CN1552816A - Hydrocarbon selective hydrogenation catalyst and preparing method thereof - Google Patents
Hydrocarbon selective hydrogenation catalyst and preparing method thereof Download PDFInfo
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- CN1552816A CN1552816A CNA031335640A CN03133564A CN1552816A CN 1552816 A CN1552816 A CN 1552816A CN A031335640 A CNA031335640 A CN A031335640A CN 03133564 A CN03133564 A CN 03133564A CN 1552816 A CN1552816 A CN 1552816A
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- hydrogenation catalyst
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Abstract
A hydrogenation catalyst, especially a highly unsaturated compound selective catalyst in hydrocarbon flow, and its preparation are disclosed. The catalyst consists of nickel 5-25w%, sulfate or phosphate and residue aluminum oxide of alkali metal or alkaline earth metal 0.5-3.5w%. The catalyst is prepared by loading active ingredient nickel onto aluminum oxide carriers, adding sulfate or phosphate of alkali metals or alkaline earth metals as assistants. The catalyst can be used for selective hydrogenation process of diolefin and acetylene hydrocarbon in mixed C4 hydrocarbons, effectively inhibiting catalyst surface polymerization on conjugated dienes and between diene and alkine, and apparently delaying catalyst use time.
Description
Technical field
The present invention relates to a kind of Hydrobon catalyst, especially a kind of hydrocarbon material flow camber unsaturated compound is selected hydrogenation catalyst and preparation method thereof.
Background technology
1,3 divinyl are elastomeric important source material, contain 1,3 divinyl about 40%, alkynes about 10% in the waste gas of rubber plant, burn mainly as waste gas, cause the waste of the carbon four hydro carbons resources of environmental pollution and preciousness; Also there is small part to use as liquefied gas with butane dilution back, but also uneconomical economically.If can develop the catalyzer of a kind of highly efficient durable and reasonable price, the above-mentioned gas hydrogenation is become directly incendiary liquefied petroleum gas (LPG), then can solve rubber plant's waste gas recycling problem.At present, alkynes in the mixed c 4 hydrocarbon-fraction and diolefine can adopt the method for catalysis selective hydrogenation to remove.Catalyst system therefor mainly tends to use with the noble metal catalyst as representative such as palladium, platinum, silver, secondly is to be the non-precious metal catalyst of representative with copper, nickel.
Different and the purpose product that the selection hydrogenation of alkynes and diolefine is formed because of raw material in the hydrocarbon material flow different, selected catalyzer and reaction conditions are also different.A kind of good selection hydrogenation catalyst also should have satisfactory stability except higher hydrogenation activity will be arranged, promptly catalyzer will have anti-impurity and anti-gelationus ability, could prolong life of catalyst like this.Therefore require carrier that lower acidity, less specific surface and bigger aperture will be arranged.In Preparation of catalysts, add the work-ing life that some auxiliary agents also can prolong catalyzer in addition.
CN85100761A, CN85106117A, CN1236333A and CN1084222C have all introduced the selection hydrogenation catalyst that is used to handle the hydrocarbon material flow that contains diolefin, they are active ingredient with precious metals such as Pd, Pt all, add auxiliary agents such as Na, K, Li, Mg again, carrier is Al
2O
3The noble metal catalyst low temperature active is good, and the reaction conditions gentleness easily runs off, costs an arm and a leg but its weak point is the catalyst activity component, is difficult for regeneration, and hydrogenation selectivity is poor slightly.
Non-precious metal catalyst needs to react under higher temperature, and hydroconversion condition is harsh, but its preparation is simple, is convenient to repeated regeneration, therefore still has certain researching value.In the process of this class hydrogenation reaction, be attracted to semihydrogenation state free radical on the catalyzer and adjacent alkynes or diolefine reaction and generate a kind of thick polymkeric substance (being commonly called as green oil), it is mainly by C
6Above compound is formed, and because of its surface that covers catalyzer, has stopped up the micropore of catalyst surface, makes catalyst activity reduction, influences the work-ing life of catalyzer.Especially for conjugated diene (as 1,3 divinyl), its polyreaction is easier carries out, and makes catalyzer inactivation at short notice, and catalyzer must often be regenerated and could reuse like this.
CN1055107C introduces a kind of distillate diolefin hydrogenation catalyzer that is used for, and it is active ingredient with NiO, and its content is 5～25w%; Lithium or alkaline-earth metal are auxiliary agent, and its content is 0.1～2.0w%; Use Al
2O
3Make carrier.This catalyst preparation process is earlier with the saturated oxide impregnation alumina supporter of solution that contains lithium or alkaline earth metal compound; Under 80～120 ℃, dry 4～8 hours; Under 600～970 ℃, high-temperature roasting 4～6 hours makes the alumina supporter that contains lithium or alkaline-earth metal then; At last, hydrogenation activity component Ni is made this catalyzer on the above-mentioned alumina supporter that contains lithium or alkaline-earth metal, the used preferred nitrate separately of the solution that contains lithium or alkaline earth metal compound in this process.This catalyzer is selected in the hydrogenation process at the pyrolysis gasoline full distillate oil, shows active and stable preferably.The spinel structure that its adding assistant composition and aluminum oxide form has dissemination preferably to active component nickel, thereby makes catalyzer that stability preferably be arranged.But do not contain very easily polymeric 1,3 divinyl or content during it is raw materials used seldom, therefore the green oil problem that generates for polymerization does not propose concrete solution.
Summary of the invention
At the deficiencies in the prior art, the object of the invention provides a kind of hydrocarbon material flow camber unsaturated compound and selects hydrogenation catalyst, especially the selection hydrogenation process that contains the unsaturated hydrocarbons of conjugated diene, the selection hydrogenation process of the mixed c 4 hydrocarbon of be specially adapted to 1,3-divinyl and alkynes content are higher.This catalyzer can prolong the work-ing life of catalyzer effectively.
So-called height unsaturated hydrocarbons is meant the molecule that contains the two keys of three key or two and contain two keys and one three key; Low unsaturated hydrocarbons is meant monoolefine.Selecting hydrogenation is exactly with diolefine in the hydro carbons or alkynes, and at first be hydrogenated to monoolefine or further be hydrogenated to alkane, thus the degree of unsaturation of reduction hydro carbons.
Catalyzer of the present invention is a kind of non-precious metal catalyst, and it is made up of the nickel of 5～25w%, the basic metal of 0.5～3.5w% or the vitriol of alkaline-earth metal or the aluminum oxide of phosphoric acid salt and surplus.The content of nickel is preferably 7～15w% in the catalyzer, and the vitriol of basic metal or alkaline-earth metal or phosphatic content are preferably 1.5～2.5w%, the vitriol preferably sulfuric acid magnesium of alkaline-earth metal wherein, alkali-metal phosphoric acid salt preferably phosphoric acid potassium.The specific surface area of this catalyzer is at 90～130m
2Between/the g, pore volume is between 0.7～1.2ml/g.
Catalyzer of the present invention is by active component nickel is loaded on the alumina supporter, add again that the vitriol of basic metal or alkaline-earth metal or phosphoric acid salt makes, wherein the preparation process of alumina supporter is: the former powder of aluminium hydroxide adds the dilute nitric acid solution of 4w%, mixes the back extrusion and is shaped; Then under 90～120 ℃, dry 2～6 hours; At last in 900～1100 ℃ of air, roasting 4～8 hours.
Preparation of catalysts method of the present invention may further comprise the steps:
A. the aqueous solution oxide impregnation alumina supporter that is made into nickel compound containing, the consumption of nickel compound containing are that to make the nickel content in the final catalyzer be 5～25w%, with soaked carrier filter, drying and roasting, make nickeliferous alumina supporter;
B. prepare the vitriol or the phosphate solution of basic metal or alkaline-earth metal, use this solution, adopt the method that sprays, the alumina carrier containing Ni that step a is obtained floods, and is dry then, makes catalyzer.
The used preferred nickelous nitrate of nickel compound containing among the above-mentioned steps a, the vitriol preferably sulfuric acid magnesium of used alkaline-earth metal among the step b, alkali-metal phosphoric acid salt preferably phosphoric acid potassium.
Used alumina supporter mainly has been the effect of dispersed activity component in the present invention, does not wish that it brings other side reaction, therefore should reduce its acidity as far as possible.Usually adopt the former powder of aluminium hydroxide to make α-Al through shaping and roasting
2O
3Or α-Al
2O
3With γ-Al
2O
3Mixture.Carrier can be bar shaped, sphere or cylindrical.The content of active ingredient can be decided according to the hydrogenation needs, generally changes the content of active ingredient by the conciliation impregnation concentration.
Catalyzer of the present invention needs under 350～450 ℃ of hydrogen existence conditions before use, reductase 12～4 hour, and hydrogen gas space velocity is 100～150h during reduction
-1
In catalyzer of the present invention, institute's adding assistant composition is the vitriol or the phosphoric acid salt of basic metal or alkaline-earth metal, and this auxiliary component finally also exists with vitriol or phos-phate forms, it can effectively stop polyreaction and take place, reducing green oil generates, prevent the obstruction of polymkeric substance, thereby make catalyzer keep active and stable preferably catalyst pores.And when adopting the prior art for preparing catalyzer, institute's adding assistant is the nitrate that contains lithium or alkaline-earth metal, this nitrate can react in the process of Preparation of Catalyst, lithium or alkaline-earth metal finally in catalyzer existence form be the spinel structure that forms with aluminum oxide, its objective is for dispersed activity component better, prevent the fusion of nickel crystallite, improve the stability of catalyzer.Prior art is different with the final existence form of the auxiliary component of catalyzer role of the present invention, and the mechanism of action is also different.
Therefore, compared with prior art, catalyzer of the present invention has the following advantages:
(1) catalyzer of the present invention not only has hydrogenation activity efficiently, and is to stop effectively the polyreaction that caused by free radical, obviously reduces the generation of green oil, has prolonged the work-ing life of catalyzer.
(2) the raw material subject range of catalyzer of the present invention is wider, especially is fit to contain the raw material of high density 1,3 divinyl.
Embodiment
The concrete preparation method of catalyzer of the present invention may further comprise the steps:
A. with alumina supporter, the aqueous solution dipping that is made into nickelous nitrate 3～6 hours, the consumption of nickelous nitrate are that to make the nickel content in the final catalyzer be 5～25w%, preferred 7～15w%; Soaked carrier is filtered, under 90～120 ℃ of temperature, dry 4～8 hours; Under 380～450 ℃ of temperature, roasting 4～8 hours makes nickeliferous alumina supporter then.
B. prepare sal epsom or potassium phosphate solution, use this solution, adopt the method that sprays, the alumina carrier containing Ni that step a is obtained floods; Then under 110～130 ℃, dry 6～12 hours, get final product catalyzer of the present invention.
Below in conjunction with embodiment the present invention is further specified.
Embodiment 1
To the Ni of 50g (NO
3)
26H
2Among the O, add distilled water its dissolving is made into 100ml solution, with this solution submergence 30gAl
2O
3Carrier flooded 3 hours, poured out the upper strata raffinate, after the carrier that will soak nickel dries, and under 90 ℃, dry 8 hours; In air, under 400 ℃, nickeliferous alumina supporter is made in roasting 8 hours then.
Embodiment 2
To the Ni of 70g (NO
3)
26H
2Among the O, add distilled water its dissolving is made into 100ml solution, with this solution submergence 30gAl
2O
3Carrier flooded 4 hours, poured out the upper strata raffinate, after the carrier that will soak nickel dries, 110 ℃ dry 6 hours down, then in air in 420 ℃ of roastings 6 hours, make nickeliferous alumina supporter.
Embodiment 3
To the Ni of 150g (NO
3)
26H
2Among the O, add distilled water its dissolving is made into 100ml solution, with this solution submergence 30gAl
2O
3Carrier flooded 6 hours, poured out the upper strata raffinate, after the carrier that will soak nickel dries, 120 ℃ dry 4 hours down, then in air in 450 ℃ of roastings 4 hours, make nickeliferous alumina supporter.
Embodiment 4
0.5gMgSO
47H
2O is dissolved in the 13ml distilled water, is sprayed at equably then on the alumina carrier containing Ni that 15g obtains by embodiment 1, and in 110 ℃ of dryings 10 hours, makes catalyst A.The Ni content of this catalyzer is 7w%, MgSO
4Be 1.6w%.Specific surface is 122m
2/ g, pore volume are 1.0ml/g.
Embodiment 5
0.3gK
2SO
4Be dissolved in the 13ml distilled water, be sprayed at equably then on the alumina carrier containing Ni that 15g obtains by embodiment 2, and, make catalyst B in 120 ℃ of dryings 8 hours.The Ni content of this catalyzer is 10w%, K
2SO
4Be 2.0w%.Specific surface is 115m
2/ g, pore volume are 1.0ml/g.
Embodiment 6
0.3gK
3PO
4Be dissolved in the 13ml distilled water, be sprayed at equably then on the alumina carrier containing Ni that 15g obtains by embodiment 3, and, make catalyzer C in 125 ℃ of dryings 6 hours.The Ni content of this catalyzer is 21w%, K
3PO
4Content is 2.0w%.Specific surface is 107m
2/ g, pore volume are 0.9ml/g.
Comparative example 1
Adopt embodiment 5 described methods among the Chinese patent CN1055107C, prepare a kind of selection hydrogenation catalyst D, this catalyzer is made up of the alumina supporter of the Mg of NiO, the 1.38w% of 15.5w% and surplus.The specific surface of this catalyzer is 85m
2/ g, pore volume are 0.34ml/g.
Comparative example 2
To the Ni of 50g (NO
3)
26H
2Among the O, add distilled water its dissolving is made into 100ml solution, with this solution submergence 30gAl
2O
3Carrier flooded 3 hours, poured out the upper strata raffinate, after the carrier that will soak nickel dries, and under 90 ℃, dry 8 hours; In air, under 400 ℃, nickeliferous catalyzer E is made in roasting 8 hours then, and the Ni content in this catalyzer is 7w%.The specific surface of this catalyzer is 83m
2/ g, pore volume are 0.33ml/g.
In reactor, be respectively charged into catalyst A, B, C, D and the E of embodiment 4-6 and comparative example 1-2,350 ℃ of hydrogen reducings 4 hours.Be cooled to 50 ℃ then and advance raw material, air speed 2.0h
-1, be warming up to 100 ℃ again and react.Reaction pressure is 3.0MPa, and the raw material that reacts used is the mixed c 4 hydrocarbon, and its composition (v/v%) is: propane 0.72; Propylene 0.32; Trimethylmethane 4.55; Normal butane 4.17; Propadiene 0.33; Positive iso-butylene 38.24; Anti-butylene 4.50; Maleic 3.07; Methylacetylene 3.68; 1,3 divinyl 29.97; 1,2 divinyl 0.38; Ethylacetylene 1.06; Vinylacetylene 9.01.The reaction product gas chromatographic analysis, the catalyst activity evaluation result sees Table 1.
Table 1 activity rating of catalyst result
| The catalyzer numbering | Reaction times, hour | Butadiene content, v% | Vinylacetylene, v% |
| A | ??8 | ???2.0 | 0 |
| ??30 | ???3.2 | 0 | |
| ??100 | ???5.3 | 0.3 | |
| B | ??8 | ???3.2 | 0 |
| ??30 | ???3.8 | 0 | |
| ??100 | ???4.2 | 0.5 | |
| C | ??8 | ???2.1 | 0 |
| ??30 | ???2.8 | 0 | |
| ??100 | ???4.6 | 0.2 | |
| D | ??8 | ???0 | 0 |
| ??30 | ???7.6 | 0.3 | |
| ??50 | ???17.8 | 0.5 | |
| ??100 | ???22.7 | 1.6 | |
| E | ??8 | ???0 | 0 |
| ??30 | ???8.0 | 0.3 | |
| ??50 | ???25.1 | 1.2 | |
| ??100 | ???27.9 | 2.3 |
Watch from drawing off the outer of catalyzer, the catalyzer D, the E surface coverage that do not add auxiliary agent of the present invention heavy-gravity green polymer (green oil), and catalyzer is inactivation.Catalyst A of the present invention, B and C surface then do not have green oil to cover, and still have activity, embody advance of the present invention thus.
Claims (10)
1, a kind of selective hydrogenation catalyst, this catalyzer is made up of the nickel of 5～25w%, the basic metal of 0.5～3.5w% or the vitriol of alkaline-earth metal or the aluminum oxide of phosphoric acid salt and surplus.
2,, it is characterized in that described specific surface area of catalyst is at 90～130m according to the selective hydrogenation catalyst of claim 1
2Between/the g, pore volume is between 0.7～1.2ml/g.
3,, it is characterized in that described catalyzer nickel content is 7～15w% according to the selective hydrogenation catalyst of claim 1.
4,, it is characterized in that the vitriol of described basic metal or alkaline-earth metal or phosphatic content are 1.5～2.5w% according to the selective hydrogenation catalyst of claim 1.
5, the preparation method of the described selective hydrogenation catalyst of a kind of claim 1, this method comprises:
A. the aqueous solution oxide impregnation alumina supporter that is made into nickel compound containing, the consumption of nickel compound containing are that to make the nickel content in the final catalyzer be 5～25w%, with soaked carrier filter, drying and roasting, make nickeliferous alumina supporter;
B. prepare the vitriol or the phosphate solution of basic metal or alkaline-earth metal, use this solution, adopt the method that sprays, the alumina carrier containing Ni that step a is obtained floods, and is dry then, makes catalyzer.
6,, it is characterized in that the time of the described aqueous solution oxide impregnation alumina supporter that is made into nickel compound containing of step a is 3～6 hours according to the preparation method of the selective hydrogenation catalyst of claim 5.
7, according to the preparation method of the selective hydrogenation catalyst of claim 5, it is characterized in that the described drying of step a is under 90～120 ℃ of temperature dry 4～8 hours, described roasting is 380～450 ℃ of roasting temperatures 4～8 hours.
8,, it is characterized in that the described drying of step b is under 110～130 ℃ of temperature dry 6～12 hours according to the preparation method of the selective hydrogenation catalyst of claim 5.
9, according to the preparation method of the selective hydrogenation catalyst of claim 5, it is characterized in that the described nickel compound containing of step a is a nickelous nitrate.
10, according to the preparation method of the selective hydrogenation catalyst of claim 5, the vitriol that it is characterized in that the described alkaline-earth metal of step b is sal epsom, and described alkali-metal phosphoric acid salt is potassiumphosphate.
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|---|---|---|---|
| CN 03133564 CN1221638C (en) | 2003-05-31 | 2003-05-31 | Hydrocarbon selective hydrogenation catalyst and preparing method thereof |
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|---|---|---|---|
| CN 03133564 CN1221638C (en) | 2003-05-31 | 2003-05-31 | Hydrocarbon selective hydrogenation catalyst and preparing method thereof |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101191078B (en) * | 2006-11-21 | 2011-07-13 | 中国石油化工股份有限公司 | Nickel catalyst with composite pore structure used for selective hydrogenation |
| CN101133006B (en) * | 2005-02-01 | 2011-10-12 | 催化剂蒸馏技术公司 | Process and catalyst for selective hydrogenation of dienes and acetylenes |
| CN113559870A (en) * | 2020-04-28 | 2021-10-29 | 中国石油化工股份有限公司 | Heavy oil hydrogenation catalyst and preparation method and application thereof |
| CN114602448A (en) * | 2020-12-03 | 2022-06-10 | 中国科学院大连化学物理研究所 | Catalyst, preparation method and application thereof |
-
2003
- 2003-05-31 CN CN 03133564 patent/CN1221638C/en not_active Expired - Lifetime
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101133006B (en) * | 2005-02-01 | 2011-10-12 | 催化剂蒸馏技术公司 | Process and catalyst for selective hydrogenation of dienes and acetylenes |
| US8227650B2 (en) | 2005-02-01 | 2012-07-24 | Catalytic Distillation Technologies | Process and catalyst for selective hydrogenation of dienes and acetylenes |
| CN101191078B (en) * | 2006-11-21 | 2011-07-13 | 中国石油化工股份有限公司 | Nickel catalyst with composite pore structure used for selective hydrogenation |
| CN113559870A (en) * | 2020-04-28 | 2021-10-29 | 中国石油化工股份有限公司 | Heavy oil hydrogenation catalyst and preparation method and application thereof |
| CN114602448A (en) * | 2020-12-03 | 2022-06-10 | 中国科学院大连化学物理研究所 | Catalyst, preparation method and application thereof |
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| CN1221638C (en) | 2005-10-05 |
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