CN1916121B - Method for preparing diene selective hydrotreating catalyst for gasoline - Google Patents
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- CN1916121B CN1916121B CN2005100904755A CN200510090475A CN1916121B CN 1916121 B CN1916121 B CN 1916121B CN 2005100904755 A CN2005100904755 A CN 2005100904755A CN 200510090475 A CN200510090475 A CN 200510090475A CN 1916121 B CN1916121 B CN 1916121B
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Abstract
This invention discloses a method for preparing hydrogenation catalyst for selectively hydrogenating diene in gasoline. The method comprises: (1) adopting Al2O3 torrefied at 900-1200 deg.C as the carrier, and immersing in a liquid prepared from ammonia solution and active metal saline solution by equal-volume immersion; (2) drying in air or in vacuum at 100-200 deg.C; (3) torrefying at 250-350 deg.C in air to obtain Ni-loaded Al2O3; (4) reducing by hydrogen at 350-450 deg.C, and sulfurizing by sulfurization agent to obtain Ni catalyst. In the immersing liquid, the weight ratio of Ni, ammonia solution and H2O is 1: (0.5-5.0): 5, wherein Ni content is 5-20%. The catalyst has high selectivity; high hydrogenation activity and high stability even at low temperature, low pressure and low hydrogen/gasoline ratio, and can effectively reduce the energy consumption.
Description
Technical field:
The present invention relates to a kind of preparation method of diene selective hydrotreating catalyst for gasoline, especially relate to and to improve diolefin hydrogenation activity, the catalytically cracked gasoline of stability, the non-noble metal Ni-based Catalysts and its preparation method of low temperature diene selection hydrogenation and the application technology condition of steam cracking gasoline.
Background technology:
At present, the subject matter that FCC gasoline exists is olefin(e) centent height, sulphur content height, can not satisfy the specification of quality of motor spirit.For this reason, need carry out following process to FCC gasoline and improve its quality, for example use to contain than the strong solid acids catalyzer, improve gasoline octane rating, reduction olefin(e) centent by technology such as isomerization, aromizing; By facing the hydrogen desulfurization technology, reduce the sulphur content in the FCC gasoline.But owing to contain diolefin and the alkynes of 0.35～1.0%w in the pressure gasoline, with respect to monoolefine, diolefin and alkynes is polymerization reaction take place under the effect of acid catalyst, sulphur, nitrogen, oxygen impurities very easily, forms oligopolymer and colloid.They can be deposited on the surfaces externally and internally of gasoline processing catalyst, the duct of blocking catalyst, and the active centre of covering catalyst, thus causing the rapid deactivation of catalyzer, reduce work-ing life.For fear of the influence of diolefin and alkynes to gasoline following process catalyzer, need carry out selective hydrogenation to catalytically cracked gasoline, steam cracking gasoline, when being removed, diolefin and alkynes do not reduce original olefin(e) centent in the raw material, and octane value is constant, helps the following process of gasoline.Use the catalyst based diolefin and the alkynes that can under lower temperature of reaction, remove wherein of non-noble metal Ni of the present invention, also can remove impurity such as part sulphur in the gasoline, nitrogen, colloid simultaneously, not only the gasoline following process is had very important significance, but also can obviously improve the stability of gasoline.
At present, the catalyzer of diene and alkynes has some patents in the selective hydrogenation and removing gasoline.These patents reflect that the activity of such catalysts component is that platinum, palladium, silver, tungsten, nickel, molybdenum, iron etc. support on inert support, and the catalyzer of loaded palladium and nickel more is subjected to general attention.For example, US 3,234, and 298 (W.C.Van zijillanghout et al) had once described sulfurized Ni/Al
2O
3Or Mo/Al
2O
3Catalyzer is used for the selection hydrogenation of pyrolysis gasoline and kerosene, to improve the stability of vapour, kerosene.US 3,847, and 835 (JeanCosyns et al) have introduced a kind of catalyzer that the pyrolysis gasoline diene selective hydrogenation is a monoolefine that is used for, and this catalyzer is carried on the solid alumina by the Ni of 2%～10% (w) or Co and is prepared from, and need use H
2S carries out pre-treatment to catalyzer, and its reactive activity component is nickelous sulfide or cobaltous sulfide, and has provided preferable surface-area and pore volume.US 3,919,341 (Germanas et al) and 5,417,844 (Boitiaux et al) have described two kinds of catalyzer that are used for the pyrolysis gasoline selective hydrogenation respectively, two kinds of activity of such catalysts components are Ni, and carrier is a solid alumina, and two kinds of catalyzer all need to carry out pre-treatment with organic compounds containing sulfur before use.Chinese patent CN 1,218,822 to have narrated a kind of be that auxiliary agent, Ni are that active ingredient, aluminum oxide are the diolefin hydrogenation catalyzer of carrier with Li or alkaline-earth metal, be mainly used in the hydrogenation process of steam cracking gasoline, the characteristics of its preparation are to be the modified additive of alumina supporter with Li or alkaline-earth metal, and, make it in conjunction with entering in the structure of alumina supporter through pyroprocessing; After obtaining stable carrier with the solution impregnating carrier of nickel salt load Ni active ingredient, obtain described catalyzer through comparatively high temps and the processing of long period.More than several patents in the method for load Ni active ingredient, employing all be the aqueous solution immersion process for preparing of nickel metal-salt.The subject matter that this method exists is in steeping fluid impregnation drying process, concentrating appears in excessive active ingredient salt, gathering becomes xln, cause the active ingredient skewness on the one hand, the gathering in aperture has also influenced the diffusion of reactant in the liquid phase reaction course on the other hand, and activity of such catalysts and stability are reduced.
Summary of the invention
It is active ingredient with the non-noble metal Ni that purpose of the present invention just is to provide a kind of, through the γ-Al of pyroprocessing
2O
3Preparation method for a kind of diene selective hydrotreating catalyst for gasoline of carrier, prepared Ni catalyzer not only low temperature (130～200 ℃), low pressure (1.0～4.0MPa), very high diolefin hydrogenation activity is arranged under the condition of low hydrogen/gasoline ratio (hydrogen to oil volume ratio is 10: 1～60: 1), very high selectivity and stability are also arranged, can effectively reduce industrial production energy consumption and cost.
The present invention is achieved in that
A kind of diene selective hydrotreating catalyst for gasoline is with through 900 ℃～1200 ℃ high temperature γ-Al of roasting once more
2O
3Be carrier, the steeping fluid that is made into ammoniacal liquor and reactive metal salt brine solution floods by equi-volume impregnating, wherein Ni in the steeping fluid: ammoniacal liquor: H
2The ratio of O is 1: 0.5: 5～1: 5.0: 5.0 (mass ratio), and Ni content is 5～20%, and the dipping back is drying or vacuum-drying down in 100 ℃～200 ℃ temperature range, roasting in the air in 250 ℃～350 ℃ temperature range again.Gained is loaded with the Al of Ni
2O
3Reduce in 350 ℃～450 ℃ temperature range with hydrogen reducing gas, and adopt vulcanizing agent to vulcanize;
Described γ-Al
2O
3Be microspheric form or other shape, thermal treatment is 1～5 hour in 900 ℃～1200 ℃ air, its bulk specific gravity 6.5～7.5mg/L, and pore volume 0.4～0.5ml/g, the aperture accounts for more than 80% greater than the hole of 4nm, and surface-area is greater than 100m
2/ g.
The nitrate that described water-soluble active metal-salt is transition metal Ni, acetate, oxymuriate etc., and be configured to dipping solution, wherein Ni in the steeping fluid: ammoniacal liquor: H with water, ammoniacal liquor
2The ratio of O is 1: 0.5: 5～1: 5.0: 5.0 (mass ratio), and the carrying capacity of reactive metal Ni element is 5～20%w.
Described drying, roasting condition be, 100 ℃～180 ℃ following dryings or vacuum-drying 3～8 hours were handled 0～2 hour in 250 ℃～350 ℃ air again.
Described catalyzer hydrogen reducing condition and cure conditions are: 350～450 ℃ of reduction temperatures, 3～8 hours recovery times, the reduction pressure be normal pressure to 0.3MPa, the reducing gas air speed is 420～600h
-1(STP).Then use sulfuration liquid pre-treatment 0.1～5 hour down at 20～100 ℃.
Catalyzer method for making of the present invention is as follows:
With γ-Al through 900 ℃～1200 ℃ of processing
2O
3Be carrier, with the nitrate of ammoniacal liquor and non-noble metal Ni, acetate, oxymuriate etc. are made into ammonia soln, are carried on by pickling process on the surface of prepared alumina supporter, and its reactive metal Ni constituent content is 5～20%w, preferably 8～17%w; After 100 ℃～180 ℃ following dryings or vacuum-drying, handled 0～2 hour in 250 ℃～350 ℃; Obtained sample reduces in nitrogen atmosphere again, 300 ℃～450 ℃ of reduction temperatures, 3～8 hours recovery times, the reduction pressure be normal pressure to 0.3MPa, the reducing gas air speed is 420～600h
-1(STP), just then vulcanize and to obtain catalyzer of the present invention.
The full distillation gasoline of catalysis (initial boiling point～200 ℃) Gu the process of selective hydrogenation and removing diene normally under gas/liquid/three-phase condition, carry out, wherein gasoline fraction is to exist with liquid form, excess hydrogen exists with the gas phase form, part hydrogen is dissolved in the gasoline fraction, be the used hydrogen of diolefin hydrogenation, catalyzer is to be present in the reactor with solid form.The full distillation gasoline diene selection hydrogenation reaction of the catalysis that the present invention carried out is to adopt after the gas-liquid mixed and the feeding manner on flowing to.The setting of reaction conditions such as pressure, temperature, liquid feeding amount and amounts of hydrogen is a purpose to remove diene in addition.Volume with catalyzer is a benchmark, and the liquid air speed of catalytic gasoline is 2～10h
-1, temperature is 130 ℃～200 ℃, and pressure is 1.0MPa～4.0MPa, and hydrogen to oil volume ratio (STP) is 10: 1～60: 1.Catalytic gasoline diene selective hydrotreating method of the present invention can be in a reactor, or carries out in the reactor of a plurality of parallel connections or polyphone.
Specified operational procedure is:
(1), γ-Al of 1～5 hour of thermal treatment in 900 ℃～1200 ℃ air
2O
3Carrier, its bulk specific gravity 6.5～7.5mg/L, pore volume 0.4～0.5cc/g, the aperture accounts for more than 80% greater than the hole of 4nm, and surface-area is greater than 100m
2/ g.
(2), with the salt of the ammonia solvent water-soluble active metal Ni of 25w%～28w%, press Ni: ammoniacal liquor: H
2O is that 1: 0.5: 5～1: 5.0: 5.0 (mass ratio) is made into ammonia soln.
(3), get the solution that a certain amount of above-mentioned (2) step is made into, the carrier that obtains through (1) step is carried out incipient impregnation, make the charge capacity of active ingredient Ni element reach 5～20%w, simultaneously in 100 ℃～200 ℃ following dryings or vacuum-drying 3～8 hours, in 250 ℃～350 ℃ air, handled 0～4 hour again, obtain the roasting sample of the catalyzer of carrying active component NiO.
(4), under 300～450 ℃, the catalyzer that step (3) is obtained with hydrogen reduced 3～8 hours, the reduction pressure be normal pressure to 0.3MPa, the reducing gas air speed is 420～600h
-1(STP), then use sulfuration liquid pre-treatment 0.1～5 hour down, obtain diolefin hydrogenation high reactivity of the present invention, highly selective and long period stable catalyst at 20～100 ℃.
Catalyzer of the present invention has good diene selective hydrotreating performance, specifically, is that diene carries out having very high diolefin hydrogenation activity, selectivity and long life, C in the process of selective hydrogenation in to catalytic gasoline
5And C
6The diolefin hydrogenation transformation efficiency reaches 100%, and total monoene reduction is less than 1.0%.
Be characterized in adopting the γ-Al of pyroprocessing
2O
3Be carrier, this carrier has very high surface-area on the one hand, and reasonable pore structure is also arranged on the other hand, the mass transfer that this has just played dispersed active metal and has helped the liquid phase reaction thing.Another characteristics of the present invention are to be that solvent prepares water-soluble Ni salt steeping fluid with ammoniacal liquor, adopt the equi-volume impregnating preparation.This special steeping fluid, the coacervation that can avoid nickel salt in the impregnation drying process, to occur, make Ni salt can in whole dipping and drying process, can on alumina surface, not take place to move and assemble, can guarantee that Ni salt is dispersed on the carrier surfaces externally and internally uniformly on the one hand, rather than concentrate on the aperture, very little to the pore distribution influence of carrier on the other hand, guaranteed to be used for liquid reactive pore distribution and pore volume.
Description of drawings
Fig. 1 is catalyzer of the present invention and commercial catalysts comparison diagram;
Fig. 2 is the hydrogenation performance map of catalyzer C of the present invention at more than 1000 hours continuous operation.
Embodiment
Further set forth catalyzer of the present invention, method for making and catalytic performance thereof with example below.
Embodiment 1:
With an amount of diameter is bead γ-Al of φ 1～2mm
2O
3Carrier in air, 1100 ℃ of following roastings 4 hours, is used for the carrier of subsequent catalyst after the cooling in retort furnace, its bulk specific gravity 0.72mg/L, and pore volume 0.41ml/g, the aperture accounts for 95% greater than the hole of 4nm, surface-area 101m
2/ g.
Embodiment 2:
Take by weighing the alumina supporter of preparation in the 70.0 gram embodiments 1, with 52.03 gram nitric acid nickel (NO
3)
26H
2After the solution that O, 35.6 ml distilled waters are made into floods 2 hours, preliminarily dried under room temperature, again 180 ℃ of following constant temperature vacuum-dryings 7 hours, 300 ℃ of roasting 1h in retort furnace again.Can prepare the catalyst A that the Ni metal content is 15.0%wt.
Embodiment 3:
With the alumina supporter of preparation in the 140 gram embodiments 1, with 69.37 gram nitric acid nickel (NO
3)
26H
2The solution that the ammoniacal liquor of O, 35.6 ml distilled waters and 45 milliliters of 25w%～28w% is made into flooded 2 hours, behind preliminarily dried under the room temperature, again 150 ℃ of following constant temperature vacuum-dryings 3 hours, in retort furnace,, can prepare the catalyst B that the Ni metal content is 10.0%wt in air, 280 ℃ of following roastings 2 hours.
Embodiment 4:
Alumina supporter, 26.02 gram nitric acid nickel (NO with preparation in the 35 gram embodiments 1
3)
26H
2The ammoniacal liquor of O, 17.6 ml distilled waters and 27.0 milliliters of 25w%～28w%, the preparation method who presses embodiment 3, can make the Ni metal content is the catalyzer C of 15.0%wt.
Embodiment 5:
The non-precious metal catalyst A that embodiment 2 is prepared in air, 450 ℃ of following roastings 2 hours, promptly gets the Ni catalyzer contrast medium D through the comparatively high temps roasting in retort furnace.
Embodiment 6:
It is active and stable to adopt the upper reaches feeding manner to estimate the diolefin hydrogenation of above-mentioned non-precious metal catalyst A～D in the small pressurized fixed-bed reactor.A certain amount of catalyzer is placed the middle part of reactor flat-temperature zone, fill with quartz sand up and down, be warming up to 380 ℃ under the hydro condition, constant temperature reduction 5 hours, reduction pressure is normal pressure, the reducing gas air speed is 420h
-1(STP), then device is cooled to room temperature, with extraordinary vulcanizing agent sulfuration 1 hour.Afterwards, be warming up to temperature of reaction, feed catalytic cracking full distillate gasoline reaction raw materials liquid and carry out the diolefin hydrogenation reaction.Facing the hydrogen hydrogenation conditions is: 150 ℃ of temperature of reaction, and reactive hydrogen dividing potential drop 1.5MPa, liquid amasss air speed 9.0h
-1, hydrogen to oil volume ratio (STP) 50: 1.The content of main component is in the catalytically cracked gasoline reaction raw materials liquid: carbon pentaene hydrocarbon 13.03% (wt), carbon five diene 0.438% (wt), C 6 olefin 10.14% (wt), total sulfur 244.9 μ g/g, total nitrogen 96.9 μ g/g.Take in test accurately to analyze being converted of carbon five, carbon six components and analyze the variation (this analytical procedure substitutes the analysis of total composition, and its accuracy reaches more than 94% by checking) of total composition with gas-chromatography.Reaction evaluating result (0～20h mean value is answered in negate) is as shown in table 1.By result in the table as can be known, the C catalyst effect is better.
The FCC gasoline diolefin hydrogenation catalytic performance of table 1, this patent catalyzer
| Catalyzer | A | B | C | D |
| C 5Diene conversion rate/% | 98.86 | 84.62 | 100 | 58.39 |
| C 5Pentaene hydrocarbon content/% (wt) | 13.19 | 12.74 | 12.93 | 12.69 |
| C 6Olefin(e) centent/% (wt) | 10.51 | 10.26 | 10.50 | 10.47 |
Embodiment 7:
With above-mentioned (embodiment 6) catalytic cracking full distillate gasoline is raw material, in the small pressurized fixed-bed reactor catalyzer C of the present invention and several industrialized catalyzer is compared.CH-24 and MH-3 are and catalyzer C of the present invention catalyzer of the same type that QSH-01 is the precious metals pd catalyzer.Reaction conditions is: 150 ℃ of temperature of reaction, and reactive hydrogen dividing potential drop 1.5MPa, liquid amasss air speed 24.0h
-1, hydrogen to oil volume ratio (STP) 50: 1.The result shows that C catalyzer of the present invention is compared with three kinds of industrialized catalyzer, all improves significantly aspect active and stable, as shown in Figure 1.
Embodiment 8:
With catalytic cracking full distillate gasoline is raw material, catalyzer C of the present invention has been carried out 1029 hours long-term operation in the small pressurized fixed-bed reactor.Reaction conditions is: 150 ℃ of temperature of reaction, and reactive hydrogen dividing potential drop 1.5MPa, liquid amasss air speed 3.0h
-1, hydrogen to oil volume ratio (STP) 50: 1.Major impurity in the raw material: total sulfur 244.9 μ g/g, total nitrogen 96.9 μ g/g.The result shows, catalyzer C in more than 1000 hour of continuous operation, C
5And C
6Diene is undetected always, and total C5 monoene, total C6 monoene reduction be all less than 1.0m%, and very stable, as shown in Figure 2.This illustrates active height of catalyzer diolefin hydrogenation of the present invention and good stability.
Claims (3)
1. the preparation method of a diene selective hydrotreating catalyst for gasoline is characterized in that: with through 900 ℃～1200 ℃ high temperature γ-Al of roasting once more
2O
3Be carrier, the γ-Al after wherein burning
2O
3Bulk specific gravity 6.5～7.5mg/L, pore volume 0.4～0.5mL/g, the aperture accounts for more than 80% greater than the hole of 4nm, and surface-area is greater than 100m
2/ g, the steeping fluid that is made into ammoniacal liquor and reactive metal salt brine solution floods by equi-volume impregnating, wherein Ni in the steeping fluid: ammoniacal liquor: H
2The mass ratio of O is 1: 0.5: 5～1: 5.0: 5.0, and Ni content is 5～20%; Dipping back is in 100 ℃～200 ℃ temperature range inner drying, roasting in the air in 250 ℃～350 ℃ temperature range again; Gained is loaded with the Al of Ni
2O
3Use hydrogen reducing, 350～450 ℃ of reduction temperatures, 3～8 hours recovery times, the reduction pressure be normal pressure to 0.3MPa, the reducing gas air speed is 420～600h
-1Use sulfuration liquid pre-treatment 0.1～5 hour down at 20～100 ℃ then.
2. press the preparation method of the described a kind of diene selective hydrotreating catalyst for gasoline of claim 1, it is characterized in that: described active metal salt is nitrate, acetate or the oxymuriate of transition metal Ni, and be configured to dipping solution with water, ammoniacal liquor, Ni in the steeping fluid wherein: ammoniacal liquor: H
2The mass ratio of O is 1: 0.5: 5～1: 5.0: 5.0, and the carrying capacity of reactive metal Ni element is 5～20%W.
3. by the preparation method of the described a kind of diene selective hydrotreating catalyst for gasoline of claim 1, it is characterized in that: described drying, roasting condition are that 100 ℃～180 ℃ were descended dry 3～8 hours, and handled 0～2 hour in 250 ℃～350 ℃ air.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102580751A (en) * | 2011-01-11 | 2012-07-18 | 中国石油大学(北京) | Diene selectivity hydrogenation catalyst and preparation method thereof |
| CN103215065B (en) * | 2012-01-18 | 2016-01-20 | 中国石油天然气股份有限公司 | Method for hydrotreating inferior catalytic cracking gasoline |
| CN112337468B (en) * | 2019-08-09 | 2023-12-22 | 中国石油天然气股份有限公司 | Olefin isomerization catalyst and preparation method and application thereof |
| CN114433092B (en) * | 2020-10-20 | 2024-01-30 | 中国石油化工股份有限公司 | Pre-sulfiding method of hydrogenation catalyst, obtained pre-sulfiding hydrogenation catalyst and application |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5534475A (en) * | 1994-03-02 | 1996-07-09 | Instituto Mexicano Del Petroleo | Catalytically active ceramic monoliths for the reduction of leaded gasoline fueled engine pollutants and the production thereof |
| CN1631526A (en) * | 2003-12-22 | 2005-06-29 | 中国石油化工股份有限公司 | Selective hydrogenation catalyst for alkadiene |
-
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5534475A (en) * | 1994-03-02 | 1996-07-09 | Instituto Mexicano Del Petroleo | Catalytically active ceramic monoliths for the reduction of leaded gasoline fueled engine pollutants and the production thereof |
| CN1631526A (en) * | 2003-12-22 | 2005-06-29 | 中国石油化工股份有限公司 | Selective hydrogenation catalyst for alkadiene |
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