CN103861647B

CN103861647B - A kind of hydrocracking catalyst containing heteropoly acid and application thereof

Info

Publication number: CN103861647B
Application number: CN201210526557.XA
Authority: CN
Inventors: 李海岩; 秦丽红; 吕倩; 王东青; 谢彬; 田然; 孙发民; 张文成; 于春梅; 戴宝琴; 王燕; 马宝利; 董春明; 徐铁刚; 马守涛; 张国甲; 杨晓东; 王亮
Original assignee: China Petroleum and Natural Gas Co Ltd
Current assignee: China Petroleum and Natural Gas Co Ltd
Priority date: 2012-12-10
Filing date: 2012-12-10
Publication date: 2016-01-20
Anticipated expiration: 2032-12-10
Also published as: CN103861647A

Abstract

The present invention relates to a kind of hydrocracking catalyst containing heteropoly acid; Comprise amorphous aluminum silicide, aluminium oxide, acidic components and hydrogenation active metals, acidic components comprise USY molecular sieve and high thermal stability heteropolyacid salt; USY molecular sieve sodium oxide content 0.01 ~ 0.1wt.%, skeleton SiO ₂: Al ₂o ₃mol ratio 6 ~ 15, specific area 600 ~ 950m ²the hole of/g, 1.7 ~ 10nm accounts for 40% ~ 60%; The heteropoly acid used is made up of Mo, W, La metal and P element, and molecular formula is H ₃pMo _12-X-Yw _xla _yo ₄₀nH ₂o, obtains nanoscale heteropolyacid salt by precipitation reaction, has resistance to 800 DEG C of high temperature and Undec heat endurance; This catalyst is used for fixed bed two-stage reforming, and catalytic production naphtha and tail oil industrial chemicals, high cetane number diesel oil, has liquid yield high, the selective height of industrial chemicals, the advantages such as good product quality.

Description

A kind of hydrocracking catalyst containing heteropoly acid and application thereof

Technical field

The present invention relates to a kind of hydrocracking catalyst containing heteropoly acid and application thereof, particularly contain the hydrocracking catalyst of ultra-low oxidized sodium content USY molecular sieve and high thermal stability heteropoly acid, belong to catalyst technical field.

Background technology

Current, countries in the world petroleum refining industry is all faced with oil reserved resources and reduces gradually, and oil property is heaviness, in poor quality increasingly, and naphtha, tail oil industrial chemicals and diesel oil demand constantly increase simultaneously.For alleviating industrial chemicals and fine-quality diesel oil situation in short supply, it is selective that the development requires hydrocracking catalyst of hydrocracking catalyst has high industrial chemicals, and object product is based on maximum naphtha and tail oil; For widening hydrocracking raw material scope, making hydrocracking catalyst have stronger adaptability to raw material, also requiring catalyst should have higher anti-nitrogen performance and height being done to the open loop cracking capability of raw material.These requirements are reacted on catalyst performance, are exactly to improve activity and anti-nitrogen, isomery performance and the open loop cracking performance that the industrial chemicals of catalyst naphtha and tail oil is selective, improve catalyst.For this reason, a kind of industrial chemicals type hydrocracking catalyst being suitable for heavy charge is needed.Existing industrial chemicals type hydrocracking catalyst mainly with modified Y molecular sieve, beta-molecular sieve etc. for acidic cracking components, with porous amorphous aluminum silicide and aluminium oxide for carrier, extrusion is shaped, and adopts infusion process preparation.

CN200710012081.7 discloses a kind of hydrocracking catalyst, containing the two micro porous molecular sieve of modification Y/ β, and other carrier material and hydrogenation active component.The aluminum weight ratio that wherein the two micro porous molecular sieve of modification Y/ β is total is 6.5 ~ 60.0, BET specific surface area 350 ~ 650m ²/ g, pore volume is 0.25 ~ 0.40ml/g, and infrared acidity is 0.50 ~ 1.5mmol/g.This invention method for preparing catalyst adopts infusion process, and the two micro porous molecular sieve of modification Y/ β carries out modification by the method for roasting after first mending silicon.This invention hydrocracking catalyst has higher activity when being used for heavy distillate hydrocracking, may be used for various types of hydrocracking process.

CN200710012080.2 discloses a kind of preparation method of high-activity hydrocracking catalyst, is acid cracking material, adopts infusion process preparation with Y/ β two micro porous molecular sieve, Y zeolite, beta-molecular sieves etc.Modification is carried out in the various molecular sieve mixing wherein related to, and processing method is first gas phase benefit silicon, hydrothermal treatment consists, ammonium salt exchange, roasting makes the processes such as ammonium salt decomposition.Hydrocracking catalyst prepared by the inventive method there is higher reactivity and intermediate oil selective, may be used for heavy distillate hydrocracking process.

CN200710012079.X discloses a kind of hydrocracking catalyst, containing modification Y/ β two micro porous molecular sieve, modified Y molecular sieve, modified beta molecular sieve and other carrier material and hydrogenation active component.Wherein the two micro porous molecular sieve aluminum weight ratio of modification Y/ β is 20.0 ~ 50.0, and BET specific surface area is 420 ~ 650m ²/ g, pore volume is 0.30 ~ 0.38ml/g, and infrared acidity is 0.65 ~ 1.2mmol/g.Method for preparing catalyst of the present invention adopts infusion process, and the two micro porous molecular sieve of modification Y/ β carries out modification by the method for roasting after first mending silicon.This invention hydrocracking catalyst has higher serviceability when being used for heavy distillate hydrocracking, may be used for various types of hydrocracking process.

CN03133815 discloses oil type hydrocracking catalyst and preparation method thereof in one, catalyst composition is carrier with amorphous aluminum silicide, with the Y zeolite through special modification for acidic components, the existing high degree of crystallinity of this molecular sieve, have again low cell parameter, acid site number is less in addition, and mainly moderate strength acid site, make this molecular sieve have very strong nitrogen resistance and break ring ability preferably, use the hydrocracking catalyst of this molecular sieve to have stronger anti-nitrogen ability.Catalyst of the present invention is used for, in heavy hydrocarbon single-stage hydrocracking technique, having the ability that higher anti-nitride is poisoning, high middle distillates oil selectivity and hydrogenation cracking activity.

One involved by CN1389545A contains Y molecular sieve 20 ~ 40wt.%, phosphorus heteropoly tungstic acid or silicotungstic heteropolyacid 5 ~ 20wt.%, nickel oxide 5 ~ 10wt.%, the catalyst of aluminium oxide 40 ~ 60wt.%.

CN100584458C contains hydrocracking catalyst of heteropoly acid and preparation method thereof, relates to hydrocracking catalyst of a kind of long chain alkane and preparation method thereof.A kind of large aperture, the highly active hydrocracking catalyst containing heteropoly acid and preparation method thereof are provided.Comprise heteropoly acid, hydrogenation component and carrier, carrier is porous heat-resistant inorganic material, hydrogenation component is bimetallic mixture, take catalyst weight as benchmark, in the content of catalyst components, heteropoly acid is 20 ~ 70wt.%, hydrogenation component nickel and cobalt total content are 5 ~ 20wt.%, and wherein cobalt is 1/10 ~ 3/5 with the content ratio of nickel.

Summary of the invention

The object of this invention is to provide a kind of hydrocracking catalyst containing heteropoly acid and application thereof.

A kind of hydrocracking catalyst containing heteropoly acid of the present invention, with amorphous aluminum silicide and aluminium oxide for carrier, with the USY molecular sieve of ultra-low oxidized sodium content and resistance to 800 DEG C and Undec heteropoly acid for acidic components, with group vib metal and VIII race's metal for hydrogenation active component.Wherein, group vib metal oxide content is 10 ~ 25wt.%, and VIII family metal oxide content is 1 ~ 10wt.%, USY molecular sieve accounts for 9 ~ 15wt.% of catalyst, heteropoly acid accounts for 1 ~ 5wt.%, and amorphous aluminum silicide accounts for 20 ~ 50wt.% of catalyst, and aluminium oxide accounts for 5 ~ 20wt.% of catalyst.

USY molecular sieve used in the present invention has following character: sodium oxide content 0.01 ~ 0.1wt.%, skeleton SiO ₂: Al ₂o ₃mol ratio 6 ~ 15, specific area 600 ~ 950m ²the hole of/g, 1.7 ~ 10nm accounts for 40 ~ 60%.

The heteropoly acid used is made up of Mo, W, La metal and P element, and its molecular components is H ₃pMo _12-X-Yw _xla _yo ₄₀nH ₂o, wherein X is 0.01 ~ 11, Y is 0.001 ~ 1, obtains nanoscale heteropolyacid salt by precipitation reaction, has resistance to 800 DEG C of high temperature and Undec heat endurance.

Catalyst preparation process of the present invention is: amorphous aluminum silicide, aluminium oxide, Y molecular sieve and heteropoly acid are mixed, and extrusion, shaping, dry and roasting obtain catalyst carrier, and after dipping mixed salt solution, drying, roasting obtain finished catalyst.In the metal salt solution related in above-mentioned preparation process, group vib metal is W and/or Mo, and VIII race's metal is Ni and/or Co.

This catalyst take heavy raw oil as raw material, adopts fixed bed two-stage reforming once by technique, main production naphtha and tail oil industrial chemicals, and byproduct is high cetane number diesel oil; Reaction temperature 300 ~ 395 DEG C, pressure 10 ~ 15MPa, volume space velocity 1 ~ 1.5h ^-1, hydrogen to oil volume ratio 1000 ~ 1500:1.

Described heavy raw oil comprises vacuum gas oil (VGO), coker gas oil, depitching wet goods inferior heavy oil.

Catalyst of the present invention, because USY molecular sieve mixes with heteropoly acid efficient uniform, promoting USY molecular sieve and heteropoly acid is synergistic while, acid site in carrier is distributed very evenly, make metal dispersity high by infusion process supported active metals, catalyst of the present invention is used for, in fixed bed two-stage reforming process, having liquid yield high, the selective height of industrial chemicals, the advantages such as good product quality.

Accompanying drawing explanation

Fig. 1 is the heteropoly acid XRD spectra of synthesis;

Fig. 2 is the thermal multigraph of synthesis heteropoly acid.

Detailed description of the invention

Embodiment 1

First, by the macropore gama-alumina of the USY molecular sieve of 15g, 5g heteropoly acid, 20g and the mixing of 60g amorphous aluminum silicide, extrusion, shaping, dry and roasting obtain catalyst carrier.Configuration 15wt.%MoO ₃with 5wt.%NiO hybrid metal co-impregnated solution, after flooding above-mentioned carrier, dry, roasting obtains finished catalyst.Table 1 lists feedstock property, and table 2 lists evaluation result.

Embodiment 2

First, by the macropore gama-alumina of the USY molecular sieve of 12g, 5g heteropoly acid, 20g, the mixing of 63g amorphous aluminum silicide, extrusion, shaping, dry and roasting obtain catalyst carrier.Configuration 15wt.%WO ₃with 5wt.%NiO hybrid metal co-impregnated solution, after flooding above-mentioned carrier, dry, roasting obtains finished catalyst.Table 1 lists feedstock property, and table 2 lists evaluation result.

Table 1 feedstock property

Table 2 catalyst 100ml experimental rig evaluating data

Catalyst	Embodiment 1	Embodiment 2	Reference agent
				Feedstock oil	VGO+CGO	VGO+CGO	VGO+CGO
Volume space velocity during liquid, h ^-1	1.5	1.5	1.5
				Hydrogen to oil volume ratio	1500:1	1500:1	1500:1
Reaction pressure, MPa	15.0	15.0	15.0
				Reaction temperature, DEG C	376	376	376
Product yield, wt.%
				Light naphthar HK ~ 65 DEG C	14.48	15.29	15.30
Heavy naphtha 65 DEG C ~ 177 DEG C	44.15	44.74	43.88
				Diesel oil 177 DEG C ~ 320 DEG C	25.24	24.93	27.04
Tail oil > 320 DEG C	16.13	15.04	13.78
				Gently, heavy naphtha and tail oil close	74.76	75.07	72.96

As can be seen from Table 2, the activity containing the hydrocracking catalyst of heteropoly acid in the present invention, compared with reference agent, is better than reference agent.

Claims

1., containing a hydrocracking catalyst for heteropoly acid, catalyst composition comprises amorphous aluminum silicide, aluminium oxide, acidic components and hydrogenation active metals, and wherein acidic components comprise a kind of USY molecular sieve and a kind of high thermal stability heteropoly acid; It is characterized in that: the USY molecular sieve used has following character: sodium oxide content 0.01 ~ 0.1wt.%, skeleton SiO ₂: Al ₂o ₃mol ratio 6 ~ 15, specific area 600 ~ 950m ²the hole of/g, 1.7 ~ 10nm accounts for 40% ~ 60%; The heteropoly acid used is made up of Mo, W, La metal and P element, and its molecular components is H ₃pMo _12-X-Yw _xla _yo ₄₀nH ₂o, wherein X is 0.01 ~ 11, Y is 0.001 ~ 1, and described heteropoly acid can obtain nanoscale heteropolyacid salt by precipitation reaction, and described heteropoly acid has resistance to 800 DEG C of high temperature and Undec heat endurance;

Described hydrogenation active metals comprises group vib and VIII race's metal, and group vib hydrogenation metal is W and/or Mo, and VIII race's hydrogenation metal is Ni and/or Co;

In described catalyst, group vib metal oxide accounts for 10 ~ 25wt.%, and VIII family metal oxide accounts for 1 ~ 10wt.%, and USY molecular sieve accounts for 9 ~ 15wt.%, and heteropoly acid accounts for 1 ~ 5wt.%, and amorphous aluminum silicide accounts for 20 ~ 50wt.%, and aluminium oxide accounts for 5 ~ 20wt.%.

2. a kind of application containing the hydrocracking catalyst of heteropoly acid according to claim 1, it is characterized in that: it is raw material that this catalyst is used for heavy raw oil, adopt fixed bed two-stage reforming once by technique, catalytic production naphtha, tail oil industrial chemicals and diesel oil; Reaction temperature 300 ~ 395 DEG C, pressure 10 ~ 15MPa, volume space velocity 1 ~ 1.5h ^-1, hydrogen to oil volume ratio 1000 ~ 1500:1;

Described heavy raw oil comprises vacuum gas oil (VGO), coker gas oil, deasphalted oil.