CN103007999A - Hydrocracking catalyst and preparation method thereof - Google Patents
Hydrocracking catalyst and preparation method thereof Download PDFInfo
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- CN103007999A CN103007999A CN2011102888377A CN201110288837A CN103007999A CN 103007999 A CN103007999 A CN 103007999A CN 2011102888377 A CN2011102888377 A CN 2011102888377A CN 201110288837 A CN201110288837 A CN 201110288837A CN 103007999 A CN103007999 A CN 103007999A
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Abstract
The invention relates to a hydrocracking catalyst and a preparation method thereof. The hydrocracking catalyst consists of hydrogenation active metal and a carrier structured by a modified composite molecular sieve and amorphous aluminium silicate; the hydrogenation active metal is molybdenum and/or tungsten, and/or cobalt, and/or nickel; the molybdenum and/or the tungsten accounts for 15.0-30.0% of the weight of the catalyst as weighed by oxide; the cobalt and/or the nickel accounts for 4.0-8.0% of the weight of the catalyst as weighed by oxide; the balance is the carrier structured by the modified composite molecular sieve and amorphous aluminium silicate; and the modified composite molecular sieve accounts for 10-20% and the amorphous aluminium silicate accounts for 80-90% by metering as the weight of the catalyst. The catalyst has the advantages that the raw materials are cheap and easy to buy; the preparation process is simple and easy to operate and has no generation of poisonous and harmful substances; the adaptability directing at the feature change of the raw materials; and the catalyst is suitable for experiment research on the existing hydrocracking process technology, can effectively solve the laboratory research difficulty and provides a reliable guarantee for the research and implementation of the hydrocracking process technology.
Description
Technical field:
The present invention relates to a kind of hydrocracking catalyst and preparation method thereof, particularly a kind of hydrocracking catalyst that contains zeolite and preparation method thereof.
Background technology:
In recent years, demand to clean fuel and high-quality industrial chemicals in the world wide increases day by day, and that the main feature of hydrocracking technology is adaptability to raw material is strong, product solution flexibly, high, the good product quality of purpose product selectivity and added value be high, can directly produce multiple high-quality oil product (such as gasoline, jet fuel, diesel oil, the lube base wet goods) and high-quality industrial chemicals (such as the raw materials for production of benzene,toluene,xylene, ethene etc.).Therefore, variation and market are to the demand of high-quality oil product year by year along with crude quality, and this just impels hydrocracking technology to be developed rapidly, and hydrocracking catalyst is one of wherein the most important and crucial factor.
The hydrocracking core technology is to develop and use suitable catalyst, and hydrocracking catalyst is a kind of bifunctional catalyst, and it has cracking activity and hydrogenation activity simultaneously, and the performance of such catalyst depends primarily on carrier.Carrier is the important component part of catalyst, usually not only disperses the place for metal active constituent provides, and carrier itself also participates in reaction simultaneously, works in coordination with other active component and finishes whole catalytic reaction.In the petroleum distillate hydrogenation catalyst, the carrier that contains amorphous aluminum silicide and molecular sieve namely has above-mentioned double action.Therefore, the performance of catalyst carrier has important function to final catalyst.Existing catalyst carrier for hydrgenating generally contains amorphous aluminum silicide, molecular sieve, aluminium oxide, and other refractory oxide.The catalyst carrier for hydrgenating that contains amorphous aluminum silicide and molecular sieve generally is used for the processes such as heavy oil hydrocracking, distillate hydrogenation removing impurities matter, hydro-upgrading of inferior diesel.
The molecular sieve carrier catalyst activity is higher, but middle distillates oil selectivity is lower than amorphous aluminum silicide carried catalyst, and the amplitude that middle distillates oil selectivity descends between on-stream period is large; For extinction recycle operation, also easily cause the gathering of condensed-nuclei aromatics.The amorphous aluminum silicide carried catalyst has very high middle distillates oil selectivity, and the amplitude that middle distillates oil selectivity descends between on-stream period is little, is difficult for causing the gathering of condensed-nuclei aromatics during extinction recycle operation.But since its acidity a little less than, make catalyst activity low, reaction temperature is high, the performance of catalyst hydrogenation performance is suppressed, and is difficult to the relatively poor raw material of Disposal quality, the device operating flexibility poor, part intermediate oil product quality neither be fine.
CNZL9811489.6 provides a kind of altogether standby heavy hydrocarbons hydrocraking catalyst of glue legal system, used molecular sieve is the Modified Zeolite Y of ZL96119840.0 report, but this Y zeolite is the molecular sieve of strong-acid type, therefore the hydrogenation cracking activity of this catalyst is higher, and middle distillates oil selectivity is relatively poor.This catalyst consists of: WO
322.0%, NiO9.0%, ZrO
27.0%, SiO
233.0%, Al
2O
329.0%, wherein Y zeolite accounts for about 7.0%, and specific surface is 254m
2/ g, pore volume are 0.312ml/g, and reaction temperature is at 396 ℃ when processing heavy distillate, and middle distillates oil selectivity is lower.
US4401556 discloses a kind of hydrocracking catalyst for the production of intermediate oil.This catalyst be take through the Y zeolite of dealuminzation as the cracking activity component, its silica alumina ratio is 4.5-35, cell parameter 2.420-2.445nm, the BET surface area is not less than 350m
2/ g.This catalyst is during take a kind of VGO as raw material, and its activity is relatively poor, and middle distillates oil selectivity is not high yet.
US5670590 discloses a kind of hydrocracking catalyst, and purpose is voluminous naphtha cut, is characterized in having used a kind of USY molecular sieve.This USY molecular sieve is by the exchange of the former powder process of NaY ammonium nitrate, roasting, and then obtains through ammonium nitrate exchange, a roasting, cell parameter 2.438～2.442nm, and sodium content is higher, generally about 1wt%.This catalyst activity is low, heavy naphtha selectively be not very high, hydrogen consumption is also larger.
Hydrocracking catalyst in the above-mentioned patent adopts the modified Y molecular sieve of different performance, and this is because method of modifying is different, has therefore also just caused the difference on the catalyst performance.
Summary of the invention:
The purpose of this invention is to provide a kind of hydrocracking catalyst and preparation method thereof, catalyst have higher catalytic activity and intermediate oil selective, the process conditions that can be applied to more relax, and the heavy naphtha that can raise productivity and improve the quality.
Hydrocracking catalyst of the present invention comprises hydrogenation active metals and the carrier that is comprised of modification composite molecular screen and amorphous silicic aluminium, and wherein said modification composite molecular screen character is as follows: specific surface 350m
2/ g～550m
2/ g, total pore volume 0.25ml/g～0.35ml/g, relative crystallinity 90%～120%, cell parameter 2.435～2.445nm, silica alumina ratio 3.5～30 is preferably 15～25, and sodium oxide content≤0.05wt% is preferably≤0.01wt%.
Described hydrogenation active metals is the metal of group vib and/or Vlll family, and the group vib metal is preferably molybdenum and/or tungsten, and the metal of Vlll family is preferably and bores and/or nickel.With the weighing scale of catalyst, the mass percent content of group vib metal (take oxide) is that the mass percent content of the 15.0～30.0%, the Vlll family metal (take oxide) is 4.0～8.0%, and surplus is carrier.
The described carrier that contains the modification composite molecular screen, with the weighing scale of carrier, 10-20% modification composite molecular screen and 80%-90% amorphous silicic aluminium.
The objective of the invention is to realize by following scheme: obtain molecular sieve by industrial NaY molecular sieve and sodium type beta-molecular sieve are carried out modification, with amorphous silicic aluminium as carrier of hydrocracking catalyst.It is characterized in that:
(1) the NaY molecular sieve carries out ammonium exchange three times, 550 ℃ of constant temperature 4h, three roastings with ammonium salt solution before chemical treatment.
(2) in chemical treatment, adopt ammonium fluosilicate dealumination complement silicon and inorganic acid or organic acid mixed aqueous solution to process the molecular sieve of ion-exchange.
(3) with phosphoric acid solution and the solution that contains rare earth compound beta-molecular sieve is flooded modification.
The method of modifying of molecular sieve of the present invention comprises the steps:
(1) the NaY molecular sieve is placed ammonium salt solution, in 80-100 ℃ of water-bath, heat, stir lower ammonium exchange 0.5～2h, filter, with 10 times deionized water washing, put into crucible in the method for Muffle furnace with temperature programming behind 110 ℃ of oven dry 2h, be cooled to normal temperature behind 550 ℃ of constant temperature 4h; In this way, carry out three exchanges, three roastings obtain three and hand over the NaY molecular sieve of three roastings.
(2) in deionized water, add three and hand over the NaY molecular sieve of three roastings, stir and be warmed up to 80～150 ℃, be preferably 90～120 ℃, add the hexafluorosilicic acid aqueous ammonium, constant temperature stirred 0.1～4 hour, preferred 1～2 hour, the isolated molecule sieve, washing molecular sieve, filtration, drying.
(3) use inorganic acid or/and then the NaY type molecular sieve of organic acid mixed aqueous solution treatment step (2) gained filters, washes and drying, obtain Modified Zeolite Y of the present invention; Inorganic acid or organic acid can be one or more in hydrochloric acid, sulfuric acid, nitric acid, acetic acid, the citric acid.
(4) with sodium type beta-molecular sieve according to molecular sieve: ammonium salt: water=1: (0.1～1): the weight ratio of (5～10) is filtered after 0.5～1 hour in room temperature to 100 a ℃ lower exchange, with phosphorus-containing compound solution and the solution that contains transistion metal compound molecular sieve is flooded modification again, wherein maceration extract adjusting pH is 6～8, then dry, roasting.
The detailed process of catalyst carrier for hydrgenating preparation of the present invention is:
With kneadings such as modified Y molecular sieve, beta-molecular sieve, amorphous silicic aluminium, adhesive, extrusion aids, extruded moulding, drying and roasting are prepared into carrier; Described drying can be carried out under 80～150 ℃ temperature 2～5 hours, and roasting is 500～600 ℃ of roastings 2～5 hours.
The load of catalyst activity metal of the present invention, the content of tungsten (take oxide) is 15.0%～30.0%, the content of metallic nickel (take oxide) is 4.0%～8.0%; Can adopt carrying method conventional in the prior art, preferred infusion process, can be saturatedly soak, excessive soak or complexing is soaked, namely with the solution impregnated catalyst carrier that contains required active component, carrier behind the dipping was 100～150 ℃ of dryings 1～12 hour, then 450-600 ℃ of roasting 2～5 hours, make final catalyst.
The invention effect:
The invention discloses a kind of hydrocracking catalyst and preparation method thereof, the method can keep higher crystallization reservation degree by the modification to molecular sieve, can reach 75%-95%.In high like this crystallization reservation degree situation, further dwindle the lattice constant of Y molecular sieve, improve silica alumina ratio, obtain pore size moderate, pore distribution concentration, secondary pore is flourishing, and acid centre is few, the catalyst carrier that acid strength is moderate.Adopt the saturated infusion process in hole, excessive infusion process or complexing infusion process to prepare active strong, middle distillates oil selectivity is high, stable good hydrocracking catalyst.Can produce clean fuel and high-quality industrial chemicals with the technology that relaxes.The invention has the beneficial effects as follows: compare with other traditional method of modifying, the method can keep higher crystallization reservation degree, can reach 75%-95%.In high like this crystallization reservation degree situation, further dwindle the lattice constant of Y molecular sieve, improve silica alumina ratio, increase secondary pore.The method of modifying of this molecular sieve possesses substantive distinguishing features and marked improvement, is applicable to the Y molecular sieve preparation, possesses good practicality.
The specific embodiment
Analytical method of the present invention: specific surface and pore volume adopt the 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 (bronsted acid) acid amount and L (lewis acid) acid amount adopt the pyridine adsorption infra-red sepectrometry, wherein the summation of B acid amount and L acid amount is the meleic acid amount, and sodium content adopts plasma emission spectrometry.
Embodiment 1
A kind of preparation process of modification composite molecular screen is:
(1) gets NaY molecular sieve 20 grams and place 500 ml beakers, add 200 milliliters of mass fractions and be 10% ammonium nitrate solution, under agitation, be warmed up to 90 ℃, constant temperature 2 hours, product through filtration, washing, 110 ℃ of dryings 2 hours, then put into the Muffle furnace Program and be warming up to 550 ℃, roasting 4 hours, the operation above repeating 2 times, the modified molecular screen product is numbered A.
(2) get A molecular sieve 10 grams and place 250 milliliters of three-necked bottles, add (the NH that 100 ml concns are 5w%
4)
2SiF
6The aqueous solution under agitation, is warmed up to 90 ℃, constant temperature 4 hours, product through filtration, washing, 110 ℃ of dryings 2 hours and 550 ℃ of roastings 2 hours, obtain the modified molecular screen product, be numbered B.
(3) get B molecular sieve 20 grams and place 500 ml beakers, add 200 milliliters of nitric acid that contain 2w% by, 0.6mol/L nitric acid and 0.2mol/L citric acid mixed solution, under agitation, be warmed up to 80 ℃, constant temperature 8 hours, product through filtration, washing, 110 ℃ of dryings 4 hours, then repeat top operation 1 time, obtain the dealuminzation molecular sieve, be numbered C.
(4) with sodium type beta-molecular sieve according to molecular sieve: ammonium salt: the weight ratio of water=1: 1: 5 is filtered after 1 hour in room temperature to 100 a ℃ lower exchange, with the phosphoric acid solution of 0.5mol/L and the lanthanum chloride solution of 1mol/L molecular sieve is flooded modification again, wherein maceration extract adjusting pH is 6-8, then dry, roasting obtains molecular sieve, is numbered D.
(5) with kneadings such as an amount of molecular sieve C, molecular sieve D, amorphous silicic aluminium, adhesive, extrusion aids, extruded moulding, drying and roasting, be prepared into after the carrier, with the solution impregnating carrier that contains nickel nitrate and ammonium metatungstate after 12 hours, drying, roasting namely obtain the hydrocracking catalyst of oxidation state.
Embodiment 2
(NH in the step (2)
4)
2SiF
6Concentration of aqueous solution becomes 8wt%, and all the other preparation process are with embodiment 1.
Embodiment 3
With the phosphoric acid solution of 1mol/L and the lanthanum chloride solution of 1mol/L molecular sieve is flooded modification in the step (4), wherein maceration extract adjusting pH is 6-8, and all the other preparation process are with embodiment 1.
Comparative example
With NaY molecular sieve 5g: the ratio preparation of the water of ammonium sulfate 6.5g: 50mL, put into there-necked flask.Ion-exchange temperature is 95 ℃, and then time 1h, filters, and the last filtration of solution secondary ion exchange of the water of 6.5g ammonium sulfate: 50mL is used in washing again, washs moist filter cake, 600 ℃ of lower roasting 2h.
Y molecular sieve after the roasting becomes fine powder through grinding, and get the 5g fine powder: the water of 6.5g ammonium sulfate: 50mL, process is the same.
Through the Y molecular sieve after above-mentioned exchange and the hydrothermal treatment consists, grind into powder is got 5.0g in there-necked flask; Take by weighing in the water that 6.5g ammonium sulfate adds 50mL and be mixed with solution, join in the flask, heating water bath to 100 ℃, and then add 10% oxalic acid and the ammonium oxalate solution of 35mL, and stir 1h, reacted rear filtration drying, roasting.Obtain modified Y molecular sieve.
The modification way of beta-molecular sieve is with embodiment 1.
Claims (2)
1. hydrocracking catalyst is comprised of hydrogen activity metal and the carrier that is comprised of modification composite molecular screen and amorphous silicic aluminium, it is characterized in that:
Described hydrogenation active metals is molybdenum and/or tungsten, and/or bores, and/or nickel; Molybdenum and/or tungsten are counted 15.0～30.0% of catalyst weight with oxide; Brill and/or nickel are counted 4.0～8.0% of catalyst weight with oxide; Surplus is the carrier that modification composite molecular screen and amorphous silicic aluminium form; With the weighing scale of carrier, the modification composite molecular screen accounts for 10～20% and amorphous silicic aluminium 80～90%;
Described modification composite molecular screen is comprised of modification sodium type Y molecular sieve and modification sodium type beta-molecular sieve, has following character: specific surface 350m
2/ g～550m
2/ g, total pore volume 0.25ml/g～0.35ml/g, relative crystallinity 90%～120%, cell parameter 2.435～2.445nm, silica alumina ratio are 15～25, sodium oxide content is≤0.01wt%.
2. the preparation method of a hydrocracking catalyst claimed in claim 1 is characterized in that:
(1) the NaY molecular sieve is placed ammonium salt solution, in 80-100 ℃ of water-bath, heat, stir lower ammonium exchange 0.5～2h, filter, with 10 times deionized water washing, put into crucible in the method for Muffle furnace with temperature programming behind 110 ℃ of oven dry 2h, be cooled to normal temperature behind 550 ℃ of constant temperature 4h; In this way, carry out three exchanges, three roastings obtain three and hand over the NaY molecular sieve of three roastings;
(2) add three in deionized water and hand over the three NaY molecular sieves that roast, stir and be warmed up to 80～150 ℃, add the hexafluorosilicic acid aqueous ammonium, constant temperature stirred 0.1～4 hour, isolated molecule sieve, washing molecular sieve, filtration, drying;
(3) use inorganic acid or/and then the NaY type molecular sieve of organic acid mixed aqueous solution treatment step (2) gained filters, washes and drying, obtain Modified NaY type molecular sieve; Inorganic acid or organic acid are selected one or more in hydrochloric acid, sulfuric acid, nitric acid, acetic acid, the citric acid;
(4) with the sodium beta molecular sieve according to molecular sieve: ammonium salt: water=1: (0.1～1): the weight ratio of (5～10) is filtered after 0.5～1 hour in room temperature to 100 a ℃ lower exchange, with phosphorus-containing compound solution and the solution that contains the hydrogenation active metals compound molecular sieve is flooded modification again, wherein maceration extract adjusting pH is 6～8, then dry, roasting.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105642336A (en) * | 2014-12-04 | 2016-06-08 | 中国石油化工股份有限公司 | Preparation technique of hydrocracking catalyst |
| CN105709801A (en) * | 2014-12-04 | 2016-06-29 | 中国石油化工股份有限公司 | Preparation method for chemical hydrocracking catalyst |
| CN107376983A (en) * | 2016-05-17 | 2017-11-24 | 中国石油化工股份有限公司 | A kind of preparation method of solid acid alkylation catalysts and the alkylation catalyst prepared by this method |
| CN116924423A (en) * | 2023-07-20 | 2023-10-24 | 中国石油大学(华东) | Amorphous aluminum silicate |
| CN116924423B (en) * | 2023-07-20 | 2024-06-07 | 中国石油大学(华东) | Amorphous aluminum silicate |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105642336A (en) * | 2014-12-04 | 2016-06-08 | 中国石油化工股份有限公司 | Preparation technique of hydrocracking catalyst |
| CN105709801A (en) * | 2014-12-04 | 2016-06-29 | 中国石油化工股份有限公司 | Preparation method for chemical hydrocracking catalyst |
| CN105709801B (en) * | 2014-12-04 | 2018-01-16 | 中国石油化工股份有限公司 | A kind of preparation method of chemical industry type hydrocracking catalyst |
| CN105642336B (en) * | 2014-12-04 | 2018-04-10 | 中国石油化工股份有限公司 | A kind of technology of preparation method of hydrocracking catalyst |
| CN107376983A (en) * | 2016-05-17 | 2017-11-24 | 中国石油化工股份有限公司 | A kind of preparation method of solid acid alkylation catalysts and the alkylation catalyst prepared by this method |
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| CN116924423B (en) * | 2023-07-20 | 2024-06-07 | 中国石油大学(华东) | Amorphous aluminum silicate |
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Application publication date: 20130403 |