding acid are middle strong acid, and 400 ~ 500 DEG C of corresponding acid are strong acid; Weak acid, middle strong acid and strong acid acid amount and be total acid content), sodium content adopt plasma emission spectrometry, relative crystallinity adopt XRD method mensuration.
In the present invention, nuclear magnetic resonance spectroscopy (NMR method) is adopted to record
27al MAS NMR spectrogram, thus obtain the ratio of framework aluminum and non-framework aluminum, in aluminium atom.Nuclear magnetic resonance spectroscopy (NMR method) adopts Bruker AVANCE III 500 type nuclear magnetic resonance spectrometer, and wherein software adopts Topspin 2.0.In survey
27during Al MAS NMR spectrogram, accepted standard material is alchlor, and resonant frequency is 133MHz, experiment condition: 4-6 microsecond pulse width, 60-120 relaxation delay second.Gained
27in Al MAS NMR spectrogram, the chemical shift that framework aluminum is corresponding is 40 ~ 65ppm, and the chemical shift that non-framework aluminum is corresponding is-10 ~ 10ppm.
Embodiment 1
Get the former powder of beta-molecular sieve and be about 3500g, its chemical sial SiO
2/ Al
2o
3(mol ratio), than being 22.68, sodium oxide content is 0.18wt%.Beta-molecular sieve is loaded in tube furnace, adopt the method (heating rate is 100 DEG C/h) of temperature programming, the water vapour introducing 100wt% is started when tube furnace temperature is raised to 300 DEG C, water vapour passes through beta-molecular sieve by every kilogram of beta-molecular sieve 40L/h, by diamond heating to 550 DEG C, constant temperature time is 8 hours.Gained molecular sieve is numbered BH-1, and character is in table 1.
Embodiment 2
Get the former powder of beta-molecular sieve and be about 3500g, with embodiment 1.Molecular sieve is loaded in tube furnace, adopt the method (heating rate is 100 DEG C/h) of temperature programming, the water vapour introducing 100wt% is started when tube furnace temperature is raised to 300 DEG C, water vapour passes through beta-molecular sieve by every kilogram of beta-molecular sieve 70L/h, by diamond heating to 620 DEG C, constant temperature time is 8 hours.Gained molecular sieve is numbered BH-2, and character is in table 1.
Embodiment 3
Take 50g BH-1 molecular sieve to put into reflux and flask that can be airtight, add concentration 0.04mol/L NaOH aqueous solution 400ml, the weight ratio of the NaOH aqueous solution and BH-1 molecular sieve is 8:1, at 95 DEG C, constant temperature stirs 2.0 hours, filter, and use hot deionized water washing leaching cake, after 7, stop washing with the pH value of cleaning solution.Filter cake 120 DEG C of dryings 5 hours in an oven, obtain beta molecular sieve of the present invention, its numbering BJ-1, molecular sieve character is in table 1.
Embodiment 4
Take 50g BH-1 molecular sieve to put into reflux and flask that can be airtight, add concentration 0.1mol/L NaOH aqueous solution 700ml, the weight ratio of the NaOH aqueous solution and BH-1 molecular sieve is 14:1, at 90 DEG C, constant temperature stirs 2.5 hours, filter, and use hot deionized water washing leaching cake, after 7, stop washing with the pH value of cleaning solution.Filter cake 120 DEG C of dryings 5 hours in an oven.Obtain beta molecular sieve of the present invention, its numbering BJ-2, molecular sieve character is in table 1.
Embodiment 5
Take 50g BH-2 molecular sieve to put into reflux and flask that can be airtight, add concentration 0.15mol/L KOH aqueous solution 1000ml, the weight ratio of the KOH aqueous solution and BH-2 molecular sieve is 20:1, at 80 DEG C, constant temperature stirs 2.0 hours, filter, and use hot deionized water washing leaching cake, after 7, stop washing with the pH value of cleaning solution.Filter cake 120 DEG C of dryings 5 hours in an oven, obtain beta molecular sieve of the present invention, its numbering BJ-3, molecular sieve character is in table 1.
Embodiment 6
Take 50g BH-2 molecular sieve to put into reflux and flask that can be airtight, add concentration 0.06mol/L (NaOH+KOH, the two molar ratio is 1:1) aqueous solution 300ml, the weight ratio of NaOH and the KOH aqueous solution and BH-2 molecular sieve is 6:1, at 90 DEG C, constant temperature stirs 3.0 hours, filter, and use hot deionized water washing leaching cake, after 7, stop washing with the pH value of cleaning solution.Filter cake 120 DEG C of dryings 5 hours in an oven, obtain beta molecular sieve of the present invention, its numbering BJ-4, molecular sieve character is in table 1.
Comparative example 1
The method in CN01106042.5 is adopted to prepare modified molecular screen.Gained molecular sieve is BD-1, and character is in table 1, and detailed process is as follows:
(1) the molecular screen primary powder 300g in Example 1, be that 10:1 exchanges with 2.0M ammonium nitrate solution with liquid-solid ratio, be warming up to 90 ~ 95 DEG C, constant temperature stirs 2 hours, is then cooled to 50 ~ 60 DEG C of filtrations, and wet cake carries out second time again and exchanges, and condition is with first time.
(2) through the beta-molecular sieve that twice ammonium salt exchanges, wash and reach 6 to pH, then put into drying box, 110 DEG C of dryings 6 hours;
(3) dried beta-molecular sieve is put into muffle furnace and was warming up to 250 DEG C at 1 hour, constant temperature 2 hours, then continues to be warming up to 400 DEG C in 1 hour, then constant temperature 4 hours, and be finally warmed up to 540 DEG C, constant temperature 10 hours, material all burns white, carbon residue≤0.2%;
(4) high-temperature roasting takes off the beta-molecular sieve of ammonium through pulverizing, sieving, and weigh 400g, add 0.4M HCl 4000ml, stir and be warming up to 80 DEG C, constant temperature stirs 2 hours, and cold filtration washs.
(5) through acid-treated beta-molecular sieve filtration washing, then 110 DEG C of dryings 6 hours, butt is 85%.
(6) sample of above-mentioned drying is placed in airtight hydrothermal treatment consists stove, even sprinkling 0.4(kg water/kg drying sample) water purification, then airtight, intensification, controlled pressure 300KPa, temperature 600 DEG C, programming rate is 500 DEG C/h, constant temperature and pressure roasting 3 hours, then Temperature fall, namely obtains comparative example modified molecular screen.
Comparative example 2
(1) commercial synthesis SiO is got
2/ Al
2o
324.35, Na
2slurries 1000ml in the Na beta-molecular sieve process of O 3.75wt% after crystallization, containing solid phase 300g(in butt), add 2M ammonium chloride solution 2000mL, stir, be warming up to 95 DEG C, constant temperature stirs 2 hours, is then cooled to 60 DEG C of filtrations, wet cake carries out second time again and exchanges, and condition is with first time;
(2) through the beta-molecular sieve that twice ammonium salt exchanges, wash and reach 6 to pH, then put into drying box, 110 DEG C of dryings 6 hours;
(3) dried beta-molecular sieve is put into muffle furnace and was warming up to 250 DEG C at 1 hour, constant temperature 2 hours, then continues to be warming up to 400 DEG C in 1 hour, then constant temperature 4 hours, and be finally warmed up to 540 DEG C, constant temperature 10 hours, material all burns white, carbon residue≤0.2%;
(4) beta-molecular sieve is put into reflux and flask that can be airtight, add concentration 0.04mol/L NaOH aqueous solution 400ml, the solvent and solute weight ratio of the NaOH aqueous solution and molecular sieve is 8:1, at 95 DEG C, constant temperature stirs 2.0 hours, filter, and use hot deionized water washing leaching cake, after 7, stop washing with the pH value of cleaning solution.Filter cake 120 DEG C of dryings 5 hours in an oven, obtain beta-molecular sieve, its numbering BD-2, molecular sieve character is in table 1.
Comparative example 3
Adopt the former powder of beta-molecular sieve with embodiment 1.Get above-mentioned molecular sieve 1000g, load in airtight hydrothermal treatment consists stove, adopt the method (heating rate is 100 DEG C/h) of temperature programming, hydrothermal treatment consists temperature 620 DEG C, hydrothermal treatment consists pressure is 0.2MPa.Alkali treatment is carried out at employing raw material, employing concentration is the NaOH solution process of 0.04mol/L, the solvent and solute weight ratio of NaOH solution and molecular sieve is 8:1, treatment temperature is 95 DEG C, processing time is 2.0 hours, after constant temperature terminates, and is filtered by slurries, and use hot deionized water washing leaching cake, after 7, stop washing with the pH value of cleaning solution.120 DEG C of dryings 5 hours in an oven, obtain beta-molecular sieve, be numbered BD-3, physico-chemical property lists in table 1.
the character of table 1 embodiment and comparative example gained molecular sieve
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 area 400m
2/ g, butt 70wt%), 133.3 grams of adhesives (butt 30wt%, the mol ratio of nitric acid and little porous aluminum oxide is 0.4) put into roller mixed grind, add water, be rolled into paste, extrusion, extrude bar 110 DEG C of dryings 4 hours, then 550 DEG C of roastings 4 hours, obtain carrier GS-1, character is 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 area 400m
2/ g, butt 70wt%), 133.3 grams of adhesives (butt 30wt%, the mol ratio of nitric acid and little porous aluminum oxide is 0.4) put into roller mixed grind, add water, be rolled into paste, extrusion, extrude bar 110 DEG C of dryings 4 hours, then 550 DEG C of roastings 4 hours, obtain carrier GS-2, character is in table 2.
The maceration extract room temperature immersion of carrier tungstenic and nickel 2 hours, 120 DEG C of dryings 4 hours, temperature programming 500 DEG C of roastings 4 hours, obtain catalyst FC-2, and carrier and corresponding catalyst character are 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 area 400m
2/ g, butt 70wt%), 133.3 grams of adhesives (butt 30wt%, the mol ratio of nitric acid and little porous aluminum oxide is 0.4) put into roller mixed grind, add water, be rolled into paste, extrusion, extrude bar 110 DEG C of dryings 4 hours, then 550 DEG C of roastings 4 hours, obtain carrier GS-3, character is 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 area 400m
2/ g, butt 70wt%), 133.3 grams of adhesives (butt 30wt%, the mol ratio of nitric acid and little porous aluminum oxide is 0.4) put into roller mixed grind, add water, be rolled into paste, extrusion, extrude bar 110 DEG C of dryings 4 hours, then 550 DEG C of roastings 4 hours, obtain carrier GS-4, character is 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 area 400m
2/ g, butt 70wt%), 133.3 grams of adhesives (butt 30wt%, the mol ratio of nitric acid and little porous aluminum oxide is 0.4) put into roller mixed grind, add water, be rolled into paste, extrusion, extrude bar 110 DEG C of dryings 4 hours, then 550 DEG C of roastings 4 hours, obtain carrier DGS-1, character is in table 2.
The maceration extract room temperature immersion of carrier tungstenic and nickel 2 hours, 120 DEG C of dryings 4 hours, temperature programming 500 DEG C of roastings 4 hours, obtain catalyst FCD-1, and carrier and corresponding catalyst character are 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 area 400m
2/ g, butt 70wt%), 133.3 grams of adhesives (butt 30wt%, the mol ratio of nitric acid and little porous aluminum oxide is 0.4) put into roller mixed grind, add water, be rolled into paste, extrusion, extrude bar 110 DEG C of dryings 4 hours, then 550 DEG C of roastings 4 hours, obtain carrier DGS-2, character is in table 2.
The maceration extract room temperature immersion of carrier tungstenic and nickel 2 hours, 120 DEG C of dryings 4 hours, temperature programming 500 DEG C of roastings 4 hours, obtain catalyst FCD-2, and carrier and corresponding catalyst character are in table 2.
Embodiment 11
This embodiment describes the catalyst activity evaluation result prepared by carrier of the present invention.Fixed bed hydrogenation experimental rig is evaluated, and appreciation condition is: reaction stagnation pressure 10.0MPa, hydrogen to oil volume ratio 700:1, volume space velocity 2.0h during liquid
-1, use catalytic diesel oil as feedstock oil, feedstock oil character lists in table 3.Catalyst FC-2, FCD-1 are evaluated under identical process conditions with FCD-2, the evaluation result obtained lists in table 4.
As can be seen from evaluation result, carrier prepared catalyst of the present invention is under identical process conditions, and diesel yield and product quality are all better than reference catalyst.
the physico-chemical property of table 2 catalyst carrier and catalyst
| Embodiment 7 | Embodiment 8 | Embodiment 9 | Embodiment 10 | Comparative example 4 | Comparative example 5 | |
| Carrier composition and character | ||||||
| Numbering | GS-1 | GS-2 | GS-3 | GS-4 | DGS-1 | DGS-2 |
| Beta-molecular sieve, wt% | 15 | 20 | 30 | 35 | 20 | 30 |
| Aluminium oxide, wt% | Surplus | Surplus | Surplus | Surplus | Surplus | Surplus |
| Specific area, m 2/g | 435 | 403 | 447 | 453 | 356 | 408 |
| Pore volume, mL/g | 0.69 | 0.64 | 0.56 | 0.55 | 0.51 | 0.47 |
| Catalyst composition and character | ||||||
| Numbering | FC-2 | FCD-1 | FCD-2 | |||
| WO 3，wt% | 24.5 | 24.7 | 22.1 | |||
| NiO，wt% | 5.9 | 6.1 | 5.8 |
table 3 feedstock oil character
| Feedstock oil | MIP catalytic diesel oil |
| Density (20 DEG C), g/cm 3 | 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 result
| Catalyst | FC-2 | FCD-1 | FCD-2 |
| Feedstock oil | MIP catalytic diesel oil | MIP catalytic diesel oil | MIP catalytic diesel oil |
| Volume space velocity during liquid, h -1 | 2.0 | 2.0 | 2.0 |
| Reaction 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 character | |||
| Naphtha | |||
| Yield, wt% | 2.0 | 3.6 | 3.5 |
| Virtue is dived, 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，℃ | 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 (20)
1. a catalyst for hydro-upgrading carrier, comprises beta-molecular sieve and aluminium oxide, and the character of described beta-molecular sieve is as follows: specific area is 400m
2/ g ~ 800m
2/ g, total pore volume is 0.4ml/g ~ 0.55mL/g, SiO
2/ Al
2o
3mol 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 aluminium
3the acid amount of the middle strong acid that-TPD method records accounts for 70% ~ 85%, Na of total acid content
2o≤0.15wt%.
2., according to catalyst carrier according to claim 1, it is characterized in that the specific area of described beta-molecular sieve is 500 ~ 750m
2/ g, total pore volume is 0.4ml/g ~ 0.55mL/g.
3., according to catalyst carrier according to claim 1, it is characterized in that the SiO of described beta-molecular sieve
2/ Al
2o
3mol ratio is 35 ~ 55.
4., according to catalyst carrier according to claim 1, it is characterized in that in described beta-molecular sieve, NH
3the acid amount of the middle strong acid that-TPD method records accounts for 75% ~ 85% of total acid content.
5. according to catalyst carrier according to claim 1, it is characterized in that: described catalyst for hydro-upgrading carrier, with the weight of carrier for benchmark, the content of beta-molecular sieve is 5% ~ 40%, and the content of aluminium oxide is 60% ~ 95%.
6. according to catalyst carrier according to claim 1, it is characterized in that: the specific area of described catalyst carrier is 300 ~ 500m
2/ g, pore volume is 0.5 ~ 1.0mL/g.
7. the preparation method of the arbitrary described catalyst carrier of claim 1 ~ 6, comprising: by beta-molecular sieve, aluminium oxide mechanical mixture, shaping, and then dry and roasting, makes catalyst carrier; The wherein preparation method of beta-molecular sieve, comprising:
(1) processed under normal pressure, dynamic water vapour condition by former for beta-molecular sieve powder, treatment temperature is 500 ~ 650 DEG C, and the processing time is 5 ~ 10 hours;
(2) with the beta-molecular sieve of highly basic weak solution treatment step (1) gained, then filter, wash and drying, obtain beta-molecular sieve.
8. in accordance with the method for claim 7, it is characterized in that step (1) beta-molecular sieve former mealiness matter is as follows: SiO
2/ Al
2o
3mol ratio 20.0 ~ 25.0, Na
2o content is for being less than 0.2wt%.
9. in accordance with the method for claim 7, it is characterized in that step (1) adopts the 100wt% steam treatment of flowing.
10., according to the method described in claim 7 or 9, it is characterized in that, in step (1), water vapour passes through beta-molecular sieve by every kilogram of beta-molecular sieve 20 ~ 100L/h.
11. according to the method described in claim 7 or 9, it is characterized in that in step (1), in step (1), the former powder of beta-molecular sieve is placed in container, and adopt temperature programming, heating rate is 50 ~ 150 DEG C/h, when rising to 250 ~ 450 DEG C, start to introduce water vapour, then while introducing water vapour, be warming up to 500 ~ 650 DEG C, and process 5 ~ 10 hours at this temperature.
12. in accordance with the method for claim 7, it is characterized in that described highly basic is one or more in lithium hydroxide, NaOH, potassium hydroxide.
13. according to the method described in claim 7 or 12, it is characterized in that, in step (2), in described highly basic weak solution, rare paper mill wastewater is with OH
-meter 0.01 ~ 0.2mol/L.
14. according to the method described in claim 7 or 12, it is characterized in that, in step (2), in described highly basic weak solution, rare paper mill wastewater is with OH
-meter 0.02 ~ 0.15mol/L.
15. in accordance with the method for claim 7, it is characterized in that the weight ratio of described highly basic weak solution and beta-molecular sieve is 5:1 ~ 20:1.
16. in accordance with the method for claim 7, it is characterized in that the treatment conditions described in step (2): temperature 40 ~ 120 DEG C, and the time is 1.0 ~ 8.0 hours.
17. in accordance with the method for claim 7, it is characterized in that the treatment conditions described in step (2): temperature 70 ~ 100 DEG C, and the time is 2.0 ~ 4.0 hours.
18. in accordance with the method for claim 7, and the drying that it is characterized in that described in step (2) is under the condition of 100 ~ 120 DEG C dry 3 ~ 6 hours.
19. in accordance with the method for claim 7, it is characterized in that: drying and the roasting of carrier are as follows: 100 DEG C ~ 150 DEG C dryings 1 ~ 12 hour, then 450 DEG C ~ 550 DEG C roastings 2.5 ~ 6.0 hours.
20. in accordance with the method for claim 7, it is characterized in that: described aluminium oxide adopts macroporous aluminium oxide and ∕ or little porous aluminum oxide, the pore volume 0.7 ~ 1.0mL/g of macroporous aluminium oxide used, specific area 200 ~ 500m
2/ g, the pore volume of little porous aluminum oxide used is 0.3 ~ 0.5mL/g, and specific area is 200 ~ 400m
2/ g.
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