CN1054151C - Catalyst for hydrodesulfurization fraction oil - Google Patents
Catalyst for hydrodesulfurization fraction oil Download PDFInfo
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- CN1054151C CN1054151C CN96120986A CN96120986A CN1054151C CN 1054151 C CN1054151 C CN 1054151C CN 96120986 A CN96120986 A CN 96120986A CN 96120986 A CN96120986 A CN 96120986A CN 1054151 C CN1054151 C CN 1054151C
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Abstract
The present invention relates to a hydrodesulfurization catalyst for distillate oil. In the catalyst, alumina pellets containing 5 to 15 w% of SiO2 are used as carriers, the catalyst contains 12.0 to 18.0 w% of MoO3 and 3.0 to 6.0 w% of CoO, the pore volume of the catalyst is from 0.45 to 0.55 ml/g, and the average pore diameter is from 7.0 to 10.0 nm. The catalyst is characterized in that the specific surface area of the unit volume catalyst is from 190 to 220 m<2>/ml under the condition that the granule diameter is from 1.5 to 2.5mm when catalyst granules are compactly stacked. The preparation method of the catalyst mainly comprises: wet rubber pellets are dried in an ammonia containing atmosphere at low speed at a low temperature (lower than 100DEG C) in the process of the preparation of the alumina pellets containing SiO2.
Description
The present invention relates to fraction oil hydrogenation refining, particularly Hydrobon catalyst and preparation thereof.
In recent years, the stock oil sulphur content that is used for hydrotreatment is more and more higher, and international environmental regulation is also more and more stricter to the restriction of sulphur content in the product, thereby the hydrogenating desulfurization technology seems particularly important, and the core content of this technology is exactly the exploitation of Hydrobon catalyst.
Typical Hydrobon catalyst is to be carrier with aluminum oxide or siliceous aluminum oxide, is active ingredient with group vib in the periodic table of elements (as Mo) and one or more metals of VIII family (as Co or Ni).
As everyone knows, in order to improve the activity of Hydrobon catalyst, require this catalyzer to have large pore volume, high-specific surface area and concentrated pore distribution, catalyzer also need possess sufficient mechanical strength to adapt to its industrial practicality simultaneously, and the above-mentioned character of supported hydrodesulphurizatiocatalyst catalyst is mainly by its carrier decision.People have carried out many researchs and exploration improving these properties of support of the catalyst.For example, aspect the spherical preparing carriers of siliceous aluminum oxide, the carrier of the catalyzer of CN 89109140.8 preparations has concentrated pore distribution (major part concentrates in the 4.0-10.0nm pore diameter range), bigger tap density (is tightly packed density, but its pore volume and specific surface area are big inadequately about 0.68g/ml) and physical strength (＞70N/ grain).Another piece CN 921111339 carries out modification by the method for adding auxiliary agents such as phosphorus to carrier, though pore volume, specific surface area are increased, the support of the catalyst tap density that makes less (about 0.54g/ml).Above-mentioned patent adopts ordinary method dry wet glueballs when the preparation support of the catalyst, prepared carrier and catalyzer thereof are difficult to make its specific surface area and tap density to reach higher value simultaneously.
For porousness loading type fraction oil hydrogenation refining, the character that comprises Hydrobon catalyst should have following requirement: (1) is when granules of catalyst is tightly packed, per volume of catalyst has largest specific surface area, and promptly the product of the specific surface area of catalyzer and tap density reaches maximum.(2) catalyzer should have moderate mean pore size.(3) pore distribution of catalyzer should concentrate on around the mean pore size as far as possible.(4) catalyzer has enough physical strengths.
The basis that (1) bar requires is: the Hydrobon catalyst that is used for fixing bed is considered its volume space velocity activity emphatically when industry is used, i.e. unit admission space activity of such catalysts, and this is because the volume of industrial reactor is limited.The petroleum fractions hydrofining reactor uses under the condition that High Temperature High Pressure and hydrogen exist, and its material is required very strict, and the material price is also expensive, so when reactor volume increases, the investment cost of construction reactor will increase considerably.In addition, the difficulty of making and transporting has also limited the volume of this type of industrial reactor.
The active centre of porousness loaded catalyst is to be located on the surface of catalyzer, and the size on this surface is characterized by common specific surface area, when the specific surface area of catalyzer is big more, under the constant condition of other factors, can provide many more active centre numbers, thereby its activity is high more.But common specific surface unit is m
2/ g promptly reflects the internal surface size (the particle outside surface can be ignored) of unit weight catalyzer.Therefore, in order to improve the activity of per volume of catalyst, must increase the specific surface area of per volume of catalyst.
The basis that (2) bar requires is: (A) distillate institute's containing metal such as Ni, V, Fe, Na etc. are very low, can not consider its deposition in the catalyzer hole, so need not pursue very big pore volume.(B) consideration that there are two aspects in moderate aperture is proposed: the one, reduce the reactant diffusional resistance, the 2nd, increase specific surface area.The aperture is too big, though diffusional resistance diminishes, specific surface area must descend, so there is optimum balance.
The basis that (3) bar requires is: (A) when the catalyzer pore distribution concentration, in the metal component steeping process, can slow down the migration of metal-salt, make its distribution comparatively even.(B) comparatively speaking, pore more for a long time, diffusional resistance is big, the hole utilization ratio is low, and gross porosity more for a long time, and the unit volume specific surface area is descended, and concentrates on suitable pore diameter range so wish pore size distribution.
It is to wish that catalyzer in use is unlikely broken and causes bed pressure drop to increase and the interruption running that (4) bar requires.
In order to make catalyzer meet this four requirements, must take following two kinds of measures: (1) select or prepare that a kind of unit volume specific surface area is big, the aperture is moderate, pore distribution concentration and the bigger carrier of physical strength.(2) making by the carrier impregnation active metal component in the process of catalyzer, reducing the loss of original specific surface area of carrier and pore volume as far as possible.
The objective of the invention is to, a kind of catalyst for hydrodesulfurizationfraction fraction oil is provided, the specific surface area of its unit volume and pore volume are improved, thereby improve catalytic activity.Another object of the present invention is to, a kind of high unit volume specific surface area and method for preparing catalyst pore volume, high activity hydrogenation and desulphurization are provided.
The main points of method for preparing catalyst of the present invention are:
(1) in the ball type carrier preparation, the drying of wet rubber ball is at room temperature, is warming up in the 50-80 ℃ of scope with 20-60 ℃/h speed, contains NH in the atmosphere
32-8v% keeps constant temperature 8.0-16.0h.Adopt this method drying, make wet rubber ball in dehydration slowly, shunk fully, thereby formed more hole number, and this method drying can make between the colloidal solid and to shrink slowly and evenly, make the hole wall of formation thin and closely knit, thereby the ball type carrier unit volume specific surface area that makes is big, the aperture is moderate, pore distribution concentration, and physical strength is also higher.
(2) select weakly alkaline Mo-Co stable ammonia solution impregnating carrier for use, and select suitable drying and roasting condition, make the pore volume and the specific surface area loss of making catalyzer very little, this is because (A) because steeping fluid is weakly alkaline (not being strongly-acid), so carrier is not had erosion, makes carrier surface character and internal structure keep more complete.(B) because steeping fluid is stable, dry and roasting condition is suitable, and carrier has stronger adsorptive power to Mo and Co, so Mo in the final catalyzer and Co (Ni) uniform distribution on the carrier internal surface does not have accumulation and plug-hole phenomenon.
Owing to taked above-mentioned two kinds of technical measures, make to make catalyzer and meet above-mentioned four requirements, therefore, catalyzer of the present invention has higher volume space velocity activity.
The main physico-chemical property of catalyzer of the present invention sees Table 1: the main physico-chemical property of table 1. catalyzer of the present invention
| Project | Measured value |
| Chemical constitution, w% MoO 3 CoO SiO 2 Al 2O 3Pore volume, the ml/g average pore diameter, the nm tap density, the g/ml physical strength, N/ grain unit volume specific surface, m 2/ ml pore distribution, %＜4.0nm 4.0-10.0nm＞10.0nm | 12.0-18.0 3.0-6.0 4.0-12.0 64.0-8 1.0 0.45-0.55 7.0-10.0 0.80-0.86 80-120 190-220 2.0-6.0 90.0-95.0 1.0-3.0 |
Hence one can see that, and support of the catalyst of the present invention is siliceous alumina globule, wherein, and SiO
2Content is 5-15w%, catalyzer MoO
3Content is 12.0-18.0w%, and CoO content is 3.0-6.0w%, and catalyzer pore volume of the present invention is 0.4 5-0.55ml/g; Pore size distribution accounts for more than 90% of total pore volume at the pore volume between the 4.0-10.0nm, mean pore size 7.0-10.0nm, and tap density is 0.8 0-0.86g/ml, physical strength is the 80-120N/ grain, particle diameter 1.5-2.5mm, the specific surface 190-220m of per volume of catalyst
2/ ml.
Because catalyzer of the present invention has good physico-chemical property, thereby it is desulphurizing activated to have higher volumes.Catalyzer of the present invention is when handling the hydrofining of distillate feedstock, particularly in the hydrodesulfurization process of reformer feed, brought into play higher hydrodesulfurization activity, show that this catalyzer can bear the higher reaction conditions of severity, and deep desulfuration has been effective.At hydrogen dividing potential drop 1.6MPa, liquid hourly space velocity 10.0h
-1Under hydrogen-oil ratio 80-100 condition, handling sulphur content is the reformer feed of 700 μ g/g, when temperature of reaction is 270 ℃, can make the sulphur content that generates oil less than 0.5 μ g/g, this result compares with typical desulfurization catalyst, and temperature of reaction has reduced by 10 ℃, more than sees the table 4 of embodiment 3.
Preparation of catalysts step of the present invention is: the preparation of (1) sial solution
To contain Al
2O
3The aluminum trichloride solution of 2-5g/100ml and contain SiO
2The acidifying sodium silicate solution of 6-9g/100ml mixes, and the mixed volume ratio is 1: 0.03, the pH 1-3 of mixed solution.(2) become glue
With step (1) product and the neutralization of alkaline matter ammoniacal liquor, contain NH in the ammoniacal liquor
38-12g/100ml, neutral temperature requires 25-60 ℃, and pH is 7-9, and be 5-15min duration of contact, total reaction time 0.5-2.0h.(3) filter and washing
Material in the step (2) is filtered and washing leaching cake, carry out 2-4 time continuously, wash temperature 20-50 ℃, washing time 20-50min.(4) peptization of wet gel
Carry out peptization by step (3) gained wet gel with mineral acid, mineral acid is the salpeter solution of 35-40%, and add-on is every kilogram of filter cake 10-30ml, stirs peptization 1.5-4.0h down.(5) balling-up
Step (4) products therefrom soaks 1.0-4.0h then with the oil ammonia column balling-up in the ammoniacal liquor of 3-6w%.(6) drying
Step (5) product is carried out drying, and drying temperature 50-80 ℃, ammonia concentration is 2-8v% in the atmosphere, time 8.0-16.0h.(7) roasting
Step (6) product is at 500-700 ℃ of roasting, roasting time 5.0-10.0h.(8) dipping
Calculate required impregnation concentration by dry bulb water-intake rate in the step (7), make Mo-Co-NH
3The aqueous solution, contain MoO in the solution
320-28g/100ml contains CoO 4-8g/100ml, floods with saturation method.(9) catalyzer drying and roasting
By step (8) product 100-150 ℃ of drying, time of drying 2.0-5.0h, then at 450-550 ℃ of roasting, roasting time 2.0-5.0h.
In above-mentioned preparation method, the concentration of steeping fluid is formed (content) by carrier water-intake rate and desired catalyzer and is determined that the water-intake rate of carrier is directly proportional with its pore volume.When carrier has bigger pore volume, for the preparation of catalyst impregnating solution brings great convenience.
Compared with prior art, catalyzer of the present invention has bigger volumetric surface area and volume pore volume, and pore distribution is also more reasonable.Therefore, under the identical situation of desulfurization degree, required temperature of reaction is lower, promptly has higher reactive behavior.Especially the present invention has taken all factors into consideration tap density and specific surface area and pore volume, makes on the certain scale production equipment, reduces temperature of reaction or increases the stock oil treatment capacity.
One section dipping has been adopted in supporting of activity of such catalysts metal component of the present invention.This is because the pore volume of carrier is big, the water-intake rate height, and a kind of advanced person's solution compound method, the strength of solution height that is made into, good stability have been adopted, one section dipping has not only been simplified preparation process, and making the catalyzer of preparation, its metal component is at the good dispersion on surface, simultaneously the appearance color of catalyzer homogeneous relatively, the cleaning of particle outside surface, no metallic dust adheres to.
The embodiment of catalyzer of the present invention is as follows:
Embodiment 1
(1) will contain Al
2O
3The aluminum trichloride solution 201 of 4g/100ml with contain SiO
2The acidifying water glass 0.61 of 8g/100ml mixes, and regulates pH to 2.7.
(2) under 40 ℃ of temperature, with the neutralization of the ammonia soln of concentration 9% by (1) gained mixed solution, control ammoniacal liquor flow, making neutralizer pH is 8.0, duration of contact 10min, total reaction time 1.5h.
(3) product in (2) is filtered, then with water purification washing, 35 ℃ of wash temperatures, washing time 40min, continuous washing 3 times.
(4) wet gel in (3) is pressed every kilogram of wet gel amount, the nitric acid that adds 20ml concentration 39% carries out peptization, continuously stirring, peptization time 3.0h.
(5) by the colloidal sol of (4) gained,, in 5% ammoniacal liquor, soak 3.0h then with the oil ammonia column balling-up.
(6) above-mentioned wet rubber ball is carried out drying.60 ℃ of drying temperatures of control, ammonia concentration 5v% in the medium that keeps dry, time of drying 14.0h.
(7) dry bulb that is obtained by (6) makes the carrier of catalyzer of the present invention at 550 ℃ of roasting temperature 3.0h.
(8) 8 5g citric acids are dissolved in the 115ml water purification, add the 60g cobaltous carbonate, boil dissolving, after the cooling, add 25% ammoniacal liquor again to 250ml, add the 150g ammonium molybdate in above-mentioned solution, the dissolving back transfers to 500ml with 25% ammoniacal liquor with liquor capacity, and is airtight.
(9) get made carrier 200g in (7), place rotary drum, spray, take out then,, place stoving oven then,, make catalyzer of the present invention in 510 ℃ of roasting 3.0h in 110 ℃ of dry 2.5h with making solution 140ml in (8).
Embodiment 2
In embodiment 1, the drying temperature of wet rubber ball changes 80 ℃ in the step (6), changes 10.0h time of drying into, i.e. the cost example.
Embodiment 3
(1) will contain Al
2O
3The aluminum trichloride solution 201 of 4g/100ml with contain SiO
2The acidifying water glass 0.61 of 9g/100ml mixes, and regulates pH to 2.7.
(2) under 30 ℃ of temperature, with the neutralization of the ammonia soln of concentration 9% by (1) gained mixed solution, control ammoniacal liquor flow, making neutralizer pH is 7.5, duration of contact 10min, total reaction time 1.5h.
(3) product in (2) is filtered, then with water purification washing, 25 ℃ of wash temperatures, washing time 40min, continuous washing 3 times.
(4) wet gel in (3) is pressed every kilogram of wet gel amount, the nitric acid that adds 18ml concentration 37% carries out peptization, continuously stirring, peptization time 2.0h.
(5) by the colloidal sol of (4) gained,, in 5% ammoniacal liquor, soak 3.0h then with the oil ammonia column balling-up.
(6) above-mentioned wet rubber ball is carried out drying.60 ℃ of drying temperatures of control, ammonia concentration 5v% in the medium that keeps dry, time of drying 14.0h.
(7) dry bulb that is obtained by (6) makes the carrier of catalyzer of the present invention at 630 ℃ of roasting temperature 3.0h.
(8) the 85g citric acid is dissolved in the 115ml water purification, adds the 60g cobaltous carbonate, boil dissolving, after the cooling, add 25% ammoniacal liquor again to 250ml, add the 150g ammonium molybdate in above-mentioned solution, the dissolving back transfers to 500ml with 25% ammoniacal liquor with liquor capacity, and is airtight.
(9) get made carrier 200g in (7), place rotary drum, spray, take out then,, place stoving oven then,, make catalyzer of the present invention in 510 ℃ of roasting 3.0h in 110 ℃ of dry 3.0h with making solution 140ml in (8).
Comparative example 1
Change step (6) temperature among the embodiment 1 into 110 ℃, do not keep the ammonia in the atmosphere, dry 3.0h.
Embodiment 4
This example is above each routine institute controlling catalyst physico-chemical property and reactivity worth.
The different example of table 2 institute controlling catalyst physico-chemical property
| Example | Embodiment 1 | Embodiment 2 | Embodiment 3 | Comparative example 1 | ||
| Chemical constitution, w% | MoO 3 | 14.9 | 15.3 | 14.5 | 14.7 | |
| CoO | 4.0 | 3.9 | 4.5 | 3.9 | ||
| SiO 2 | 7.0 | 9.5 | 11.5 | 1.6 | ||
| Pore volume, ml/g | 0.51 | 0.48 | 0.46 | 0.43 | ||
| The unit volume specific surface, m 2/ml | 209 | 194 | 190 | 174 | ||
| Pore distribution ' % | 4.0nm | 5.1 | 4.6 | 3.8 | 4.9 | |
| 4.0- 10.0nm | 92.8 | 91.5 | 89.3 | 90.5 | ||
| 10.0nm | 1.1 | 3.9 | 6.9 | 4.6 | ||
| Mean pore size, nm | 9.6 | 9.9 | 9.8 | 9.1 | ||
| Tap density, g/ml | 0.81 | 0.84 | 0.85 | 0.83 | ||
| Physical strength, the N/ grain | 103 | 90 | 85 | 80 | ||
Table 3 evaluating catalyst stock oil character
| Stock oil | Iran's straight-run spirit |
| Boiling range; ℃ IBP 10% 30% 50% 70% 90% 95% EBP density, (20 ℃) g/cm3N, μ g/g S, μ g/g bromine valency, gBr/100g | 47 111 127 138 148 159 164 180 0.7517 1.0 700 1.10 |
Table 4 different catalysts hydrogenating desulfurization result
| Example | Embodiment 1 | Embodiment 2 | Embodiment 3 | Comparative example 1 | |
| Worker's second condition | The hydrogen dividing potential drop, MPa | 1.6 | 1.6 | 1.6 | 1.6 |
| Hydrogen-oil ratio (v) | 80 | 80 | 80 | 80 | |
| Volume space velocity, h-1 | 8.0 | 8.0 | 8.0 | 8.0 | |
| Temperature of reaction, ℃ | 295 | 298 | 300 | 310 | |
| Generate oily sulphur, μ g/g | 0.5 | 0.5 | 0.5 | 0.5 | |
This embodiment explanation, catalysis of the present invention has good physico-chemical property and use properties.
Claims (3)
1. a catalyst for hydrodesulfurizationfraction fraction oil is a carrier with the siliceous alumina globule of porousness, is active metal component with Mo and Co, it is characterized in that when granules of catalyst is tightly packed the specific surface area 190-220m of per volume of catalyst
2/ ml, the catalyzer mean pore size is 70-10.0nm, pore volume 0.45-0.55ml/g contains MoO
312-18w%, CoO 3.0-6.0w%, SiO
24-12w%, all the other are Al
2O
3
2. according to the described catalyzer of claim 1, it is characterized in that the aperture of catalyzer accounts for more than 90% of total pore volume at the pore volume between the 4.0-10.0nm.
3. Preparation of catalysts method is characterized in that being finished by following steps:
(1) preparation aluminum salt solution and silicon sol acid mixed solution;
(2) mixed solution that obtains by (1) with the alkaline matter neutralization;
(3) filter also washing leaching cake wet gel;
(4) use the mineral acid peptization by (3) gained wet gel;
(5) the false sol solutions by (4) gained is dripped by water dropper, and by oil ammonia column, wet bulb soaks in ammoniacal liquor;
(6) wet bulb takes out from ammoniacal liquor, and is dry at a slow speed under low temperature＜100 ℃ in ammoniated atmosphere;
(7) roasting is by (6) gained bead;
(8) flood by (7) gained bead carrier with the ammonia soln that contains Mo and Co or Ni, drying, roasting make final catalyzer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN96120986A CN1054151C (en) | 1996-12-10 | 1996-12-10 | Catalyst for hydrodesulfurization fraction oil |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN96120986A CN1054151C (en) | 1996-12-10 | 1996-12-10 | Catalyst for hydrodesulfurization fraction oil |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1184844A CN1184844A (en) | 1998-06-17 |
| CN1054151C true CN1054151C (en) | 2000-07-05 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN96120986A Expired - Lifetime CN1054151C (en) | 1996-12-10 | 1996-12-10 | Catalyst for hydrodesulfurization fraction oil |
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Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1094968C (en) * | 1999-11-04 | 2002-11-27 | 中国石油化工集团公司 | Gasoline fraction hydrogenating and modifying catalyst containing zeolite |
| CN1102640C (en) * | 2000-07-11 | 2003-03-05 | 石油大学(华东) | Catalytic cracking and desulfurizing catalyst for refining light oil products |
| CN102049270B (en) * | 2009-10-27 | 2013-01-09 | 中国石油化工股份有限公司 | Selective hydrogenation catalyst for gasoline and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN1085594A (en) * | 1992-10-14 | 1994-04-20 | 中国石油化工总公司抚顺石油化工研究院 | A kind of Wax hydrofining catalyst |
| US5482617A (en) * | 1993-03-08 | 1996-01-09 | Mobil Oil Corporation | Desulfurization of hydrocarbon streams |
| SU686441A1 (en) * | 1978-06-28 | 1996-04-10 | Л.Н. Осипов | Method of hydrorefining distillate oil fractions |
-
1996
- 1996-12-10 CN CN96120986A patent/CN1054151C/en not_active Expired - Lifetime
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SU686441A1 (en) * | 1978-06-28 | 1996-04-10 | Л.Н. Осипов | Method of hydrorefining distillate oil fractions |
| 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 |
| CN1085594A (en) * | 1992-10-14 | 1994-04-20 | 中国石油化工总公司抚顺石油化工研究院 | A kind of Wax hydrofining catalyst |
| US5482617A (en) * | 1993-03-08 | 1996-01-09 | Mobil Oil Corporation | Desulfurization of hydrocarbon streams |
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|---|---|
| CN1184844A (en) | 1998-06-17 |
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