CN105080598B - A kind of palladium series catalyst and preparation method thereof - Google Patents
A kind of palladium series catalyst and preparation method thereof Download PDFInfo
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- CN105080598B CN105080598B CN201410194074.3A CN201410194074A CN105080598B CN 105080598 B CN105080598 B CN 105080598B CN 201410194074 A CN201410194074 A CN 201410194074A CN 105080598 B CN105080598 B CN 105080598B
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Abstract
The present invention relates to a kind of palladium series catalysts.The catalyst is carried on aluminium oxide titanium oxide compound by Metal Palladium active component, beta-molecular sieve complex carrier is made, and total weight of the content of Metal Palladium based on the catalyst is 0.3% 1.8% in the catalyst；Beta-molecular sieve accounts for 30 weight % 70 weight %, TiO in complex carrier2/Al2O3Account for 30 weight %, 70 weight %；The catalyst specific surface is 90 240m20.7 1.8ml/g of/g, Kong Rongwei.The catalyst can also be increased into heavy aromatics while heavy aromatics conversion ratio is improved for heavy aromatics catalytic hydrogenation and add hydrogen products obtained therefrom BTX yields.
Description
Technical field
The invention belongs to heavy aromatics hydrogenation catalyst technical field, be related to a kind of palladium series catalyst and preparation method thereof and
Application of the catalyst in heavy aromatics hydro-dealkylation technique.
Background technology
The aromatic hydrocarbons of by-product, predominantly C in oil and coal process9And C10Aromatic hydrocarbons, the C of an also minimum part10With
On aromatic hydrocarbons, referred to as heavy aromatics.Oil plant catalytic reforming unit is mainly derived from, ethylene unit by-product drippolene and ethylene are burnt
Oil and coal high-temperature coking by-product coal tar etc..Throwing is built up with the increase and megaton large size ethylene of refining capacity
Production, heavy aromatics yield will greatly improve.
The U.S., the former Soviet Union and Japan begin to the comprehensive utilization of research and development heavy aromatics in the 1950s, main
If by heavy aromatics lighting, heavy aromatics is converted into the basic petrochemical industry production such as higher benzene,toluene,xylene of added value
Product.At abroad, this technology has become most advanced and most potential technology in heavy aromatics comprehensive utilization, it is to improve weight
The important means of aromatic hydrocarbons utilization rate, the catalytic hydrodealkylation technique as one of heavy aromatics lighting technology have more conversion ratio
The features such as height, high selectivity, temperature are low, hydrogen consumes low and liquid product high income, is grinding for current heavy aromatics lighting technology
Study carefully hot spot.At present, the technique of external heavy aromatics lighting is important HAD techniques, DETOL techniques, TAC9 techniques and IEOLYST/
The techniques such as SK.Catalyst mainly uses alumina load metallic catalyst and molecular sieve carried metallic catalyst.
But heavy aromatics hydro-dealkylation is reacted, it is to urge to improve heavy aromatics conversion ratio and BTX (light aromatics) yield
Agent designs and has to the major issue solved in developing.Therefore, the exploitation of new catalyst is converted mainly along heavy aromatics
How rate improves accounts for how product BTX yields increase by two aspects.
Therefore, the technical issues that need to address are that a kind of raising heavy aromatics conversion ratio of research and development and product BTX are received at present
The novel heavy aromatic hydrogenation dealkylation catalyst of rate.
Invention content
The technical problems to be solved by the invention are in view of the deficiencies of the prior art, to provide a kind of palladium series catalyst, this is urged
Agent is made by aluminium oxide-titanium oxide compound, beta-molecular sieve composite carrier load Metal Palladium active component.The catalyst is used for
Heavy aromatics hydro-dealkylation technique can effectively improve heavy aromatics conversion ratio and product BTX yields.
For this purpose, first aspect present invention provides a kind of palladium series catalyst, including aluminium oxide-titanium oxide compound
(TiO2/Al2O3) with beta-molecular sieve complex carrier and the Metal Palladium that is supported on the complex carrier, wherein in the catalyst
Total weight of the content of Metal Palladium based on the catalyst is 0.3%-1.8%.
According to the present invention, in the complex carrier, the beta-molecular sieve accounts for 30 weight %-70 weight %.
According to the present invention, in the complex carrier, the aluminium oxide-titanium oxide compound accounts for 30 weight %-70 weights
Measure %.In the aluminium oxide-titanium oxide compound, the weight ratio of aluminium oxide and titanium oxide is 2.3-5:1.It is preferred that aluminium oxide with
The weight ratio of titanium oxide is 4:1.
In the present invention, the specific surface of the catalyst is 90-240m2/ g, preferably 120-200m2/g.The catalyst
Kong Rongwei 0.7-1.8ml/g, preferably 0.85-1.25ml/g.
Second aspect of the present invention provides a kind of preparation method for preparing catalyst as described above, including：
Step A, prepares complex carrier：By beta-molecular sieve and TiO2/Al2O3Mixing, add in aqueous solution of nitric acid kneading, extrusion into
Type, dry, complex carrier is made in roasting；
Catalyst is carried on complex carrier by step B：Drying and roasting after complex carrier is impregnated in palladium compound solution
Palladium series catalyst is made.
According to the method for the present invention, the pH value of the palladium compound solution is 4-5.
In one embodiment of the invention, the palladium compound includes palladium bichloride, palladium nitrate, preferably palladium sulfate, palladium
Conjunction object is palladium bichloride.The dosage of palladium compound solution is equal with complex carrier total pore volume to be impregnated or more than institute for its volume
State carrier total pore volume.It is preferred that the dosage of palladium compound solution is equal with complex carrier total pore volume for its volume.
Heretofore described term " complex carrier total pore volume " refers to the Kong Rong of complex carrier, is by measuring complex carrier
Water absorption rate obtain, it is therefore an objective to obtain the liquid volume of configuration maceration extract.
In the specific embodiment of the present invention, in step, by a certain amount of beta-molecular sieve with it is a certain amount of
TiO2/Al2O3It mixes, the aqueous solution of nitric acid kneading of addition a concentration of 2%, extruded moulding, 120 DEG C of dryings, 500 DEG C of roastings in air
It burns 4 hours and both obtains complex carrier.
In the another embodiment of the present invention, in stepb, by complex carrier in palladium under the pH value of 4-5
It is impregnated 7-10 hours in compound solution, impregnated aluminium oxide-titanium oxide compound, beta-molecular sieve complex carrier is dried, and
It is roasted 4-7 hours at a temperature of 300-800 DEG C；The wherein weight ratio 4 of aluminium oxide and titanium oxide:1.
In the still another embodiment of the present invention, the preparation method of the catalyst, which further includes, prepares aluminium oxide-oxygen
The step of changing titanium compound, including：Aluminium oxide is impregnated into 3-6 in above-mentioned compound titanium solution at a temperature of 79-81 DEG C
Hour, it is 8-10 hours dry by filtering out, and at a temperature of 100-120 DEG C, then roasted at a temperature of 300-700 DEG C
It burns and obtains within 3-6 hours aluminium oxide-titanium oxide compound, the wherein weight ratio of aluminium oxide and titanium oxide is 4:1.
In the present invention, the titanium compound includes acetate, the sulfate and nitrate of titanium.The use of compound titanium solution
It measures equal with aluminium oxide total pore volume or more than aluminium oxide total pore volume for its volume.It is preferred that the dosage of compound titanium solution is its body
Product is equal with aluminium oxide total pore volume.If the dosage of compound titanium solution is more than aluminium oxide total pore volume, must will be mixed after the completion of dipping
It closes after object filtering drains and is dried again.
Heretofore described term " aluminium oxide total pore volume " refers to the Kong Rong of aluminium oxide, is the water suction by measuring aluminium oxide
What rate obtained, it is therefore an objective to obtain the liquid volume of configuration compound titanium solution.
The catalyst that third aspect present invention provides described in a kind of first aspect present invention as described above adds in heavy aromatics
Application in hydrogen.
Metal Palladium active component is carried on aluminium oxide-titanium oxide compound and is made with beta-molecular sieve complex carrier by the present invention
A kind of palladium series catalyst, the weight ratio of aluminium oxide and titanium oxide is 4 in the catalyst:1, the content of Metal Palladium is based on the catalysis
The total weight of agent is 0.3%-1.8%；The specific surface of the catalyst is 90-240m2/ g, Kong Rongwei 0.7-1.8ml/g.It should
Catalyst can also increase heavy aromatics while heavy aromatics conversion ratio is improved for heavy aromatics catalytic hydrogenation and add hydrogen products obtained therefrom
BTX yields.
Specific embodiment
To make the present invention easier to understand, below in conjunction with embodiment, the present invention will be described in detail, these embodiments are only
Serve illustrative, it is not limited to application range of the invention, unmentioned specific experiment method in the following example, usually
It is carried out according to routine experiment method.
Embodiment
Embodiment 1：
The preparation of carrier
It is 160m by 100g specific surfaces2The cylindrical shaped alumina 50ml titanium sulfates of/g and Kong Rongwei 0.85ml/g
0.6g/ml dilution heat of sulfuric acid impregnates 4 hours, 10 hours dry at a temperature of 120 DEG C, and it is small that 6 are roasted at a temperature of 700 DEG C
When, 125g aluminium oxide-titanium oxide compounds are obtained, the wherein weight ratio of aluminium oxide and titanium oxide is 4:1.
By the beta-molecular sieve of 54g and the TiO of 125g2/Al2O3Mixing adds in a concentration of 2% aqueous solution of nitric acid kneading, squeezes
Item is molded, 120 DEG C of dryings, in air 500 DEG C of roastings 4 hours both complex carrier 1.Wherein beta-molecular sieve accounts for 30%, TiO2/
Al2O3Account for 70%.
The preparation of catalyst
120g complex carriers 1 are immersed in the 0.0064g/ml aqueous solutions of 102ml palladium bichlorides, dipping drains the water after 4 hours
Point, it with the hydrazine hydrate reduction 2 hours of 120ml a concentration of 40%, is washed with deionized, until without chlorion, then 110
It is 5 hours dry at a temperature of DEG C, it is roasted 6 hours at a temperature of 700 DEG C, obtains catalyst.Wherein palladium content is carried for catalyst
The 0.3% of body weight, catalyst specific surface 156m2/ g, Kong Rongwei 0.83ml/g.
Embodiment 2：
The preparation of carrier
The preparation method is the same as that of Example 1 for following aluminium oxide-titanium oxide compound.Cylindrical shaped alumina specific surface is 120m2/g
With Kong Rongwei 0.95ml/g.By the beta-molecular sieve of 40g and the TiO of 60g2/Al2O3Mixing adds in a concentration of 2% aqueous solution of nitric acid
Kneading, extruded moulding, 120 DEG C of dryings, in air 500 DEG C of roastings 4 hours both complex carrier 2.Wherein beta-molecular sieve accounts for 40%,
TiO2/Al2O3Account for 60%.
The preparation of catalyst
100g complex carriers 2 are immersed in the 0.012g/ml aqueous solutions of 85ml palladium bichlorides, dipping drains the water after 5 hours
Point, it with the hydrazine hydrate reduction 2 hours of 120ml a concentration of 40%, is washed with deionized, until without chlorion, then 110
It is 4 hours dry at a temperature of DEG C, it is roasted 6 hours at a temperature of 700 DEG C, obtains catalyst.Wherein palladium content is carried for catalyst
The 0.6% of body weight.Catalyst specific surface is 127m2/ g, Kong Rongwei 0.92ml/g.
Embodiment 3：
The preparation of carrier
Cylindrical shaped alumina specific surface is 180m2/ g and Kong Rongwei 1.15ml/g.By the beta-molecular sieve of 50g and the TiO of 50g2/
Al2O3It mixes, the aqueous solution of nitric acid kneading of addition a concentration of 2%, extruded moulding, 120 DEG C of dryings, 500 DEG C of roastings 4 are small in air
When both complex carrier 3.Wherein beta-molecular sieve accounts for 50%, TiO2/Al2O3Account for 50%.
The preparation of catalyst
100g complex carriers 3 are immersed in the 0.017g/ml aqueous solutions of 96ml palladium bichlorides, dipping drains the water after 6 hours
Point, it with the hydrazine hydrate reduction 2 hours of 120ml a concentration of 40%, is washed with deionized, until without chlorion, then 120
It is 6 hours dry at a temperature of DEG C, it is roasted 7 hours at a temperature of 600 DEG C, obtains catalyst.Wherein palladium content is carried for catalyst
The 1% of body weight.Catalyst specific surface is 186m2/ g, Kong Rongwei 1.07ml/g.
Embodiment 4：
The preparation of carrier
Cylindrical shaped alumina specific surface is 200m2/ g and Kong Rongwei 1.2ml/g.By the beta-molecular sieve of 60g and the TiO of 40g2/
Al2O3It mixes, the aqueous solution of nitric acid kneading of addition a concentration of 2%, extruded moulding, 120 DEG C of dryings, 500 DEG C of roastings 4 are small in air
When both complex carrier 4.Wherein beta-molecular sieve accounts for 60%, TiO2/Al2O3Account for 40%.
The preparation of catalyst
100g complex carriers 4 are immersed in the 0.035g/ml aqueous solutions of 85ml palladium bichlorides, dipping drains the water after 6 hours
Point, it with the hydrazine hydrate reduction 2 hours of 120ml a concentration of 40%, is washed with deionized, until without chlorion, then 110
It is 5 hours dry at a temperature of DEG C, it is roasted 4 hours at a temperature of 800 DEG C, obtains catalyst.Wherein palladium content is carried for catalyst
The 1.8% of body weight.Catalyst specific surface is 205m2/ g, Kong Rongwei 1.17ml/g.
Embodiment 5：
The preparation of carrier
Cylindrical shaped alumina specific surface is 180m2/ g and Kong Rongwei 1.25ml/g.By the beta-molecular sieve of 70g and the TiO of 30g2/
Al2O3It mixes, the aqueous solution of nitric acid kneading of addition a concentration of 2%, extruded moulding, 120 DEG C of dryings, 500 DEG C of roastings 4 are small in air
When both complex carrier 5.Wherein beta-molecular sieve accounts for 70%, TiO2/Al2O3Account for 30%.
The preparation of catalyst
100g complex carriers 5 are immersed in the 0.016g/ml aqueous solutions of 85ml palladium bichlorides, dipping drains the water after 6 hours
Point, it with the hydrazine hydrate reduction 2 hours of 120ml a concentration of 40%, is washed with deionized, until without chlorion, then 110
It is 5 hours dry at a temperature of DEG C, it is roasted 4 hours at a temperature of 800 DEG C, obtains catalyst.Wherein palladium content is carried for catalyst
The 0.8% of body weight.Catalyst specific surface is 186m2/ g, Kong Rongwei 1.12ml/g.
Embodiment 6：
The catalyst prepared by embodiment 4 and similar non-palladium series catalyst are used for heavy aromatics catalytic hydrogenation process respectively,
Hydroconversion condition and reaction result are as shown in table 1：
Table 1
It can be seen that from the heavy aromatics catalytic hydrogenation result of above-described embodiment and similar non-palladium series catalyst by the present invention's
Catalyst can also increase heavy aromatics while heavy aromatics conversion ratio is improved for heavy aromatics catalytic hydrogenation and add hydrogen products obtained therefrom
BTX yields.
Using scanning electron microscope (AIS2100C types, South Korea's generation human relations science and technology) to being catalyzed in above-described embodiment and comparative example
Abundance and distributed architecture of the active component of agent on carrier are characterized, the results showed that catalyst of the invention has preferable
Activity.
The foregoing is merely presently preferred embodiments of the present invention, is not intended to limit the invention, it is all the present invention spirit and
Within principle, any modification, equivalent replacement, improvement and so on should all be included in the protection scope of the present invention.
Claims (13)
1. a kind of palladium series catalyst including aluminium oxide-titanium oxide compound and beta-molecular sieve complex carrier and is supported on described
Metal on complex carrier, wherein the metal being supported on the complex carrier is made of Metal Palladium, in the catalyst
Total weight of the content of Metal Palladium based on the catalyst is 0.3%-1.8%.
2. catalyst according to claim 1, it is characterised in that：In the complex carrier, the beta-molecular sieve accounts for 30 weights
Measure %-70 weight %.
3. catalyst according to claim 1, it is characterised in that：
In the complex carrier, the aluminium oxide-titanium oxide compound accounts for 30 weight %-70 weight %；
In the aluminium oxide-titanium oxide compound, the weight ratio of aluminium oxide and titanium oxide is 2.3-5: 1.
4. catalyst according to claim 3, it is characterised in that：The weight ratio of aluminium oxide and titanium oxide is 4: 1.
5. according to the catalyst described in any one in claim 1-4, it is characterised in that：The specific surface of the catalyst is
90-240m2/g。
6. according to the catalyst described in any one in claim 1-4, it is characterised in that：The specific surface of the catalyst is
120-200m2/g。
7. according to the catalyst described in any one in claim 1-4, it is characterised in that：The Kong Rongwei 0.7- of the catalyst
1.8ml/g。
8. according to the catalyst described in any one in claim 1-4, it is characterised in that：The Kong Rongwei of the catalyst
0.85-1.25ml/g。
9. a kind of preparation method of the catalyst in 1-8 such as claim as described in any one, including：
Step A, prepares complex carrier：By beta-molecular sieve and TiO2/Al2O3Mixing, addition aqueous solution of nitric acid kneading, extruded moulding,
Dry, complex carrier is made in roasting；
Catalyst is carried on complex carrier by step B：Drying and roasting is made after complex carrier is impregnated in palladium compound solution
Palladium series catalyst.
10. according to the method described in claim 9, it is characterized in that：The pH value of the palladium compound solution is 4-5.
11. method according to claim 9 or 10, it is characterised in that：The palladium compound include palladium bichloride, palladium nitrate,
Palladium sulfate.
12. according to the method for claim 11, it is characterised in that：The palladium compound is palladium bichloride.
13. a kind of application of the catalyst in heavy aromatics adds hydrogen in 1-8 such as claim as described in any one.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1752058A (en) * | 2004-09-24 | 2006-03-29 | 中国石油化工股份有限公司 | Method of heavy arene hydrogenation dealkylation and alkylation transfer |
| CN103721711A (en) * | 2012-10-10 | 2014-04-16 | 中国石油化工股份有限公司 | Heavy aromatic hydrodealkylation palladium catalyst and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP5340230B2 (en) * | 2010-06-30 | 2013-11-13 | Ｊｘ日鉱日石エネルギー株式会社 | C heavy oil composition |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1752058A (en) * | 2004-09-24 | 2006-03-29 | 中国石油化工股份有限公司 | Method of heavy arene hydrogenation dealkylation and alkylation transfer |
| CN103721711A (en) * | 2012-10-10 | 2014-04-16 | 中国石油化工股份有限公司 | Heavy aromatic hydrodealkylation palladium catalyst and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| MCM-22分子筛的合成及其在重芳烃轻质化反应中的应用;朱瑾等;《华东理工大学学报（自然科学版）》;20080831;第34卷(第4期);全文 * |
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