CN1060097C - Catalyst for hydrogenation of fraction oil, and method for preparing same - Google Patents

Catalyst for hydrogenation of fraction oil, and method for preparing same Download PDF

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CN1060097C
CN1060097C CN96120875A CN96120875A CN1060097C CN 1060097 C CN1060097 C CN 1060097C CN 96120875 A CN96120875 A CN 96120875A CN 96120875 A CN96120875 A CN 96120875A CN 1060097 C CN1060097 C CN 1060097C
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CN1184707A (en
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王致善
李坚
夏国富
扈林杰
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Sinopec Research Institute of Petroleum Processing
China Petrochemical Corp
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China Petrochemical Corp
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Abstract

The present invention relates to a hydrocarbon hydrotreating catalyst which comprises active components and an assistant catalyzing component, wherein the active components comprise Ni, W and Co, and the assistant catalyzing component comprises P or the mixture of P and Mg. A carrier is gamma-Al2O3. The catalyst is used for the treatment of distillate hydrogenation, has high activity of hydrodesulfurization and hydrodenitrogenation and has the advantages of simple preparation method and high catalyst intensity.

Description

A kind of catalyst for hydrogenation of fraction oil and preparation method thereof
The present invention relates to hydrocarbon hydrogenizing treamtent catalyst, more particularly, is a kind of about the particularly hydrogenating desulfurization, hydrodenitrogenation catalyst and preparation method thereof of light ends oil and intermediate oil of distillate.
Hydrofining is petroleum refining industry method commonly used, and its main purpose is sulphur, nitrogen, oxygen compound or the metal of removing in the petroleum hydrocarbon etc.For example the raw material petroleum naphtha used of reformer generally must carry out pre-hydrogenation before entering the reforming reaction system, to remove wherein the catalyzer objectionable impurities, comprises sulphur, nitrogen and other impurity.For other distillate such as kerosene, diesel oil distillate, for guaranteeing quality product, often need hydrofining, remove wherein sulphur, nitrogen and aromatic hydrocarbons etc., to improve smoke point and diesel-fuel index number etc.The used catalyzer of hydrogenation process plays an important role to hydrogenation, and the catalyzer that above-mentioned fraction oil hydrogenation refining is commonly used adopts γ-Al more 2O 3, also sneak into SiO sometimes 2Representative catalyst used for hydrogenation of distilled oil fraction is that trade names are the catalyzer of S-12, and it is a kind of Co-Mo/Al 2O 3The type catalyzer, be used for the pre-hydrogenation of reforming raw oil, have higher desulphurizing activated, but temperature of reaction and pressure are higher, at least 310 ℃ of temperature of reaction, the minimum 2.5MPa of pressure (China PetroChemical Corporation's production and operation coordination portion is compiled, " oil refining production equipment basic data compilation; oil fuel part ", 1994).
In recent years, for adapting to the protection environment requirement, reported many and had high desulfurization, denitrogenation and take off the active catalyst used for hydrogenation of distilled oil fraction of aromatic hydrocarbons, the phosphorated catalyzer is exactly one of them.The introduction of US5135902 patent be a kind of be the load hydrogenation catalyst of active component with Ni, W, P, its carrier is the Herba Galii Bungei shape bar with narrow pore size distribution (60～80A accounts for 85%) of drying, 625 ± 30 ℃ of roastings.The arene saturating activity of this catalyzer all is significantly increased than conventional Ni-W catalyzer and Ni-Mo-P catalyzer.The US5472595 patent also is the hydrocarbons hydrogenation catalyzer of a kind of Ni-W-P, the catalyzer that provides in the example is that the active component of nickeliferous ≈ 7%, tungsten＞35%, phosphorus＞1% was immersed on the gac through two steps or three steps, and the catalyzer that this catalyzer takes off the Ni-W/ carbon that the aromatic hydrocarbons specific activity do not phosphorate is high by 78%.Above-mentioned two kinds of catalyzer all have the higher aromatic hydrocarbons activity of taking off, but hydrogenating desulfurization, hydrodenitrogenationactivity activity do not improve.
EP 0482817A 1Mo-Ni-P or Co-Mo-P hydrogenization catalyst preparation method have been reported, it is with the complexing agent of hydroxycarboxylic acid as the reactive metal element, with its metering join in the co-impregnated solution of reactive metal element and phosphoric acid, carrier impregnation is in wherein, can make catalyzer being lower than 200 ℃ of dryings.This catalyzer has higher desulphurizing activated.The strict control of needs drying temperature when the decomposition of complex compound prepares this catalyzer, and this catalyzer is the same with the described catalyzer of US5472595, without roasting, active element exists with salt or complex form, be subjected to the influence of environment such as water, temperature bigger, poor stability is unfavorable for preserving and long-distance transport
The purpose of this invention is to provide a kind ofly have simultaneously that high alkene is saturated, the catalyst for hydrogenation of fraction oil of hydrogenating desulfurization and hydrodenitrification.
Another object of the present invention provides a kind of simple and can obtain high-intensity Preparation of catalysts method.
Catalyzer of the present invention is to be active ingredient with W, Ni, Co, and the mixture of P or P and Mg is as co-catalyst component.The composition content of following catalyzer is that the weight with catalyzer is benchmark, and metallic element is in oxide form, and concrete content is as follows: WO 310～30%, NiO1.0～7.O%, CoO0.01～1.0%, co-catalyst component MgO0.1～5.0%, P0.3～5.0%, optimum content: active ingredient WO 316～27%, NiO1.5～4.0%, CoO0.02～0.3%, co-catalyst component MgO0.5～4.0%, P0.5～4.0%, all the other are γ-Al 2O 3
Described γ-Al 2O 3Precursor is selected from any in unformed aluminum oxide, false boehmite, pseudo-boehmite, gibbsite, the surge aluminium stone, a preferably false diaspore and pseudo-boehmite, gama-alumina aperture 50～100 account for more than 90%, and carrier adopts special-shaped bar, preferably cloverleaf pattern.
Described catalyzer routinely method before use carries out prevulcanized.
Preparation of catalysts method of the present invention comprises the following steps:
(1) γ-Al 2O 3Precursor is through moulding, drying, and 500～700 ℃ of roastings 1～6 hour under the existence of air or water vapor again make γ-Al 2O 3, (2) are with γ-Al 2O 3Soak in P that immersion prepares or P and the Mg blended compound water solution, filtration, drying 400～700 ℃ of following roastings 2～8 hours, obtain containing the γ-Al of co-catalyst component then 2O 3γ-the Al that contains co-catalyst component that carrier (3) obtains (2) step 2O 3Carrier impregnation is in the compound water solution that contains W, Ni, Co for preparing in advance, and filtration, drying promptly obtained catalyst prod in 2～5 hours 400～600 ℃ of following roastings then.
Described active ingredient Co can add in (2) step, makes the γ-Al that contains Co and co-catalyst component 2O 3
Described co-catalyst component P can make aqueous solution proofing γ-Al again with active ingredient Ni, W, Co in (3) step 2O 3Or contain γ-Al of Mg 2O 3
Above-mentioned preparation process (2), (3) step can also adopt the saturated dipping method in hole.
Described Ni, W, Co compound water solution make according to a conventional method, and wherein the compound of Ni, Co element is nitrate, acetate, carbonate, subcarbonate, preferably nitrate, subcarbonate.
Described P, Mg compound water solution make according to a conventional method, and the compound of Mg is a magnesium nitrate, and the aqueous solution of P is phosphoric acid, metaphosphoric acid or its esters.
Catalyzer of the present invention can be used for reforming that the alkene of pre-refining stock oil, gasoline fraction and intermediate oil is saturated, hydrodenitrification, hydrodesulfurization process, and its operational condition can be adjusted in following ranges according to stock oil character with to the requirement of oil quality: 200～400 ℃ of temperature of reaction, volume space velocity 3～15h -1, hydrogen dividing potential drop 0.8～6.0MPa, hydrogen/oil 50～800: 1 (body).
Major advantage of the present invention: owing to adopt Ni-W and micro-Co as main active component, and obtain best proportioning, introduce P again as co-catalyst component, adjust the performance of catalyzer, therefore catalyzer of the present invention is used for the distillate hydrogenation processing, can have high hydrogenating desulfurization and hydrodenitrogenationactivity activity simultaneously, as be mixed with the reformer feed of the triumph coker gasoline of 2.5% (body), can under low pressure, low hydrogen/gasoline ratio and high-speed condition, produce qualified reformer feed; In addition, owing to introduce P, also increased the hydrogenation aromatics-removing activity of catalyzer.
Preparation of catalysts method of the present invention is simple, and used raw material all is commercially available prod, and the catalyst strength of acquisition is than higher.
Further specify characteristics of the present invention with example below.
Example 1
This example is the carrier of preparation catalyzer.
In the false boehmite powder that 200g Shandong Aluminum Plant produces, add 7.0g sesbania powder, mix.Take by weighing the 7.0g citric acid, measure 1.4ml nitric acid and water and be made into 130ml solution, this solution under agitation is added in the compound powder, pinch through mixing, to make D be the wet bar of 1.6mm cloverleaf pattern to extrusion.This extrudate is down put into the steam-treated stove after dry 3 hours at 120 ℃ and is handled, and than 1: 1, constant temperature 6 hours made carrier a in 550 ℃, aqua.Carrier a specific surface 202M 2/ g, pore volume 0.39ml/g can a few aperture 64 , intensity 20.2N/mm.
Example 2
This example is the γ-Al that contains P with the pseudo-boehmite preparation 2O 3Carrier.
In the pseudo-boehmite powder that 150g Wenzhou catalyst plant is produced, add 4.5g sesbania powder, mix.4.5g citric acid, 14.8g85% phosphoric acid and 1ml nitric acid water are made into 105ml solution, this solution slowly is added in the powder mix, constantly stir, pinch through mixing then, extrusion makes D=1.6mm cloverleaf pattern bar.Should wet bar 140 ℃ dry 2 hours down, 580 ℃ of following roastings 3 hours make carrier b.Carrier b specific surface 180m 2/ g, pore volume 0.37ml/g can a few aperture 66 , intensity 30.0N/mm.
Example 3
This example is to prepare γ-Al with pseudo-boehmite 2O 3Carrier.
Pseudo-boehmite powder 400g and 12g sesbania powder with Wenzhou catalyst plant production mix.16g citric acid and 3.2ml nitric acid water are made into 300ml solution.Solution is mixed with powder, and warp mixes and pinches, extrusion, makes D=1.6mm cloverleaf pattern bar.Should wet bar 120 ℃ dry 4 hours, 600 ℃ of roastings 4 hours make carrier c.Carrier specific surface 190m 2/ g, pore volume 0.40ml/g can a few aperture 90 , intensity 26N/mm.
Example 4
This example is preparation Ni-W-Co/Al 2O 3-P catalyzer.Concrete preparation process:
(1) takes by weighing 7.95g 85%H 3PO 4Be made into 43ml solution with water, with hole saturation method dipping 50g carrier a3 hour, then 120 ℃ of dryings 2 hours, 560 ℃ of roastings 4 hours made phosphorated γ-Al with this solution 2O 3Carrier.
(2) with 0.12g Xiao Suangu, 4.91g nickelous nitrate, ammonium metawolframate (hereinafter to be referred as AMT) solution (concentration 77.6gWO 3/ 100ml) 13.5ml is made into 45ml solution.The phosphorous carrier that makes by (1) step with hole saturation method dipping with this solution 3 hours, then 120 ℃ dry 2 hours down, 420 ℃ of following roastings 4 hours make catalyst A.
Example 5
This example is preparation Ni-W-Co/Al 2O 3-P-Mg catalyzer.Concrete preparation process:
(1) adds water with 85% phosphatase 11 .95g, magnesium nitrate 12.4g and be made into calcium 43ml solution.With hole saturation method dipping 50g carrier a3 hour, then 120 ℃ of dryings 2 hours, 570 ℃ of roastings 4 hours made the γ-Al that contains P-Mg with this solution 2O 3Carrier.
(2) get 0.13g Xiao Suangu, 9.53g nickelous nitrate and AMT solution (concentration such as example 4) 20.8ml, add water and be made into the 42ml co-impregnated solution.With above-mentioned same method dipping 50g by (1) step make contain the P-Mg carrier, drying, roasting make catalyst B.
Example 6
This example is preparation Ni-W-Co/Al 2O 3-P catalyzer.
Get 0.12g Xiao Suangu, 5.61g nickelous nitrate and 1.72ml AMT solution (concentration 73gWO 3/ 100ml), be made into the 32ml co-impregnated solution with water dissolution, with this solution impregnation 40g carrier b4 hour, then 110 ℃ dry 3 hours down, 440 ℃ of following roastings 4 hours make catalyzer C.
Example 7
This example is preparation Ni-W-Co/Al 2O 3-P catalyzer.
(1) takes by weighing 10.7g 85%H 3PO 4Be made into 44ml solution with water.With this solution impregnation 50g carrier c3 hour, then 120 ℃ dry 2 hours down, 570 ℃ of following roastings 4 hours make and contain the P carrier.
(2) take by weighing 0.30g Xiao Suangu, 7.62g nickelous nitrate and 23.5ml AMT solution (concentration 73gWO 3/ 100ml), be made into the 39ml co-impregnated solution with water dissolution, above-mentioned with the saturated dipping of this solution by the carrier that makes of (1) step 4 hours, then 120 ℃ dry 3 hours down, 420 ℃ of following roastings 4 hours make catalyzer D.
Example 8
This example is preparation Ni-W-Co/Al 2O 3-P catalyzer.Concrete preparation process:
(1) weighing 85% phosphoric acid 5.79g, water is made into the 51ml phosphoric acid solution.Phosphoric acid solution was added among the 60g carrier c dipping 3 hours, and wet bar drying and roasting get phosphorous carrier.
(2) take by weighing Xiao Suangu 0.12g, nickelous nitrate 5.50g, measure AMT solution 24.2ml (concentration such as example 6) and be made into co-impregnated solution 52ml with water.By the phosphorous carrier that makes of (1) step 4 hours, wet bar drying, roasting made catalyzer D with this solution impregnation 62.5g.
Example 9
This example is according to EP0,482, and 817A 1The catalyzer that example 13 makes in the patent application is called comparative example 1.
Use the dry glue powder (Al (OH) that Chang Ling, Hunan oil-refining chemical factory catalyst plant is sold in Chang Ling in this comparative example 1 3Powder) as support material.Concrete preparation process:
(1) adds 3g sesbania powder in the dry glue powder of 100g Chang Ling, mix.Measure 3.51ml nitric acid, 4.0g citric acid, water is made into 95ml solution.Solution is mixed with powder, pinch through mixing, extrusion makes wet this extrudate of bar of D=1.6mm cloverleaf pattern 120 ℃ of dryings 3 hours, 600 ℃ of roastings 4 hours make carrier.After measured, this carrier specific surface 261m 2/ g, pore volume 0.63ml/g, with EP0,482,817A 1Patent application example 13 used carrier character are close.
(2) take by weighing 7.7g molybdenum oxide, 3.24g nickelous carbonate, 2.46g 85% phosphoric acid, add water, heating for dissolving is made into the 38ml co-impregnated solution.The carrier that is made by (1) step with co-impregnated solution dipping 40g 4 hours, the wet bar behind the dipping made comparative example 1 catalyzer down in dry 5 hours through 115 ℃.
The catalyst property of above-mentioned example 4～example 9 is listed in table 1.
Example 10
This example is mixed 2.5v% triumph coker gasoline with grand celebration straight-run spirit and grand celebration straight-run spirit and catalyst A, B, C, D are carried out activity rating and is compared with comparative example 1 and comparative example 2 activity of such catalysts.
The catalyst activity evaluation is carried out in the 50ml fixed-bed reactor, and hydrogen once passes through.Must prevulcanized handle before the evaluating catalyst.Vulcanized oil is to contain 2%CS 2Straight-run spirit.Cure conditions is respectively:
Comparative example 1 catalyzer:
Sulfide stress 1.6MPa, hydrogen to oil volume ratio 300: 1, volume space velocity 2.0h -1, be warming up to 130 ℃ by 30～50 ℃/h during sulfuration and advance vulcanized oil, rise to 260 ℃ by 80 ℃/h then, constant temperature 1 hour, 60 ℃/h are warming up to 350 ℃, constant temperature 5 hours, sulfuration finishes.
Other catalyzer:
Sulfide stress 1.6MPa, hydrogen to oil volume ratio 300: 1, volume space velocity 2.0h -1, be warming up to 150 ℃ by 30～50 ℃/h during sulfuration and advance vulcanized oil, rise to 230 ℃ by 50 ℃/h then, constant temperature 3 hours rises to 290 ℃ with same heat-up rate then, constant temperature 3 hours, sulfuration finishes.
Change into to estimate after the sulfuration end and use stock oil, under reaction conditions, need stablize and to begin to estimate activity through 24～30 hours.The data that all logical oil of each catalyst activity running in 100 hours post analysis obtains.
Estimate and list in table 2 with stock oil character.The catalyst activity evaluation result is listed in table 3.
As can be seen from Table 3, the catalyzer made from the inventive method, under high-speed, low hydrogen/gasoline ratio, low pressure and lesser temps, no matter use straight-run spirit, still with containing a certain amount of nitrogen and gelationus low grade oils, sulphur and nitrogen can be reduced to below the 0.5ppm fully, meet the catalytic reforming feedstock requirement, its activity is apparently higher than the comparative example catalyzer.In addition, the aromatic hydrogenation performance of the catalyzer made from the inventive method is compared with comparative example, and raising is also arranged.
Table 1 catalyst property [notes]
Figure 96120875000911
[notes] comparative example 2 catalyzer are that the trade mark of being produced by Uop Inc. is the catalyzer of S-12, and its character is measured result.
Table 2 stock oil character
Figure 96120875001011
Table 3 catalyst activity test-results [notes]
Figure 96120875001111
[notes] reaction conditions: reaction pressure 1.6MPa, volume space velocity 10h -1, hydrogen to oil volume ratio 90: 1.

Claims (7)

1. a hydrocarbon hydrogenizing treamtent catalyst is characterized in that forming and contains active ingredient Ni, W, Co, and co-catalyst component is selected from P or P and Mg mixture, and carrier is γ-Al 2O 3, be benchmark with the catalyst weight, specifically form content and be: WO 310～30%, NiO1.O～7.0%, CoO0.01～1.0%, P0.3～5.0%, MgO0.1～5.0%, all the other are γ-Al 2O 3
2. according to the described catalyzer of claim 1, it is characterized in that WO 316～27%, NiO1.5～4.0%, CoO0.02～0.3%, P0.5～4.0%, MgO0.05～4.0%.
3. the described Preparation of catalysts method of claim 1 is characterized in that preparation process and preparation condition comprise: (1) γ-Al 2O 3Precursor is through moulding, drying, and 500～700 ℃ of roastings 1～6 hour under the existence of air or water vapor again make γ-Al 2O 3, (2) are with γ-Al 2O 3Soak in P that immersion prepares or P and the Mg blended compound water solution, filtration, drying 400～700 ℃ of following roastings 2～8 hours, obtain containing the γ-Al of co-catalyst component then 2O 3Carrier, the γ-Al that contains co-catalyst component that (3) obtain (2) step 2O 3Carrier impregnation is in the compound water solution that contains W, Ni, Co, and filtration, drying promptly made catalyzer in 2～5 hours 400～600 ℃ of following roastings then.
4. in accordance with the method for claim 3, it is characterized in that active ingredient Co can add in (2) step, P is mixed with the aqueous solution with co-catalyst component, floods γ-Al again 2O 3
5. in accordance with the method for claim 3, it is characterized in that co-catalyst component P can make the aqueous solution with active ingredient Ni, W, Co and flood γ-Al again in (3) step 2O 3Or contain γ-Al of Mg 2O 3
6. in accordance with the method for claim 3, it is characterized in that described γ-Al 2O 3Precursor is selected from any one in amorphous alumina, false boehmite, pseudo-boehmite, gibbsite, the surge aluminium stone, γ-Al 2O 3Aperture 50～100 dusts account for more than 90% of total pore volume.
7. the application of the described catalyzer of claim 1 in reformation pre-refining stock oil, gasoline fraction and intermediate oil hydrotreatment.
CN96120875A 1996-12-11 1996-12-11 Catalyst for hydrogenation of fraction oil, and method for preparing same Expired - Lifetime CN1060097C (en)

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EP2173477B1 (en) * 2007-08-06 2019-04-10 Shell International Research Maatschappij B.V. Method for the production of a catalyst for hydrocarbon hydrotreatment.
CN103521236B (en) * 2013-10-11 2015-08-19 中国海洋石油总公司 A kind of method for making of high activity coking gasoline hydrogenation refining catalyst
CN104624215A (en) * 2013-11-15 2015-05-20 中国石油天然气股份有限公司 Distillate oil hydrofining catalyst and preparation method and application ofdistillate oil hydrofining catalyst
CN109647450B (en) * 2017-10-10 2022-02-01 中国石油化工股份有限公司 Hydrogenation catalyst for synthesizing cyclohexylamine

Citations (4)

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Publication number Priority date Publication date Assignee Title
CN85103891A (en) * 1984-05-18 1986-11-12 国际壳牌研究有限公司 The preparation method of the hydrogenation conversion catalyst on the carrier and the catalyst for preparing in this way
CN1052501A (en) * 1989-12-11 1991-06-26 中国石油化工总公司抚顺石油化工研究院 Hydrobon catalyst and method for making
US5068025A (en) * 1990-06-27 1991-11-26 Shell Oil Company Aromatics saturation process for diesel boiling-range hydrocarbons
US5472595A (en) * 1994-08-09 1995-12-05 Texaco Inc. Process for hydrodearomatization of hydrocarbon oils using carbon supported metal sulfide catalysts promoted by phosphate

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN85103891A (en) * 1984-05-18 1986-11-12 国际壳牌研究有限公司 The preparation method of the hydrogenation conversion catalyst on the carrier and the catalyst for preparing in this way
CN1052501A (en) * 1989-12-11 1991-06-26 中国石油化工总公司抚顺石油化工研究院 Hydrobon catalyst and method for making
US5068025A (en) * 1990-06-27 1991-11-26 Shell Oil Company Aromatics saturation process for diesel boiling-range hydrocarbons
US5472595A (en) * 1994-08-09 1995-12-05 Texaco Inc. Process for hydrodearomatization of hydrocarbon oils using carbon supported metal sulfide catalysts promoted by phosphate

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