CN103055924B - Preparation method of bulk phase hydrocracking catalyst - Google Patents
Preparation method of bulk phase hydrocracking catalyst Download PDFInfo
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Abstract
The invention discloses a preparation method of a bulk phase hydrocracking catalyst. The method comprises the steps of preparing an acidic mixed solution A containing hydrogenation reactive metals, silicon and organic solvents, and filling CO2 into the solution A; preparing a sodium metaaluminate alkaline solution B, and subjecting the solution B to react with the solution A into which CO2 is filled to prepare gel; and then adding turbid liquid of a Y type molecular sieve, mixing the substances uniformly, filtering and drying the obtained mixture, and then forming, washing, drying and roasting the filter cake, thus preparing the hydrocracking catalyst. The catalyst obtained by the method has the advantages of big specific surface area, big pore volume, high strength and high dispersibility of reactive metal components, and is especially suitable for producing more heavy hydrocarbon catalytic reforming raw materials, jet fuel and diesel through hydrocracking.
Description
Technical field
The present invention relates to a kind of preparation method of hydrocracking catalyst, particularly a kind of preparation method of high activity medium oil type hydrocracking catalyst.
Background technology
At present, worldwide petroleum resources are not enough, and crude quality is deteriorated year by year, intermediate oil demand increases, petroleum chemicals upgrading and environmental regulation are more and more strict, all greatly facilitate heavy oil lighting, and form the very strong driving force of accelerated development hydrogen addition technology.The main feature of hydrocracking technology is that adaptability to raw material is strong, products scheme, object product selectivity are high, good product quality and added value is high, directly can produce multiple high-quality oil product (as gasoline, jet fuel, diesel oil, lube base wet goods) and high-quality industrial chemicals (as the production such as benzene,toluene,xylene, ethene raw material).
Hydrocracking catalyst is a kind of bifunctional catalyst, and it has cracking activity and hydrogenation activity simultaneously, namely simultaneously containing acidic components and hydrogenation active component.Wherein acidly mainly provided by various molecular sieve and/or the heat-resistant inorganic oxide that forms carrier, the character of acidic components has very important impact to the activity of hydrocracking catalyst and the selective of intermediate oil.In order to meet the different requirements to hydrocrackates, need to carry out adaptive modulation to the acidic components in catalyst and hydrogenation active component.Be faced with the trend of the serious heaviness of raw material that current industrial hydrocracking processes and in poor quality, the activity improving hydrocracking catalyst becomes the problem that people more and more pay close attention to.
Bulk phase catalyst refers to that the loaded catalyst be dispersed on carrier with active constituent is relative, not with inactive carrier for carrier.Catalyst major part is made up of active component, and the content of active constituent is generally unrestricted, sometimes also claims body catalyst.Compared with load hydrogenation catalyst, body phase hydrogenation catalyst activated centre density wants high a lot, but how to effectively utilize highdensity hydrogenation sites, makes bulk phase catalyst have high hydrogenation activity.
Compared with load hydrogenation catalyst, bulk phase catalyst does not have the support of carrier, its pore passage structure is made up of activated metal component completely, surface that can be close at reactant molecule all can play active function, therefore specific area and the pore volume of bulk phase catalyst is increased, the harmony improved between activated metal component dispersiveness and active metal can improve the utilization rate of hydrogenation sites, thus also becomes the key affecting bulk phase catalyst hydrogenation activity height.
The petroleum refining industry of 21st century must follow the strategy of sustainable development, the principle that must pay attention to economic benefit, protection of the environment simultaneously and economize on resources.Therefore, adopt the preparation method of non-environmental-pollution to produce bulk phase catalyst and become more important.Existing coprecipitation method Kaolinite Preparation of Catalyst technology, uses NH mostly
3h
2o is as precipitating reagent, and this is by producing a large amount of waste water containing ammonia, nitrogen, to environment.
Hydrocracking catalyst disclosed in US 3954671, hydrogenation conversion catalyst disclosed in US 4313817, the hydrocracking catalyst of nitrogen-resistant type fecund intermediate oil disclosed in CN1253988A, heavy hydrocarbons hydrocraking catalyst disclosed in CN1253989A, these catalyst are that glue legal system is standby altogether in employing, alkaline precipitating agent used is all Ammonia, though can obtain for the treatment of the comparatively ideal hydrocracking catalyst of heavy hydrocarbon fecund intermediate oil performance, the too not effective control measures of ammonia nitrogen pollution on the environment.CN101239324A discloses a kind of glue legal system altogether for the method for high activity, medium oil type hydrocracking catalyst, and precipitating reagent adopts alkalescent ammoniac compounds, still there is the problem of ammonia and nitrogen pollution.
Adopt sodium metaaluminate aqueous slkali to be the method that hydrogenation catalyst prepared by precipitating reagent disclosed in CN101172261A, precipitation is mainly from meta-aluminic acid radical ion and hydroxide ion, easily larger deposit seed is formed like this in precipitation process, the bad adhesion of catalyst feed, cause the specific area of catalyst and intensity to decline to some extent simultaneously, can have an impact to the serviceability of catalyst.
The disclosed hydrocracking catalyst such as CN1854261A, CN101757931A, CN101733149A, CN101144033A is made up of acid active component, hydrogenation active component and organic additive, and catalyst have employed conventional impregnation methods preparation.Due to the restriction by preparation method, catalyst activity increases, but is immersed in catalyst surface due to organic reagent and easily decomposes, and when going into operation to refinery facilities, catalyst drying and sulfuration all bring many difficulties.Meanwhile, for processing raw material of more and more heaviness and in poor quality, catalyst activity still can not meet the demands.
Existing coprecipitation method Kaolinite Preparation of Catalyst technology, adopts sodium metaaluminate to do aluminium source and precipitating reagent, avoid producing ammonia, polluted by nitrogen in catalyst preparation process, but catalyst feed adhesivity is poor.The caking property of precipitated metal thing can be increased in body phase method metalliferous material containing suitable heteroion, contribute to metalliferous material extruded moulding.If sodium metaaluminate instead of the solvable inorganic aluminates such as aluminium chloride, aluminum nitrate, aluminum sulfate and does aluminium source, a large amount of NO will be reduced
3 -, Cl
-, SO
4 2-deng heteroion, the composite oxides precursor peptization of preparation is poor, metalliferous material difficult forming.Coprecipitation method Kaolinite Preparation of Catalyst also has a difficult point to be that the metal mixture grain size difference that obtains of different aluminium sources and precipitating reagent is large and then have considerable influence to the specific area of catalyst, intensity.In order to decreasing pollution, how to solve the problem adopting sodium metaaluminate replacement ammoniacal liquor to do the materials from bonding difference of the body phase clean method for preparing generation of precipitating reagent.How to allow Ni prepared by coprecipitation method
xw
yo
zcomposite oxides and Al
2o
3the mixture crystal grain homoepitaxial of precursor, catalyst has the feature of bigger serface, good pore structure, activated metal component good dispersion, make the active metal in constituting body phase catalyst duct dispersed, strengthen active metal be exposed to outer, close to the chance of reactant molecule, thus improve bulk phase catalyst active metal utilization rate, strengthen its Hydrogenation.
Summary of the invention
For the deficiencies in the prior art, the invention provides that a kind of specific area is large, pore volume is large, intensity is high, the preparation method of the body phase hydrocracking catalyst of active metal component good dispersion, this hydrocracking catalyst is specially adapted to heavy hydrocarbons hydrocraking fecund catalytic reforming raw material (heavy naphtha), jet fuel and diesel oil.
The preparation method of body phase hydrocracking catalyst of the present invention, described hydrocracking catalyst comprises amorphous aluminum silicide, Y zeolite, hydrogenation active metals component, wherein hydrogenation active metals is group vib metal and group VIII metal, preparation process is as follows: preparation, containing the acidic mixed solution A of hydrogenation active metals, silicon and organic solvent, passes into CO in solution A
2gas, preferably makes CO in solution A
2concentration is saturated; Preparation sodium metaaluminate alkaline solution B, by solution B with pass into CO
2the solution A reaction plastic of gas, at the end of reaction, the pH value controlling slurries in retort is 7.0 ~ 9.0; Then the suspension adding Y zeolite mixes, and the mixture of gained filters, the filter cake drying obtained, then obtains hydrocracking catalyst through shaping, washing, drying, roasting; Add CO
2al in the total amount of gas and alkaline solution B
2o
3mol ratio be 2 ~ 8; Organic solvent used is selected from containing one or more in oxygen or nitrogenous organic compound, described organic solvent with the mol ratio of the group vib metal of oxide basis and group VIII metal sum for 0.1 ~ 3.0, be preferably 0.3 ~ 2.0, i.e. the ratio of molal quantity and the group vib metal oxide of organic solvent and the molal quantity sum of group VIII metal oxide.
In the inventive method, controlling gelling temperature in acidic mixed solution A, alkaline solution B plastic process is 40 ~ 70 DEG C, controls gelation time at 0.5 ~ 3.0 hour.CO used
2the volumetric concentration of gas is 80v% ~ 95v%.
In the inventive method, solution B with pass into CO
2when the solution A of gas reacts plastic, can adopt and flow plastic method, also can adopt tank plastic method and change pH values plastic method, solution B is added to and pass into CO
2plastic in the solution A of gas, also can pass into CO
2the solution A of gas adds plastic in solution B.Also above-mentioned two kinds of methods can be combined.And when flowing plastic, the pH value regulating slurries in retort is 7.0 ~ 9.0.
In hydrocracking catalyst of the present invention, with the weight of catalyst for benchmark, the content of group vib metal oxide is 10wt% ~ 50wt%, preferably 20wt% ~ 30wt%, the content of group VIII metal oxide is 1wt% ~ 20wt%, preferably 5wt% ~ 15wt%, the content of Y zeolite is 10wt% ~ 40wt%, preferably 20wt% ~ 30wt%, the content of amorphous aluminum silicide is 30wt% ~ 60wt%, preferably 30wt% ~ 40wt%.
Organic solvent used is selected from containing one or more in oxygen or nitrogenous organic compound, wherein oxygen-containing organic compound is preferably one or more in Organic Alcohol and organic acid, such as: one or more in ethylene glycol, glycerine, diethylene glycol, butanediol, aminotriacetic acid etc., one or more in the preferred organic amine of organic compounds containing nitrogen, such as: one or more in ethylenediamine, ethylenediamine tetra-acetic acid, tetraethylammonium bromide, tetraethyl ammonium hydroxide, 4-propyl bromide, softex kw etc.
In hydrocracking catalyst of the present invention, also can contain adjuvant component, described adjuvant component is IVB race metal, and the content of IVB family metal oxide in hydrocracking catalyst is 1wt% ~ 10wt%.Described IVB race metal is preferably Ti and/or Zr.In hydrocracking catalyst preparation process of the present invention, preparing in acid solution A process the compound added containing adjuvant component, i.e. titanium source and/or zirconium source.
In hydrocracking catalyst of the present invention, Y zeolite used can adopt all Y zeolites that can be used in hydrocracking catalyst in prior art, such as: Y zeolite disclosed in CN101380588A, CN102049280A, CN1174756A, CN102049308A.Y zeolite disclosed in preferred CN101380588A in the present invention, with NH
4naY molecular sieve is raw material, dealumination complement silicon is carried out with hexafluorosilicic acid aqueous ammonium, the Y zeolite obtained is at gauge pressure 0.05 ~ 0.4MPa, temperature 560 ~ 620 DEG C, time is carry out hydrothermal treatment consists in the condition and range of 0.5 ~ 50 hour, Y zeolite after process aluminium salt and inorganic acid or organic acid mixed aqueous solution process 0.5 ~ 4.0 hour at temperature 60 ~ 120 DEG C, and wherein aluminium salinity is (with Al
3+meter) 0.2 ~ 4.0mol/L, inorganic acid or organic acid concentration are (with H
+meter) 0.2 ~ 2.0mol/L, aluminium salt is (with Al
3+meter) with inorganic acid or organic acid (with H
+meter) mol ratio be 0.2 ~ 20, the weight ratio 3:1 ~ 50:1 of aluminium salt and inorganic acid or organic acid mixed solution and molecular sieve.The Y zeolite character obtaining the present invention's use is as follows: specific area 800m
2/ g ~ 900 m
2/ g, total pore volume 0.40ml/g ~ 0.50ml/g, relative crystallinity 90% ~ 130%, sial (SiO
2/ Al
2o
3) mol ratio 20 ~ 100, preferably 30 ~ 100, cell parameter is 2.434 ~ 2.440nm, and meleic acid amount 0.3 ~ 0.8mmol/g, B acid/L acid is more than 7.0, preferably more than 8.0, sodium oxide content≤0.05wt%, preferably≤0.01wt%.
The preferred Y zeolite of the present invention is not when removing framework aluminum, not only can remove the non-framework aluminum fragment be almost all deposited in secondary pore, but also the non-framework aluminum fragment be filled in a large number in micropore can be removed, when keeping molecular sieve high-crystallinity, improve the amount of removing of non-framework aluminum in the molecular sieve after hydrothermal treatment consists, improve the silica alumina ratio of molecular sieve, increase the specific area of molecular sieve, adopt suitable hydrothermal conditions simultaneously, improve acidity and the acid distribution of molecular sieve, especially the distribution of B acid and L acid, and the secondary pore duct formed after making hydrothermal treatment consists becomes very " unobstructed ".The formation of secondary pore, be favourable to macromolecular reaction, large molecule more easily enters crystals can touch more activated centre, makes product more easily diffuse out simultaneously, and the acid centre of Y molecular sieve after process is evenly distributed, and can reduce second pyrolysis.Sodium oxide content in this modified Y molecular sieve can drop to below 0.01wt%, and the activity that can to make by this molecular sieve be the hydrocracking catalyst of active component increases, simultaneously can the performance of promoting catalyst Hydrogenation better.Catalyst of the present invention adopts this Y type molecular sieve as acidic components, the suitable hydrocracking catalyst as high-output qulified naphtha, jet fuel and diesel oil, improves the activity and selectivity of catalyst.
In hydrocracking catalyst preparation method of the present invention, described washing can adopt conventional method to carry out, such as adopt deionized water washing 2 ~ 5 times, drying condition before shaping is as follows: drying 2 ~ 10 hours at 100 ~ 150 DEG C, drying condition after shaping is as follows: at 100 ~ 150 DEG C dry 2 ~ 10 hours, and described roasting is roasting 3 ~ 10 hours at 450 ~ 650 DEG C.
Hydrocracking catalyst of the present invention adopts coprecipitation method preparation, and acidic components and active metal component coprecipitation get off, and metal loading is unrestricted, and metal dispersion is good.And the present invention is not with the NH that coprecipitation method is conventional
3.h
2o is precipitating reagent, avoids a large amount of ammonia and nitrogen pollutions.
Present invention employs sodium metaaluminate is aluminium source, by its be dissolved with CO
2gas carry out plastic reaction containing in Ni, W component salt and organic solvent mixed solution, to make in plastic thing, except forming precipitation of hydroxide, after reaction, to define CO
3 2-or HCO
3 -, after adding heteroion, precipitated metal thing caking property strengthens, and makes catalyst easily shaping, improves the intensity of catalyst, simultaneously CO
3 2-or HCO
3 -can remove during ion roasting, pollution-free and without the need to washing, and generate Ni
xw
yo
zcomposite oxides and Al
2o
3the mixture homogeneous grain size of precursor, improves the physico-chemical property of catalyst, has larger specific area and pore volume, reasonably pore structure.In roasting process, release a certain amount of carbon dioxide, under the percussion of gas, not only improve the pore structure of catalyst, but also make more metal active position be exposed to the surface of catalyst.Add organic solvent during plastic and enhance active metal dispersiveness, improve the utilization rate of active metal.The inventive method is pollution-free in preparation process, catalyst easy-formation, has larger specific area and pore volume, reasonably pore size distribution, originally intensive active metal decentralization can be improved, fully expose the high hydrogenation sites of Ni-W, add the coordinative role between active metal.Make have more multimachine close to active and acid centre, can effectively improve the activity of hydrocracking catalyst containing heteroatomic labyrinth hydrocarbon molecule.
It is dispersed that catalyst of the present invention has bigger serface, large pore volume, reasonably pore size distribution and good active metal, between active metal, coordinative role strengthens, a large amount of active metals comes out equably, and acid centre can be made fully to contact with hydrogenation sites.The preferred Y zeolite of the present invention is dispersed in the homogeneous system of amorphous silicon aluminium carrier and active metal formation, active metal and acid function can be made to play one's part to the full, thus the hydrocracking catalyst of gained is applicable in the hydrocracking process process of high-output qulified naphtha, jet fuel and diesel oil.
Detailed description of the invention
In hydrocracking catalyst of the present invention, hydrogenation active metals is group vib metal and group VIII metal, and group vib metal is preferably W and/or Mo, group VIII metal Co and/or Ni.Auxiliary agent is IVB race metal, is preferably Ti and/or Zr.Contain hydrogenation active metals, silicon in preparation, preferably contain in the process of acidic mixed solution A of auxiliary agent, hydrogenation active metals and auxiliary agent can adopt water soluble compound soluble in water formulated, such as tungsten source can adopt one or more in ammonium metatungstate, sodium tungstate, molybdenum source can adopt molybdenum trioxide, ammonium molybdate, cobalt source can adopt cobalt nitrate, nickel source can adopt in nickel nitrate, nickel chloride, basic nickel carbonate one or more, silicon source can adopt in Ludox, sodium metasilicate one or more.Titanium source can adopt in Titanium Nitrate, titanium sulfate, titanium chloride etc. one or more, zirconium source can adopt in zirconium nitrate, zirconium chloride, zirconium oxychloride etc. one or more.Containing Al in described sodium metaaluminate alkaline solution B
2o
3concentration is 10 ~ 40g/L solution.
The heavy charge scope that catalyst prepared by the inventive method is suitable for is very wide, they comprise vacuum gas oil (VGO), coker gas oil, deasphalted oil, thermal cracking gas oil, catalytic gas oil, the various hydrocarbon ils of catalytic cracking circulation wet goods, also can combinationally use, raw material is the hydro carbons of 250 ~ 550 DEG C usually containing boiling point, and nitrogen content can at 50 ~ 2500 μ g/g.
Hydrocracking catalyst of the present invention can be used in conventional hydrocracking process, be specially adapted to the hydrocracking process of product for the purpose of high-output qulified naphtha, jet fuel and diesel oil, its hydrocracking operation condition is as follows: reaction temperature is 300 ~ 500 DEG C, is more preferably 350 ~ 450 DEG C; Pressure is 6 ~ 20MPa, is more preferably 13 ~ 17MPa; During liquid, volume space velocity is 0.5 ~ 3 hr
-1, preferably 0.8 ~ 1.5 h
-1; Hydrogen to oil volume ratio is 400:1 ~ 2000:1, preferably 800:1 ~ 1500:1.
In the present invention, specific area and pore volume adopt low temperature liquid nitrogen physisorphtion, relative crystallinity and cell parameter adopt x-ray diffraction method, silica alumina ratio adopts chemical method, meleic acid amount, B acid amount and L acid amount adopt Pyridine adsorption IR spectra method, wherein the summation of B acid amount and L acid amount is meleic acid amount, and sodium content adopts plasma emission spectrometry.In the present invention, wt% is mass fraction, and v% is volume fraction.
Embodiment 1
Concrete preparation process is as follows:
(1) acid solution A is prepared: configuration is the nickel chloride solution 200 milliliters of 145g/l containing NiO, containing WO
3the ammonium metatungstate of 92g/l 1000 milliliters, containing ZrO
2120g/l zirconyl chloride solution 130 milliliters, and be mixed in after in the container of 5 liters, add 200 grams of tetraethylammonium bromides in container, add 800 milliliters of water purification dilutions.Preparation is containing SiO
2rare water glass solution of 72g/l 550 milliliters, adds in mixing salt solution above under agitation, prepares acid solution A.The CO that concentration is 85v% is passed in solution A
2, make CO in the gas in tank
2concentration is 80v%, hermetically sealed can;
(2) alkaline sodium aluminate solution B is configured: configuration is containing Al
2o
3concentration is 28g/l alkaline solution 3000ml;
(3) react plastic with working solution A, gelling temperature 45 DEG C, gelation time 1 hour in retort solution B being added sealing, at the end of the pH value of plastic slurries be 7.8.CO in water purification neutralization reaction tank
2al in the total amount of gas and alkaline working solution B
2o
3mol ratio is 3.5;
(4) after cemented into bundles, when constantly stirring, add the Y zeolite suspension (preparing by CN101380588A embodiment 1) accounting for total catalyst weight 15wt% through hydrothermal treatment consists modification, character is in table 4, in make it be dispersed in mixed serum that plastic obtains, leave standstill aging 4 hours at about 70 DEG C;
(5) filter, 60 DEG C of dryings 6 hours, roll, with the orifice plate extruded moulding of diameter 3 millimeters.Wash with water purification under room temperature.Then 110 DEG C of dryings 8 hours, 500 DEG C of roastings 4 hours, obtain catalyst A.Catalyst composition and main character are in table 1.
Embodiment 2
Compared with embodiment 1, by the catalyst B constituent content proportioning in table 1, the organic solvent added in acid solution is 180 grams of ethylene glycol, Kaolinite Preparation of Catalyst B, and difference is: will be dissolved with CO
2the solution A of gas and solution B stream adds plastic in retort, the pH value regulating slurries in retort is 8.5, and gelling temperature 45 DEG C, finally obtains catalyst B, and composition and main character are in table 1.
Embodiment 3
Compared with embodiment 1, by the catalyst component C content proportioning in table 1, the organic solvent added in acid solution is 150 grams of tetraethylammonium bromides, Kaolinite Preparation of Catalyst C, difference is: just gelling temperature is transferred to 60 DEG C, and with adjusting hole structure, catalyst composition and main character are in table 1.
Embodiment 4
Compared with embodiment 1, by the catalyst D constituent content proportioning in table 1, the organic solvent added in acid solution is 180 grams of ethylenediamines, Kaolinite Preparation of Catalyst D, and difference is: will be connected with CO
2the solution A of gas adds in solution B reaction plastic in retort, and catalyst composition and main character are in table 1.
Comparative example 1
According to method preparation disclosed in CN101239324A, catalyst composition forms identical with embodiment 1, and concrete steps are as follows:
(1) preparation is containing Al
2o
3concentration is the liquor alumini chloridi 1120 milliliters of 75g/l, is the nickel chloride solution 200 milliliters of 145g/l, containing ZrO containing NiO
2120g/l zirconyl chloride solution 130 milliliters, and be mixed in the container of 5 liters, add 2000 milliliters of water purification dilutions;
(2) rare water glass solution is prepared, containing SiO
2(2) are added in (1) by the water glass solution of 72g/l 550 milliliters under agitation;
(3) ammoniacal liquor is added under agitation the mixture of (1) and (2) until pH value 5.2;
(4) sodium tungstate solution 1000 milliliters is prepared, containing WO
3for 92g/l, and join in the mixture of (1)+(2)+(3) under agitation;
(5) continue to add ammoniacal liquor until pH value is 7.8;
(6) whole plastic process should be carried out at 60 DEG C;
(7) mixture leaves standstill aging 4 hours within the scope of 70 DEG C; Add the Y molecular sieve that molecular sieve is prepared by CN101380588A embodiment 1 before aging, Y molecular sieve accounts for 15% of total catalyst weight, and character is in table 4;
(8) filter, 60 DEG C of oven dryings 6 hours, roll, with the orifice plate extruded moulding of diameter 3 millimeters; Wash with the ammonium acetate solution of pH=8.8 under room temperature; Then 110 DEG C of oven dryings 8 hours, 500 DEG C of roastings 4 hours, obtain reference agent E, composition and main character are in table 1.
Comparative example 2
According to method preparation disclosed in CN101172261A, catalyst composition forms identical with embodiment 1, and add molecular sieve after cemented into bundles, concrete steps are as follows:
(1) acid solution A is prepared: configuration is the nickel chloride solution 200 milliliters of 145g/l containing NiO, containing WO
3the ammonium metatungstate of 92g/l 1000 milliliters, containing ZrO
2120g/l zirconyl chloride solution 150 milliliters, and be mixed in the container of 5 liters, add 1100 milliliters of water purification dilutions.Preparation is containing SiO
2rare water glass solution of 68g/l 550 milliliters, adds in mixing salt solution above under agitation;
(2) alkaline solution B is configured: configuration is containing Al
2o
3concentration is 28g/l alkalescence sodium aluminate solution 3000ml;
(3) by A, B solution drip enters plastic in plastic cans, gelling temperature remains on 60 DEG C, and pH value is in 6.5 ~ 8.5 scopes.A, B solution will ensure to drip off simultaneously, constant to ensure that catalyst distribution evenly forms;
(4) after cemented into bundles, when constantly stirring, the Y molecular sieve prepared by CN101380588A embodiment 1 is added, molecular sieve accounts for total catalyst weight 18wt%, character, in table 4, in make it be dispersed in mixed serum that plastic obtains, leaves standstill aging 4 hours at about 70 DEG C;
(5) filter, 60 DEG C of dryings 6 hours, roll, with the orifice plate extruded moulding of diameter 3 millimeters.Wash with water purification under room temperature.Then 110 DEG C of dryings 8 hours, 500 DEG C of roastings 4 hours, obtain reference agent E, and composition and main character are in table 1.
Comparative example 3
By embodiment 2 catalyst composition and preparation method, do not add organic reagent, prepare reference agent G.Composition and main character are in table 1.
Embodiment 5
Middle oil type hydrocracking catalyst A, B, D of the present invention and reference catalyst E, F evaluation result on midget plant are compared.Process conditions: reaction pressure is 14.7MPa, hydrogen to oil volume ratio 1200, volume space velocity 1.0h
-1, evaluate the Iranian VGO heavy distillate of raw material, its main character is in table 2, and table 3 lists evaluation result;
As can be seen from catalyst preparation process, in reference agent F plastic process, prepare metalliferous material bad adhesion, material particles be large, intensity difference.Can find out that catalyst A, B, D activity and the middle distillates oil selectivity adopting the present invention to prepare all slightly is better than reference agent E and F from the data of table 3.
Table 1 catalyst composition and character
| Catalyst is numbered | A | B | C | D | E | F | G |
| Catalyst forms | |||||||
| NiO， wt% | 11 | 8 | 10 | 14 | 11 | 11 | 8 |
| WO 3，wt% | 25 | 22 | 23 | 21 | 25 | 25 | 22 |
| SiO 2，wt% | 27 | 31 | 32 | 27 | 27 | 27 | 31 |
| Al 2O 3，wt% | 30 | 33 | 30 | 38 | 30 | 30 | 33 |
| Other/wt% | ZrO 2/7.0 | ZrO 2/6.0 | TiO 2/5.0 | - | ZrO 2/7.0 | ZrO 2/7.0 | ZrO 2/6.0 |
| The content of Y molecular sieve in catalyst, wt% | 15 | 18 | 13 | 17 | 15 | 15 | 18 |
| Catalyst property | |||||||
| Specific area, m 2/g | 286 | 296 | 301 | 297 | 209 | 196 | 288 |
| Pore volume, mL/g | 0.345 | 0.354 | 0.351 | 0.349 | 0.238 | 0.245 | 0.298 |
| Intensity, N/mm | 20.1 | 21.5 | 20.5 | 20.7 | 18.7 | 17.5 | 20.3 |
Table 2 feedstock oil main character
| Project | Analysis result |
| Density (20 DEG C), g/cm 3 | 0.9206 |
| Boiling range scope, DEG C | |
| IBP/10% | 328/413 |
| 30%/50% | 450/471 |
| 70%/90% | 493/522 |
| 95%/EBP | 534/545 |
| N，mg/g | 1575 |
| C，wt% | 85.35 |
| H，wt% | 12.10 |
| Carbon residue, wt% | 0.32 |
Table 3 evaluating catalyst result
| Catalyst is numbered | A | B | D | E | F | G |
| Reaction temperature, DEG C | 368 | 367 | 369 | 376 | 378 | 375 |
| Product yield and character | ||||||
| Heavy naphtha | ||||||
| Yield, wt% | 9.2 | 9.4 | 9.3 | 10.9 | 10.8 | 10.0 |
| Virtue is dived, wt% | 61.3 | 61.1 | 61.3 | 60.3 | 60.0 | 60.3 |
| Jet fuel | ||||||
| Yield, wt% | 36.9 | 37.0 | 36.8 | 33.9 | 32.5 | 35.5 |
| Smoke point, mm | 27 | 28 | 27 | 23 | 24 | 25 |
| Aromatic hydrocarbons, v% | 6.4 | 6.3 | 6.2 | 7.8 | 8.0 | 7.6 |
| Diesel oil | ||||||
| Yield, wt% | 21.0 | 20.9 | 20.8 | 18.6 | 19.4 | 20.2 |
| Cetane number | 59.8 | 59.6 | 60.1 | 57.3 | 56.8 | 58.1 |
| Tail oil | ||||||
| Yield, wt% | 29.1 | 28.7 | 28.9 | 29.8 | 31.1 | 29.0 |
| BMCI value | 7.2 | 6.8 | 7.0 | 13.1 | 13.9 | 10.0 |
| Chemical hydrogen consumption, wt% | 2.35 | 2.32 | 2.33 | 2.43 | 2.46 | 2.38 |
| Liquid is received, wt% | 96.1 | 96.0 | 95.8 | 93.2 | 93.8 | 94.7 |
The character of the Y zeolite that table 4 the present invention relates to
| Character | Y zeolite |
| Relative crystallinity, % | 104 |
| Cell parameter, nm | 2.432 |
| SiO 2/Al 2O 3，mol/mol | 50.6 |
| Specific area, m 2/g | 869 |
| Pore volume, ml/g | 0.462 |
| Infrared total acid, mmol/g | 0.456 |
| B acid/L acid | 9.03 |
| Na 2O，wt% | 0.093 |
Claims (6)
1. the preparation method of a body phase hydrocracking catalyst, described hydrocracking catalyst comprises amorphous aluminum silicide, Y zeolite, hydrogenation active metals component, wherein hydrogenation active metals is group vib metal and group VIII metal, preparation process is as follows: preparation, containing the acidic mixed solution A of hydrogenation active metals, silicon and organic solvent, passes into CO in solution A
2gas; Preparation sodium metaaluminate alkaline solution B, by solution B with pass into CO
2the solution A reaction plastic of gas, at the end of reaction, the pH value controlling slurries in retort is 7.0 ~ 9.0; Then the suspension adding Y zeolite mixes, and the mixture of gained filters, the filter cake drying obtained, then obtains hydrocracking catalyst through shaping, washing, drying, roasting; Add CO
2al in the total amount of gas and alkaline solution B
2o
3mol ratio be 2 ~ 8; Organic solvent used is selected from containing one or more in oxygen or nitrogenous organic compound, described organic solvent with the mol ratio of the group vib metal of oxide basis and group VIII metal sum for 0.1 ~ 3.0;
In described acidic mixed solution A, alkaline solution B plastic process, controlling gelling temperature is 40 ~ 70 DEG C, controls gelation time at 0.5 ~ 3.0 hour;
CO is passed in solution A
2gas, makes CO in solution A
2concentration reaches capacity; CO used
2the volumetric concentration of gas is 80v% ~ 95v%;
Described oxygen-containing organic compound is one or more in ethylene glycol, glycerine, diethylene glycol, butanediol, aminotriacetic acid, and organic compounds containing nitrogen is one or more in ethylenediamine, ethylenediamine tetra-acetic acid, tetraethylammonium bromide, tetraethyl ammonium hydroxide, 4-propyl bromide, softex kw;
Containing adjuvant component in described hydrocracking catalyst, described adjuvant component is IVB race metal, the content of IVB family metal oxide in hydrocracking catalyst is 1wt% ~ 10wt%, in hydrocracking catalyst preparation process, preparing in acid solution A process the compound added containing adjuvant component;
The character of Y zeolite used is as follows: specific area 800m
2/ g ~ 900m
2/ g, total pore volume 0.40ml/g ~ 0.50ml/g, relative crystallinity 90% ~ 130%, SiO
2/ Al
2o
3mol ratio 20 ~ 100, cell parameter is 2.434 ~ 2.440nm, and meleic acid amount 0.3 ~ 0.8mmol/g, B acid/L acid is more than 7.0, sodium oxide content≤0.05wt%;
The drying condition of shaping front gained filter cake is as follows: at 100 ~ 150 DEG C dry 2 ~ 10 hours, and the drying condition after shaping is as follows: at 100 ~ 150 DEG C dry 2 ~ 10 hours, and described roasting is roasting 3 ~ 10 hours at 450 ~ 650 DEG C.
2. in accordance with the method for claim 1, it is characterized in that described solution B and pass into CO
2during the solution A reaction plastic of gas, adopt and flow plastic method, tank plastic method or method that both combine; And when flowing plastic, the pH value regulating slurries in retort is 7.0 ~ 9.0.
3. in accordance with the method for claim 1, it is characterized in that in described hydrocracking catalyst, with the weight of catalyst for benchmark, the content of group vib metal oxide is 10wt% ~ 50wt%, the content of group VIII metal oxide is 1wt% ~ 20wt%, the content of Y zeolite is 10wt% ~ 40wt%, and the content of amorphous aluminum silicide is 30wt% ~ 60wt%.
4. in accordance with the method for claim 3, it is characterized in that described group vib metal is W and/or Mo, group VIII metal is Co and/or Ni.
5. in accordance with the method for claim 1, it is characterized in that described IVB race metal is Ti and/or Zr.
6. in accordance with the method for claim 1, it is characterized in that described organic solvent with the mol ratio of the group vib metal of oxide basis and group VIII metal sum for 0.3 ~ 2.0.
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| CN106179514B (en) * | 2015-04-30 | 2018-10-12 | 中国石油化工股份有限公司 | A kind of hydrocracking catalyst and preparation method thereof containing heteropoly acid |
| CN106179288B (en) * | 2015-04-30 | 2018-10-12 | 中国石油化工股份有限公司 | A kind of hydrocracking catalyst and its preparation method |
| CN106179480B (en) * | 2015-04-30 | 2018-10-12 | 中国石油化工股份有限公司 | A kind of Hydrobon catalyst composition and preparation method thereof |
| CN106179466B (en) * | 2015-04-30 | 2019-01-25 | 中国石油化工股份有限公司 | The preparation method of hydrocracking catalyst |
| CN106179380B (en) * | 2015-04-30 | 2018-10-12 | 中国石油化工股份有限公司 | A kind of Hydrobon catalyst and preparation method thereof |
| CN106179465B (en) * | 2015-04-30 | 2018-12-21 | 中国石油化工股份有限公司 | The preparation method of hydrocracking catalyst |
| CN106179463B (en) * | 2015-04-30 | 2018-10-12 | 中国石油化工股份有限公司 | Hydrocracking catalyst and its preparation method |
| CN106179464B (en) * | 2015-04-30 | 2018-11-02 | 中国石油化工股份有限公司 | A kind of preparation method of hydrocracking catalyst |
| CN106179391B (en) * | 2015-04-30 | 2019-01-25 | 中国石油化工股份有限公司 | Hydrocracking catalyst and preparation method thereof |
| CN106179461B (en) * | 2015-04-30 | 2018-10-12 | 中国石油化工股份有限公司 | A kind of preparation method of hydrocracking catalyst |
| CN111822020B (en) * | 2019-04-18 | 2023-04-14 | 中国石油化工股份有限公司 | Rare earth-containing hydrofining catalyst and preparation method thereof |
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