CN1211466C - Y-zeolite containing anti-nitrogen hydrocracking catalyst - Google Patents

Y-zeolite containing anti-nitrogen hydrocracking catalyst Download PDF

Info

Publication number
CN1211466C
CN1211466C CN 02144958 CN02144958A CN1211466C CN 1211466 C CN1211466 C CN 1211466C CN 02144958 CN02144958 CN 02144958 CN 02144958 A CN02144958 A CN 02144958A CN 1211466 C CN1211466 C CN 1211466C
Authority
CN
China
Prior art keywords
zeolite
pore volume
catalyst
catalyzer
sio
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
CN 02144958
Other languages
Chinese (zh)
Other versions
CN1508228A (en
Inventor
陈松
关明华
谷明镝
王继锋
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
China Petroleum and Chemical Corp
Sinopec Fushun Research Institute of Petroleum and Petrochemicals
Original Assignee
China Petroleum and Chemical Corp
Sinopec Fushun Research Institute of Petroleum and Petrochemicals
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by China Petroleum and Chemical Corp, Sinopec Fushun Research Institute of Petroleum and Petrochemicals filed Critical China Petroleum and Chemical Corp
Priority to CN 02144958 priority Critical patent/CN1211466C/en
Publication of CN1508228A publication Critical patent/CN1508228A/en
Application granted granted Critical
Publication of CN1211466C publication Critical patent/CN1211466C/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Landscapes

  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
  • Catalysts (AREA)

Abstract

The present invention relates to a nitrogen resistant type hydrocracking catalyst containing Y zeolite. The catalyst has high activity and high medium oil selectivity by matching selected Y zeolite having suitable properties with acidic amorphous silicon-aluminum having specific properties, a raw material having a high nitrogen content can be directly treated under the condition of no prerefining section, and the catalyst can meet the requirement of cracking activity of complete cycle operation. The catalyst can be used for a single-section and single-catalyst hydrocracking technology or a firstly-cracking and secondly-refining hydrocracking technology for producing clean fuel to the maximum.

Description

A kind of anti-nitrogen type hydrocracking catalyst that contains Y zeolite
Technical field
The present invention relates to a kind of hydrocracking catalyst that contains Y zeolite, particularly relate to a kind of anti-nitrogen type that contains Y zeolite, can be used for the hydrocracking catalyst of recycle to extinction technology.
Background technology
Hydrocracking process mainly can be divided into one-stage process and two-stage method, and operating method mainly can be divided into recycle to extinction and once pass through.Nobel metal hydrogen cracking catalyst is owing to the sulphur in the stock oil, nitrogen sensitivity, generally be used for two-stage method.Non-noble metal hydrocracking catalyst is widely used in the one-stage process technology single hop technology in other words, according to the characteristics at acidity of catalyst cracking center or the difference of anti-nitrogen poisoning performance, can be divided into one-stage serial or single hop list agent technology again.
Hydrocracking catalyst is a kind of dual-function catalyst, promptly has hydrogenating function and has the cracking function again, produces clean fuel so be particularly suitable for handling heavy hydrocarbon feedstocks inferior.On technology, amorphous type hydrocracking catalyst acidic cleavage central characteristics can directly be handled high nitrogen charging, is used for single hop list agent technology more, but the temperature of reaction height because the cracking ability is relatively poor, generally can not adopt the extinction recycle operation mode.The zeolite hydrocracking catalyst has satisfactory stability, life-span and activity, and the zeolite hydrocracking catalyst generally need have a hydrofining section to carry out denitrogenation, and Here it is, and one-stage serial technology is better, and it strengthens the flexibility of operation of hydrocracking process.
US5190903 discloses the low acidity zeolite that generally is used for oil type hydrocracking catalyst, and purpose is to improve the middle distillates oil selectivity of catalyzer, is characterized in having used a kind of NH 4-TPD acidity is preferably less than 1.5mmol/g low acidity Y zeolite, SiO 2/ Al 2O 3Mol ratio is less than 6, and lattice constant is 2.420-2.440nm, and the main preparation characteristic of the related zeolite of this patent is that the low natrolite after the hydrothermal treatment consists is carried out dry type roasting dehydroxylation, and the dehydroxylation temperature is more than 426 ℃.Handle a kind of VGO with this zeolite as the hydrocracking catalyst of acidic cleavage component preparation, when transformation efficiency was controlled at 85wt%, temperature of reaction was up to 405-425 ℃, and middle distillates oil selectivity has only 55-63%, and the middle distillates oil selectivity of catalyzer improves not obvious.CN1253859A discloses a kind of medium oil type hydrocracking catalyst, catalyzer contains 4～40% Y zeolite and 10～50% components such as amorphous aluminum silicide, because the zeolite content of this catalyzer is higher relatively and amorphous aluminum silicide content is relatively low, therefore anti-nitrogen is not strong, can only be used for the hydrocracking process with pre-refining.
Summary of the invention
At the deficiencies in the prior art, the invention provides a kind of active high, middle distillates oil selectivity is high, be applicable to and contain the Y zeolite hydrocracking catalyst in the no pre-refining section hydrocracking process.
The composition of nitrogen-resistant type zeolite type hydrocracking catalyst of the present invention comprises: (a) Y zeolite 1-10wt%; (b) acid amorphous aluminum silicide＞50wt% to 80wt%; (c) aperture aluminum oxide 0-30wt%; (d) group vib metal oxide 10-40wt%; (e) VIII metal oxide 1-10wt%.The surface-area of catalyzer is 200～300m 2/ g, pore volume 0.30-0.40ml/g.
Wherein Y zeolite has following character: SiO 2/ Al 2O 3Mol ratio is 5-20, is preferably 6-17, lattice constant 2.420～2.445nm, and the secondary pore pore volume of 2～10nm accounts for 30%～60% of total pore volume, specific surface 500-750m 2/ g, infrared acidity 0.25-0.50mmol/g, Na 2O content＜0.2wt%.
Wherein acid amorphous aluminum silicide has following character: SiO 2Content is 20～60%, specific surface 350-600m 2/ g, pore volume 0.9～1.5ml/g, infrared acidity 0.30-0.60mmol/g.
Pore volume 0.4～the 0.8ml/g of wherein little porous aluminum oxide, specific surface 150～300m 2/ g.
Wherein the group vib metal oxide mainly comprises the oxide compound of tungsten or molybdenum, and the VIII metal oxide mainly comprises the oxide compound of cobalt or nickel.
Hydrocracking catalyst of the present invention contains two kinds of character and the specific acid material of consumption is the cracking component, has guaranteed the lytic activity of catalyzer on the one hand, has improved selectivity of catalyst simultaneously.The more important thing is, the Y zeolite of selecting has lower acidity, and the content that selection suits cooperates with specific amorphous aluminum silicide, make it on catalyzer, have moderate acid site density, the catalyzer coking inactivation of avoiding the multidigit condensation reaction of intensive strong acid center to cause, with suitable hydrogenation active centre synergy, therefore have stronger anti-nitrogen performance simultaneously, can directly contact and carry out hydrocracking reaction with unpurified raw material.
Embodiment
Catalyzer of the present invention can adopt conventional method preparation, as adopting coprecipitation method, blending method or pickling process etc.Usually adopt pickling process, as amorphous aluminum silicide and zeolite component are mixed, add aperture alumina adhesive through the peroxy-nitric acid peptization mix pinch, extruded moulding obtains carrier, obtain by flooding hydrogenation active metals again.
The acid amorphous aluminum silicide that catalyzer of the present invention relates to can require to select in existing amorphous silicon aluminum according to character.The Y zeolite that relates to also can require to select in existing Y zeolite material according to character, but the Y zeolite that preferably adopts following process to handle.
With Na 2O content is raw material less than the Y zeolite of 3.0wt%, places the high-temperature roasting stove, at self water vapor or feed water vapor, and 450-600 ℃, under the 0.01-0.2MPa pressure water steam roasting 0.5-3.0 hour.Carry out ion-exchange techniques then and make Na 2O content is less than the Y zeolite of 0.2wt%.Na with above-mentioned preparation 2O content places the high-temperature roasting stove less than the Y zeolite of 0.2wt%, and at self water vapor or feeding water vapor, 550-700 ℃, 0.01-1.0MPa pressure water steam was handled 0.5-10 hour down, promptly got SiO 2/ Al 2O 3Mol ratio is the super-hydrophobic Y zeolite of 5.2-6.0.The above-mentioned super-hydrophobic Y zeolite that obtains with chemical process dealuminzation optionally, can be got SiO 2/ Al 2O 3Mol ratio is the super-hydrophobic Y zeolite of 5-20.
Catalyzer of the present invention can be used for the hydrocracking process of single hop list agent, or purified hydrocracking process after the first cracking, is used for maximum and produces clean fuel.Further specify the solution of the present invention and effect below by embodiment.
Embodiment 1
Take by weighing a kind of macroreticular acidic amorphous aluminum silicide (specific surface 520m 2/ g, pore volume 1.1ml/g, SiO 235wt%, infrared acidity 0.40mmol/g) 77.2g and a kind of Y zeolite 6.1g, add behind the mixing 120g (adding rare nitric acid peptization preparation) tackiness agent by the little porous aluminum oxide of 24.6g pore volume 0.42ml/g roll agglomerating after, after putting into the banded extruder extruded moulding, 110 ℃ of dryings 10 hours, 500 ℃ of activation made carrier in 4 hours, be total to the steeping fluid dipping with Mo-Ni again, then 110 ℃ of dryings 12 hours, and 500 ℃ of activation obtained catalyzer after 3 hours.Catalyzer finally consists of: amorphous aluminum silicide 51wt%, Y zeolite 5wt%, aluminum oxide 14wt%, nickel oxide 7.5wt%, Tungsten oxide 99.999 22.5wt%.Specific surface area of catalyst is 220m 2/ g, pore volume 0.33ml/g.
Wherein Y zeolite type treating processes is as follows:
Get 500g SiO 2/ A1 2O 3Be 5.2 NaY zeolite, be added to the NH that the 5000ml degree is 2M 4NO 3In the solution, stir down at 100 ℃, ion-exchange 2 hours exchanges secondary altogether, and filter then, wash to neutrality, and oven dry, obtain product I.Product I is placed the high-pressure rotary stove, and at 550 ℃, roasting is 2 hours under the 100% water vapor 0.1MPa pressure, obtains product II.Again product II is put into the NH that 5000ml concentration is 2M 4NO 3In the solution, stir ion-exchange 2 hours down, exchange altogether 3 times, filter then, wash to neutrality at 100 ℃, and oven dry, product III obtained.As in the high-pressure rotary stove, at 550 ℃, roasting is 4 hours under the 100% water vapour 0.2MPa pressure, obtains product IV with product III.Product IV is put into 4 liters of hydrochloric acid solns that concentration is 0.4M, handled 2 hours, filter, wash, dry, obtain the SiO of Y zeolite to neutral 2/ Al 2O 3Mol ratio is 8.5, lattice constant 2.430nm, specific surface 650m 2/ g, infrared acidity 0.36mmol/g, the pore volume of 2～10nm accounts for 35% of total pore volume.
This zeolite acidity is lower, but the characteristics of strength of acid are the acid sitess with all kinds of intensity of suitable proportion distribution, NH as shown in the table 4-TPD acidity (weighing by desorption temperature) distributes and finds out, its acidity distribution mainly is a 250-500 ℃ of represented middle strong acid center, its acidity accounts for 50.4% of total acidity, ℃ represented strong acid center simultaneously＞500, its acidity accounts for 21.1% of total acidity, thereby has also guaranteed the cracking activity to heavy hydrocarbon material when being used for catalyzer.
Zeolite NH involved in the present invention 4-TPD acidity and varying strength acidity distribution thereof
Acidity Acidity distribution
mmol/g 150-250℃ 250-400℃ 400-500℃ ＞500℃
1.21 28.5％ 35.2％ 15.2％ 21.1％
Embodiment 2
Take by weighing a kind of macroreticular acidic amorphous aluminum silicide (specific surface 460m 2/ g, pore volume 1.2ml/g, SiO 245wt%, infrared acidity 0.50mmol/g) 85.8g and a kind of Y zeolite 12.1g, add behind the mixing 120g (adding rare nitric acid peptization preparation) tackiness agent by the little porous aluminum oxide of 15.6g pore volume 0.42ml/g roll agglomerating after, after putting into the banded extruder extruded moulding, 110 ℃ of dryings 10 hours, 500 ℃ of activation made carrier in 4 hours, be total to the steeping fluid dipping with Mo-Ni again, then 110 ℃ of dryings 12 hours, and 500 ℃ of activation obtained catalyzer after 3 hours.Catalyzer finally consists of: amorphous aluminum silicide 60wt%, Y zeolite 10wt%, aluminum oxide 10wt%, nickel oxide 5.5wt%, Tungsten oxide 99.999 14.5wt%.Specific surface area of catalyst is 255m 2/ g, pore volume 0.41ml/g.
Wherein Y zeolite type treating processes is as follows:
Get 500g SiO 2/ Al 2O 3Be 5.2 NaY zeolite, be added to the NH that the 5000ml degree is 2M 4NO 3In the solution, stir down at 100 ℃, ion-exchange 2 hours exchanges secondary altogether, and filter then, wash to neutrality, and oven dry, obtain product I.Product I is placed the high-pressure rotary stove, and at 550 ℃, roasting is 2 hours under the 100% water vapor 0.1MPa pressure, obtains product II.Again product II is put into the NH that 5000ml concentration is 2M 4NO 3In the solution, stir ion-exchange 2 hours down, exchange altogether 3 times, filter then, wash to neutrality at 100 ℃, and oven dry, product III obtained.As in the high-pressure rotary stove, at 600 ℃, roasting is 4 hours under the 100% water vapour 0.4MPa pressure, obtains product IV with product III.Product IV is put into 4 liters of hydrochloric acid solns that concentration is 0.4M, handled 2 hours, filter, wash, dry, obtain the SiO of Y zeolite to neutral 2/ Al 2O 3Mol ratio is 11, lattice constant 2.428nm, specific surface 700m 2/ g, infrared acidity 0.22mmol/g, the pore volume of 2～10nm accounts for 40% of total pore volume.
Embodiment 3
According to embodiment 2 methods, adjust each amounts of components, final catalyzer consists of amorphous aluminum silicide 72wt%, Y zeolite 3wt%, aluminum oxide 5wt%, nickel oxide 5.5wt%, Tungsten oxide 99.999 14.5wt%.Other is with embodiment 2.
Embodiment 4 evaluating catalysts
It is a kind of heavy distillate that embodiment handles raw material: the wax tailings CGO of 90% heavy vacuum distillate VGO blending 10%, this petroleum hydrocarbon material main character is: proportion 0.9045cm 3/ g, 350 ℃-565 ℃ of boiling ranges, carbon residue 0.40wt%, sulphur 2.06wt%, nitrogen 2226 μ g/g.
Evaluating catalyst condition: reaction pressure 15MPa, hydrogen-oil ratio 1200, volume space velocity 1.0hr -1, adopt＞370 ℃ of extinction recycle operation modes, control per pass conversion 70wt%, stock oil directly contacts with hydrocracking catalyst with hydrogen heating back, need not make with extra care.It is to obtain divided by the liquid yield that has transformed (100 deduct tail oil) by intermediate oil (rocket engine fuel and/or diesel oil distillate) yield that middle distillates oil selectivity calculates.
Embodiment 1 Embodiment 2 Embodiment 3
Deactivation rate, ℃/day 0.05 0.04 0.04
Initial reaction temperature, ℃ 398 395 397
Middle distillates oil selectivity, % 80.3 79.8 80.1

Claims (7)

1, a kind of anti-nitrogen type hydrocracking catalyst that contains Y zeolite is characterized in that comprising in its composition of final catalyst weight: (a) Y zeolite 1-10wt%; (b) acid amorphous aluminum silicide＞50wt% to 80wt%; (c) aperture aluminum oxide 0-30wt%; (d) group vib metal oxide 10-40wt%; (e) VIII metal oxide 1-10wt%; Wherein said group vib metal oxide comprises the oxide compound of tungsten or molybdenum, and the VIII family metal oxide comprises the oxide compound of cobalt or nickel.
2,, it is characterized in that described Y zeolite has following character: SiO according to the described catalyzer of claim 1 2/ Al 2O 3Mol ratio is 5-20, lattice constant 2.420～2.445nm, and the secondary pore pore volume of 2～10nm accounts for 30%～60% of total pore volume, specific surface 500-750m 2/ g, infrared acidity 0.25-0.50mmol/g, Na 2O content＜0.2wt%.
3,, it is characterized in that the SiO of described Y zeolite according to the described catalyzer of claim 2 2/ Al 2O 3Mol ratio is 6-17.
4,, it is characterized in that described acid amorphous aluminum silicide has following character: SiO according to the described catalyzer of claim 1 2Content is 20～60%, specific surface 350-600m 2/ g, pore volume 0.9～1.5ml/g, infrared acidity 0.30-0.60mmol/g.
5,, it is characterized in that the pore volume 0.4～0.8ml/g of described little porous aluminum oxide, specific surface 150～300m according to the described catalyzer of claim 1 2/ g.
6, according to the described catalyzer of claim 1, the surface-area that it is characterized in that catalyzer is 200～300m 2/ g, pore volume 0.30-0.40ml/g.
7,, it is characterized in that described Y zeolite adopts following process to handle: with Na according to the described catalyzer of claim 1 2O content is raw material less than the Y zeolite of 3.0wt%, places the high-temperature roasting stove, at self water vapor or feed water vapor, and 450-600 ℃, under the 0.01-0.2MPa pressure water steam roasting 0.5-3.0 hour; Carry out ion-exchange techniques then and make Na 2O content is less than the Y zeolite of 0.2wt%; The Y zeolite of above-mentioned preparation is placed the high-temperature roasting stove, and at self water vapor or feeding water vapor, 550-700 ℃, 0.01-1.0MPa pressure water steam was handled 0.5-10 hour down; With the above-mentioned Y zeolite that obtains with chemical process dealuminzation optionally, SiO 2/ Al 2O 3Mol ratio is the super-hydrophobic Y zeolite of 5-20.
CN 02144958 2002-12-19 2002-12-19 Y-zeolite containing anti-nitrogen hydrocracking catalyst Expired - Lifetime CN1211466C (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN 02144958 CN1211466C (en) 2002-12-19 2002-12-19 Y-zeolite containing anti-nitrogen hydrocracking catalyst

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN 02144958 CN1211466C (en) 2002-12-19 2002-12-19 Y-zeolite containing anti-nitrogen hydrocracking catalyst

Publications (2)

Publication Number Publication Date
CN1508228A CN1508228A (en) 2004-06-30
CN1211466C true CN1211466C (en) 2005-07-20

Family

ID=34232189

Family Applications (1)

Application Number Title Priority Date Filing Date
CN 02144958 Expired - Lifetime CN1211466C (en) 2002-12-19 2002-12-19 Y-zeolite containing anti-nitrogen hydrocracking catalyst

Country Status (1)

Country Link
CN (1) CN1211466C (en)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102311784B (en) * 2010-07-07 2014-01-01 中国石油化工股份有限公司 Method for producing environment-friendly aromatic oil
CN112570016B (en) * 2019-09-30 2022-07-12 中国石油化工股份有限公司 Anti-nitrogen aromatic hydrocarbon type hydrocracking catalyst and preparation method and application thereof

Also Published As

Publication number Publication date
CN1508228A (en) 2004-06-30

Similar Documents

Publication Publication Date Title
CN101380589B (en) Hydrocracking catalyst and preparation method thereof
CN101380588B (en) Hydrocracking catalyst carrier and preparation method thereof
CN100513531C (en) Hydrocracking method of midbarrel oil circulation
CN100422295C (en) Method for producing food grade white oil by hydrogenating tail oil
CN100497547C (en) Hydrocracking method
CN103372457A (en) Catalytic cracking diesel oil hydro-upgrading catalyst and application thereof
CN109201072B (en) Catalytic cracking gasoline pre-hydrogenation catalyst and preparation method thereof
CN101402048B (en) Process for producing high-performance catalyst for hydrocracking
CN100497543C (en) Combined hydrocracking method
CN1202216C (en) Hydrocracking process for maximally producing middle distillate
CN1730614A (en) Catalytic cracking catalyst and its preparation method
CN1211466C (en) Y-zeolite containing anti-nitrogen hydrocracking catalyst
CN1211463C (en) One-time through hydrocracking process
CN100439479C (en) Combined processing method of faulty catalytic cracking diesel oil
JPS60219295A (en) Hydrogenation of heavy hydrocarbon oil
CN101328430B (en) Method for hydro-dearomatization for catalyzing diesel
CN1219031C (en) Beta-zeolite containing anti-nitrogen hydrocracking catalyst
CN100497545C (en) Parallel hydrocracking method
CN1188493C (en) Hydrocracking technology for increase production of low solidifying point diesel oil and ethylene producing raw material
CN100439478C (en) Hydrocracking method
CN100497544C (en) Distillate oil hydrogenation catalyst and its preparation method
CN104611049A (en) Catalytic diesel fuel reaction distillation method
CN102533315A (en) Method for hydro-dearomatization in catalytic cracking of diesel
CN109097096B (en) Method for pre-hydrogenation of catalytic cracking gasoline
CN1202217C (en) Recycle-cracking hydrocracking process

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant
CX01 Expiry of patent term

Granted publication date: 20050720

CX01 Expiry of patent term