CN102728375B - Preparation method of Mo-Ni catalyst for C4 fraction low-temperature hydrogenation - Google Patents
Preparation method of Mo-Ni catalyst for C4 fraction low-temperature hydrogenation Download PDFInfo
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Abstract
The invention discloses a method of Mo-Ni catalyst for C4 fraction low-temperature hydrogenation. The Mo-Ni catalyst for C4 fraction low-temperature hydrogenation adopts gamma-Al2O3 as a carrier, contains main active ingredients of Mo and Ni and is prepared by a co-impregnation or stepwise impregnation method. The Mo-Ni catalyst for C4 fraction low-temperature hydrogenation comprises: by weight, 8.0 to 25.0% of Mo2O3, 6.0 to 25.0% of NiO and 60 to 80% of gamma-Al2O3 as a carrier, and has a specific surface area of 120 to 200m<2>/g. The Mo-Ni catalyst for C4 fraction low-temperature hydrogenation is especially suitable for C4 fraction low-temperature hydrogenation and does not need prevulcanization before use. In a heat insulation or tubular fixed bed reactor, a reaction temperature is in a range of 25 to 105 DEG C; reaction pressure is in a range of 1.5 to 3.0MPa; a liquid hourly space velocity is in a range of 1.0 to 6.0h<-1>; and a hydrogen/olefin mole ratio is in a range of 1.02 to 1.2. Aiming at C4 fractions having various olefin content values, the Mo-Ni catalyst for C4 fraction low-temperature hydrogenation can realize that olefin content after hydrogenation is less than 1%.
Description
Technical field
The present invention relates to a kind of Catalysts and its preparation method for olefins hydrogenation, particularly a kind of Mo-Ni catalyst is for the method for C 4 fraction low temperature hydrogenation.
Background technology
The a large amount of C of the device by-product such as often decompression of refinery, catalytic cracking, hydrocracking, delayed coking, cracking of ethylene
4hydrocarbon, the C of most domestic enterprise
4hydrocarbon is all used as liquefied gas and sells, and chemical utilization rate is not high.
Ethene is the basic material of petrochemical industry, and current domestic ethene production capacity volume increase rapidly.In ethylene production, cost of material accounts for 60～80% of production cost.At present ethylene production be take hydrocarbon raw material steam cracking as main, and cracking stock mainly contains ethane, LPG, raffinates oil, naphtha, hydrogenation tail oil etc.Ethylene cracking material is heavier, and byproduct is more, and material treating capacity is larger, and the equipment, public work and the auxiliary equipment expense that need are higher, causes the increase of investment of ethylene unit.With decompression diesel oil, making its material treating capacity of raw material is 3.78 times that ethane is made raw material.Therefore ethylene raw high quality, lighting are a kind of trend, can improve the economic benefit of ethene enterprise.C
4it after hydrogenation is saturated, is the ethylene cracking material of high-quality.
C after saturated to hydrogenation
4carry out separation, iso-butane can be made solvent, and normal butane can be used to produce cis-butenedioic anhydride, and cis-butenedioic anhydride is the raw material of producing BDO, gamma-butyrolacton, oxolane.
Therefore, by C
4cut fraction hydrogenation is saturated is C
4an important channel of the utilization of resources.
CN 101081998 B disclose a kind of C
4the method of cut fraction hydrogenation, fills in the series connection of hydrogenation catalyst I and hydrogenation catalyst II or segmentation in one or two fixed bed reactors C
4after cut and hydrogen mix, first contact with catalyst I that to carry out diene hydrogenation saturated, then contact and carry out impurity removal and olefin saturated with hydrogenation catalyst II.Hydrogenation catalyst I be take a kind of aluminium oxide as carrier, contains 0.5～8% heavy cobalt and/or nickel, 2～15% heavy molybdenums and/or tungsten, 2～8% heavy alkali metal; Hydrogenation catalyst II be take aluminium oxide as carrier, active component is with oxide note and take catalyst as benchmark, its content is: tungsten 10～30% is heavy, nickel 1～7% is heavy, cobalt 0.01～1.0% is heavy, co-catalyst 0.1～10% weight, is selected from arbitrary element in magnesium, zinc, iron, calcium.Catalyst I, II all need through presulfurization before using.Hydrogenation conditions is: volume space velocity 0.5～4.0h when reaction pressure 1.0～5.0MPa, 120～250 ℃ of average reaction temperature, liquid
-1, hydrogen to oil volume ratio 150～500Nm
3/ m
3.This catalyst hydrogenation reaction temperature is high, and alkene is polymerization gum deposit at high temperature easily, causes catalyst to shorten service life.
CN 101037613A discloses a kind of preparation method of nickel series hydrogenating catalyst, this catalyst take aluminium oxide and or silica be carrier, adopt the method for co-precipitation to make, main active component is Ni, La, auxiliary agent X
1with carrier X
2o forms, the weight percentage forming in catalyst: NiO40～70%, La
2o
32～5%, X
1o2～5%, X
2o20～50%, wherein X
1be selected from Cu, Mg, Zr, X
2be selected from Al, Si; Its specific area 80～200m
2/ g, specific pore volume 0.4～0.8ml/g, this catalyst is applicable to monoolefin hydrogenation, is particularly useful for C
9cut fraction hydrogenation, has higher hydrogenation activity, also has certain sulfur poisoning-resistant, anti-coking performance.But this catalyst is high-nickel catalyst, adopt coprecipitation method to produce, pass through raw material dissolving, precipitation, filtration, washing, oven dry, moulding, roasting making step, technical process is relatively loaded down with trivial details.
CN 101433853A discloses a kind of hydrogenation catalyst, preparation method and application thereof, and this catalyst be take aluminium oxide as carrier, active component palladium 0.3～0.5wt%, auxiliary agent X
11.0～3.0wt%, is selected from one or more in B, P, Si, auxiliary agent X
20.01～5wt%, is selected from one or more in Ag, Pb, Au, Co, Cu, Bi, Ni, Pt, Ti, alkali metal and/or alkaline-earth metal 0.5～4.0wt%; Catalyst surface area 50～150m
2/ g, specific pore volume 0.2～1.0ml/g.This catalyst is specially adapted to the C of catalytic cracking process and steam cracking byproduct in process
4cut fraction hydrogenation is saturated.But this catalyst be take precious metal palladium as active component, and cost is high.And noble metal requires strict to the poisonous substance such as sulphur, arsenic in raw material.
CN 1508103A, ZL01114177.8 disclose respectively and have been applicable to C
4the catalyst of cut fraction hydrogenation, but they take noble metal as active component, exist equally catalyst cost high, to the strict defect of the poisonous substance such as sulphur, arsenic requirement in raw material.
US Patent No. P4482767 discloses a kind of Pd/Al
2o
3catalyst, for C
3cut fraction hydrogenation.
In sum, olefin hydrogenation catalyst be take aluminium oxide substantially as carrier, load active component at present.According to active component, classify, mainly containing palladium system, nickel system, cobalt-molybdenum-nickel is three classes.Cobalt-molybdenum-nickel catalyst needs sulfuration before using, reaction temperature high (200～300 ℃), easily causes olefin high-temperature polymerization; Palladium series catalyst reaction temperature is low, but noble metal catalyst cost is high, easily poisoning; Nickel catalyst, because nickel content is high, needs to adopt coprecipitation preparation, compares with load method preparation, and catalyst preparation process is complicated, loaded down with trivial details.
In view of present disclosed C
4the catalyst of cut fraction hydrogenation, or hydrogenation temperature is high or preparation process is complicated, loaded down with trivial details or take precious metal palladium as active component, cost is high, and the poisonous substance such as sulphur, arsenic in raw material is required to the problems such as strict, from economy or practicality, consider, can bring certain difficulty to industrial applications.Therefore be necessary to find the non-precious metal catalyst that a kind of cost is low, manufacture process is relatively simple, low temperature active is high, for C
4cut fraction hydrogenation is saturated.
Summary of the invention
The invention provides a kind of Mo-Ni catalyst for method of C 4 fraction low temperature hydrogenation and preparation method thereof.Main purpose is high for existing catalyst or hydrogenation temperature, or preparation process is complicated, loaded down with trivial details, or take precious metal palladium as active component, cost high, and the poisonous substance such as sulphur, arsenic in raw material is required to the problems such as strict, provide that a kind of cost is low, manufacture process is relatively simple, the active high catalyst of low temperature hydrogenation, for C
4cut fraction hydrogenation is saturated.
Content of the present invention is:
A kind of Mo-Ni catalyst is for C
4the method of cut low temperature hydrogenation, is characterized in that: take gama-alumina as carrier, the mode by dipping is by active constituent loading on the carrier after moulding, through oven dry, roasting, make, this catalyst activity component is molybdenum, nickel, in total catalyst weight 100%, containing Mo
2o
38.0%～25.0%, NiO6.0%～25.0%, the catalyst making is stripe shape, trifolium-shaped or the ball-type of Φ 3 * 3～5mm, specific area 120～200m
2/ g; This catalyst does not need to carry out presulfurization before using, in hydrogen atmosphere, with 3 ℃/min, rise to 120 ℃, insulation 1h, then with 2 ℃/min, rise to 300 ℃, insulation 4h, then in hydrogen atmosphere, bed temperature is down to below 150 ℃, close hydrogen terminal valve, be naturally cooled to room temperature or required feeding temperature, can carry out hydrogenation reaction; Its process conditions are: in thermal insulation or calandria type fixed bed reactor, and 20～40 ℃ of feeding temperatures, 20～105 ℃ of reaction temperatures, reaction pressure 1.5～3.0MPa, volume liquid hourly space velocity (LHSV) 1.0～10.0h
-1, hydrogen/olefin molar ratio 1.02～1.2.
The content of active component is in total catalyst weight 100%, containing Mo
2o
310.0%～20.0%, NiO8.0%～15.0%.
Active component is introduced in the mode of salting liquid, and the soluble-salt of nickel is a kind of in nitrate, acetate, formates, and the soluble-salt of molybdenum is ammonium molybdate.
It is characterized in that: in the preparation process of catalyst, active component simultaneously or step load on carrier, then make finished catalyst after drying, roasting.
By active component step load on carrier time, first load active component molybdenum, load active component nickel again after oven dry, then makes finished catalyst after drying, roasting.
During load active component, bake out temperature is higher than 110 ℃, lower than 120 ℃.
During load active component, 350～375 ℃ of sintering temperatures.
Be applicable to C
4any alkene low temperature hydrogenation in hydrocarbon, after hydrogenation, olefin(e) centent is less than 1%.
Advantage of the present invention is: the prepared catalyst of the present invention is specially adapted to C
4cut low temperature hydrogenation, and do not need to carry out presulfurization before using.While carrying out hydrogenation reaction, under cryogenic conditions, carry out, in thermal insulation or calandria type fixed bed reactor, 20～40 ℃ of feeding temperatures, 25～105 ℃ of reaction temperatures, reaction pressure 1.5～3.0MPa, volume liquid hourly space velocity (LHSV) 1.0～10.0h
-1, hydrogen/olefin molar ratio 1.02～1.2, the C of any olefin(e) centent
4cut, after hydrogenation, olefin(e) centent all can be less than 1%.
The specific embodiment
Catalyst of the present invention can be stripe shape, trifolium-shaped or the ball-type of Φ 3 * 3～5mm, specific area 120～200m
2/ g.
Catalyst of the present invention be take gama-alumina as carrier, and take nickel, molybdenum is active component.In total catalyst weight 100%, containing Mo
2o
38.0～25.0%, NiO6.0～25.0%.
Catalyst of the present invention, the mode by active component by dipping is carried on the gamma-aluminium oxide carrier after moulding, through oven dry, roasting, makes required C
4cut fraction hydrogenation catalyst.
In method for preparing catalyst of the present invention, active component is steeped by total immersion or the mode of step impregnation is carried on the alumina support after moulding.Impregnation method and impregnation sequence have a certain impact to hydrogenation activity.Preferred first load molybdenum, the mode of loading of nickel-loaded again.
In method for preparing catalyst of the present invention, active component is to introduce in the mode of salting liquid.The soluble-salt of nickel can be nitrate, acetate, formates.The soluble-salt of molybdenum is ammonium molybdate.
In hydrogenation catalyst preparation method of the present invention, 110～130 ℃ of bake out temperatures, preferably 118～120 ℃.
In hydrogenation catalyst preparation method of the present invention, 350～500 ℃ of sintering temperatures, preferably 350～375 ℃.
Catalyst of the present invention does not need to carry out presulfurization before using, and after only need reducing in hydrogen atmosphere, can be used for hydrogenation reaction.
After catalyst hydrogenation activity of the present invention reduces, reduction again in hydrogen atmosphere, hydrogenation activity can recover.
Below by embodiment, further illustrate the present invention, but the present invention is not limited to embodiment, authority of the present invention is as the criterion with claims.
The preparation of catalyst: take the gamma-aluminium oxide carrier after a certain amount of moulding, with the soluble-salt of nickel, the soluble-salt of molybdenum, make and the isopyknic solution of carrier, at room temperature carrier is soaked in to certain hour in this solution, incline and residue soak, after oven dry, roasting, make required catalyst.
Evaluating catalyst condition: 20～40 ℃ of feeding temperatures, 20～105 ℃ of reaction temperatures, reaction pressure 1.5～3.0MPa, volume liquid hourly space velocity (LHSV) 1.0～10.0h
-1, hydrogen/olefin molar ratio 1.02～1.2.
Embodiment 1
Take the gamma-aluminium oxide carrier I 20g (about 30ml) after moulding, take nickel nitrate 14.86g, ammonium molybdate 5.52g is made into 30ml solution.At room temperature carrier is soaked in this mixed solution to 12 hours, inclines and residue soak, after 120 ℃ of oven dry, 350 ℃ of roasting 6h, the catalyst of preparation is JH-1.In the same way gamma-aluminium oxide carrier II, III are made respectively to catalyst JH-2, JH-3.
JH-1, JH-2, JH-3 are carried out to performance evaluation, and evaluation result is in Table 1.
Catalyst performance prepared by table 1 different carriers
Embodiment 2
Take the gamma-aluminium oxide carrier III 30g (about 45ml) after moulding, take nickel nitrate 22.29g, ammonium molybdate 8.28g is made into 45ml solution.At room temperature carrier is soaked in solution to 12 hours, inclines and residue soak.After 125 ℃ of oven dry, be divided into three parts, respectively at 375 ℃, 400 ℃, 500 ℃ roasting 6h.The catalyst of preparation is JH-4, JH-5, JH-6.
JH-4, JH-5, JH-6 are evaluated, and with the comparison of JH-3 evaluation result, evaluation result table 2.
Catalyst performance prepared by the different sintering temperatures of table 2
Embodiment 3
The gama-alumina taking after moulding is carrier II 20g (about 30ml), takes nickel nitrate 29.72g, ammonium molybdate 11.04g is made into 60ml solution.Get 30ml mixed liquor, at room temperature carrier is soaked in mixed liquor to 12 hours, incline and residue soak, in 120 ℃ of oven dry; Get again residue 30ml mixed liquor, at room temperature the carrier after a load is soaked in this mixed liquor to 12 hours, incline and residue soak, in 120 ℃ of oven dry, 350 ℃ of roasting 6h.The catalyst of preparation is JH-7.
JH-7 is evaluated, and with the comparison of JH-2 evaluation result, evaluation result table 3.
The Hydrogenation of the catalyst of table 3 single-steeping and double-steeping
Embodiment 4
Take the gamma-aluminium oxide carrier III 20g (about 30ml) after moulding, take nickel nitrate 14.86g and be made into 30ml solution, at room temperature carrier is soaked in solution to 12 hours, incline and residue soak, in 120 ℃ of oven dry; Take again ammonium molybdate 5.52g and be made into 30ml solution, at room temperature the carrier after nickel-loaded is soaked in ammonium molybdate solution to 12 hours, incline and residue soak, in 120 ℃ of oven dry, 350 ℃ of roasting 6h.The catalyst of preparation is JH-8.
JH-8 is evaluated, and evaluation result is in Table 4.
Embodiment 5
Take the gamma-aluminium oxide carrier III 20g (about 30ml) after moulding, take ammonium molybdate 5.52g and be made into 30ml solution, at room temperature carrier is soaked in solution to 6 hours, incline and residue soak, in 120 ℃ of oven dry; Take again nickel nitrate 14.86g and be made into 30ml solution, at room temperature the carrier after load molybdenum is soaked in nickel nitrate solution to 6 hours, incline and residue soak.In 120 ℃ of oven dry, 350 ℃ of roasting 6h.The catalyst of preparation is JH-9.
JH-9 is evaluated, and with JH-8, the comparison of JH-3 evaluation result, evaluation result is in Table 4.
The standby catalyst performance of table 4 active component different loads sequential system
Embodiment 6
Take the gamma-aluminium oxide carrier III 20g (about 30ml) after moulding, take ammonium molybdate 5.52g and be made into 30ml solution, at room temperature carrier is soaked in solution to 6 hours, incline and residue soak, in 120 ℃ of oven dry; Take again nickel acetate 9.03g and be made into 30ml solution, at room temperature the carrier after load molybdenum is soaked in nickel nitrate solution to 6 hours, incline and residue soak.In 120 ℃ of oven dry, 350 ℃ of roasting 6h.The catalyst of preparation is JH-10.
JH-10 is evaluated, and compare with JH-9, the results are shown in Table 5.
Catalyst performance prepared by the different nickel raw materials of table 5
Embodiment 7
Take the gamma-aluminium oxide carrier III 20g (about 30ml) after moulding, take ammonium molybdate 5.52g and be made into 30ml solution, at room temperature carrier is soaked in solution to 6 hours, incline and residue soak, in 120 ℃ of oven dry; Take again nickel nitrate 9.98g and be made into 30ml solution, at room temperature the carrier after load molybdenum is soaked in nickel nitrate solution to 6 hours, incline and residue soak.In 120 ℃ of oven dry, 350 ℃ of roasting 6h.The catalyst of preparation is JH-11.
JH-11 is evaluated, and evaluation result is in Table 6.
Embodiment 8
Take the gamma-aluminium oxide carrier III 20g (about 30ml) after moulding, take ammonium molybdate 4.02g and be made into 30ml solution, at room temperature carrier is soaked in solution to 4 hours, incline and residue soak, in 120 ℃ of oven dry; Take again nickel nitrate 9.98g and be made into 30ml solution, at room temperature the carrier after load molybdenum is soaked in nickel nitrate solution to 4 hours, incline and residue soak.In 120 ℃ of oven dry, 350 ℃ of roasting 6h.The catalyst of preparation is JH-12.
JH-12 is evaluated, and compare with JH-11JH-9, evaluation result is in Table 6.
The performance of the catalyst of table 6 different loads amount
Evaluating catalyst
The hydrogenation catalyst JH-9 that embodiment 5 is made carries out different C4 raw material Hydrogenations and investigates, and investigates and the results are shown in Table 7.
Table 7JH-9 is to different C4 raw material Hydrogenations
The hydrogenation catalyst JH-9 that embodiment 5 methods are made remains C with ethene
4raw material continuous operation, carries out catalyst life investigation, investigates and the results are shown in Table 8.
Olefin(e) centent and catalyst runs cycle in table 8 raw material
Claims (8)
1. a Mo-Ni catalyst is for C
4the method of cut low temperature hydrogenation, is characterized in that: take gama-alumina as carrier, the mode by dipping is by active constituent loading on the carrier after moulding, through oven dry, roasting, make, this catalyst activity component is molybdenum, nickel, in total catalyst weight 100%, containing Mo
2o
38.0%～25.0%, NiO6.0%～25.0%, the catalyst making is stripe shape, trifolium-shaped or the ball-type of Φ 3 * 3～5mm, specific area 120～200m
2/ g; This catalyst does not need to carry out presulfurization before using, in hydrogen atmosphere, with 3 ℃/min, rise to 120 ℃, insulation 1h, then with 2 ℃/min, rise to 300 ℃, insulation 4h, then in hydrogen atmosphere, bed temperature is down to below 150 ℃, close hydrogen terminal valve, be naturally cooled to room temperature or required feeding temperature, can carry out hydrogenation reaction; Its process conditions are: in thermal insulation or calandria type fixed bed reactor, and 20～40 ℃ of feeding temperatures, 20～105 ℃ of reaction temperatures, reaction pressure 1.5～3.0MPa, volume liquid hourly space velocity (LHSV) 1.0～10.0h
-1, hydrogen/olefin molar ratio 1.02～1.2.
2. Mo-Ni catalyst according to claim 1 is for C
4the method of cut low temperature hydrogenation, is characterized in that: the content of active component is in total catalyst weight 100%, containing Mo
2o
310.0%～20.0%, NiO8.0%～15.0%.
3. Mo-Ni catalyst according to claim 1 is for the method for C 4 fraction low temperature hydrogenation, it is characterized in that: active component is introduced in the mode of salting liquid, the soluble-salt of nickel is a kind of in nitrate, acetate, formates, and the soluble-salt of molybdenum is ammonium molybdate.
According to the Mo-Ni catalyst described in claim 1 or 2 or 3 for the method for C 4 fraction low temperature hydrogenation, it is characterized in that: in the preparation process of catalyst, active component simultaneously or step load on carrier, then make finished catalyst after drying, roasting.
5. Mo-Ni catalyst according to claim 4 is for the method for C 4 fraction low temperature hydrogenation, it is characterized in that: by active component step load on carrier time, first load active component molybdenum, load active component nickel again after oven dry, then makes finished catalyst after drying, roasting.
6. Mo-Ni catalyst according to claim 5, for the method for C 4 fraction low temperature hydrogenation, is characterized in that: during load active component, bake out temperature is higher than 110 ℃, lower than 120 ℃.
7. Mo-Ni catalyst according to claim 5, for the method for C 4 fraction low temperature hydrogenation, is characterized in that: during load active component, and 350～375 ℃ of sintering temperatures.
8. Mo-Ni catalyst according to claim 5, for the method for C 4 fraction low temperature hydrogenation, is characterized in that: be applicable to C
4any alkene low temperature hydrogenation in hydrocarbon, after hydrogenation, olefin(e) centent is less than 1%.
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|---|---|---|---|---|
| CN1217293A (en) * | 1997-10-13 | 1999-05-26 | 法国石油公司 | 2:1 laminated silicate catalyst with very large crystal lattice lattice span for bridging two octabedras and inversion method |
| CN101239892A (en) * | 2008-03-10 | 2008-08-13 | 上海华谊丙烯酸有限公司 | Method for preparing iso-butyraldehyde and isobutyl alcohol by methylacrolein hydrogenation |
| CN102886262A (en) * | 2011-07-21 | 2013-01-23 | 北京石油化工学院 | C4 alkyne selective hydrogenation catalyst and preparation method and application thereof |
-
2011
- 2011-04-15 CN CN201110094567.6A patent/CN102728375B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1217293A (en) * | 1997-10-13 | 1999-05-26 | 法国石油公司 | 2:1 laminated silicate catalyst with very large crystal lattice lattice span for bridging two octabedras and inversion method |
| CN101239892A (en) * | 2008-03-10 | 2008-08-13 | 上海华谊丙烯酸有限公司 | Method for preparing iso-butyraldehyde and isobutyl alcohol by methylacrolein hydrogenation |
| CN102886262A (en) * | 2011-07-21 | 2013-01-23 | 北京石油化工学院 | C4 alkyne selective hydrogenation catalyst and preparation method and application thereof |
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