CN1252224C - Paraffin hydrorefining catalyst and its prepn process - Google Patents
Paraffin hydrorefining catalyst and its prepn process Download PDFInfo
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- CN1252224C CN1252224C CN 200310104915 CN200310104915A CN1252224C CN 1252224 C CN1252224 C CN 1252224C CN 200310104915 CN200310104915 CN 200310104915 CN 200310104915 A CN200310104915 A CN 200310104915A CN 1252224 C CN1252224 C CN 1252224C
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Abstract
The present invention discloses a catalyst for hydrorefining paraffin wax and a preparation method thereof. The preparation method comprises the steps that a novel gamma Al2O3 carrier is firstly prepared, wherein a boron-containing compound or a boron-containing halide compound is added in the preparation process of the carrier so that the carrier has good surface structure and is favorable for the dispersion of active metal (Mo and Ni); then, the carrier is immersed in an MoNiP solution and the mixed solution is dried, roasted, etc. to prepare the MoNiP or B2O3 Al2O3 catalyst. In the preparation process of the catalyst through the strict control of the preparation process and the optimization of preparation conditions, the metal can be uniformly dispersed on the surface of B2O3 Al2O3, the dispersion of the active ingredients can be coordinated, and reducibility is good. Therefore, under the condition of low metal carrying capacity, the catalyst can still keep good hydrorefining performance and has superior paraffin wax decolourizing performance.
Description
Technical field
The present invention relates to a kind of Hydrobon catalyst, especially have catalyst for hydrogen refining of paraffin wax of high hydrofining performance and high decoloration performance and preparation method thereof concurrently.
Background technology
The oil wax material contains a small amount of objectionable impurities usually, coloured and destabilization components etc. as some harmful aromatics and some.The main purpose of hydrorefining paraffin wax is to remove contained coloured, destabilization component and harmful material in the oil wax material, to reach the requirement of the harmless even edible food-grade paraffin wax of preparation by hydrofining.Therefore need the saturated performance of a kind of existing very high hydrogenation, the catalyst for hydrogen refining of paraffin wax of the very high ability that removes aromatic organic compounds is arranged again.
Catalyst for hydrogen refining of paraffin wax is an active ingredient with group VIII (Ni or Co) and group vib (Mo or W) metallic element mainly, with γ-Al
2O
3Be carrier.It is generally acknowledged: catalyst for hydrogen refining of paraffin wax should have very high hydrofining performance.But also exist being difficult in some paraffin raw material has a colour substance by what hydrogenation was taken off, and these materials can cause refining wax product to be a bit darkish in color, and can not meet the requirement of food-grade paraffin wax to color.Therefore, require prepared catalyzer both to possess high hydrofining performance, also should be pointed, the higher ability that colour substance is arranged in the paraffin that removes.
U.S. Pat P 4,186, and 078 (contains SiO by adding a large amount of silicon in carrier
25w%～25w%) prepares SiO
2-Al
2O
3Carrier has than large specific surface, larger aperture and concentrated pore distribution to guarantee carrier.In order to reduce the acidity of catalyzer, in the process of preparation carrier, add the basic metal of 0.2w%～5w% simultaneously.CN 1085594A discloses a kind of catalyst for hydrogen refining of paraffin wax, also adopts the SiO that contains high silicon in this catalyzer
2-Al
2O
3(contain SiO
25w%～10w%) makes carrier.Be with U.S. Pat P 4,186,078 difference: in preparation process, add H
3PO
4Reduce the acidity of carrier (catalyzer).
How the starting point of above-mentioned two patents mainly is physicals such as specific surface area, pore size and the pore distribution and the acidity etc. of modulation catalyst for hydrogen refining of paraffin wax.But the hydrorefining paraffin wax process mainly to be the hydrogenation to destabilization and objectionable impurities (as mononuclear aromatics, polynuclear aromatics) saturated and paraffin in removing of colour substance arranged.Though above-mentioned catalyzer (and other catalyst for hydrogen refining of paraffin wax) is pretty good at the saturated aspect of performance of hydrogenation, the aspect of performance that removes of coloring matter still seems not enough in to paraffin.Therefore, for some paraffin that is difficult to decolour, adopt the existing catalyzer still can't the qualified food-grade paraffin wax of production color.
Summary of the invention
At the deficiencies in the prior art, the invention provides the catalyst for hydrogen refining of paraffin wax that a kind of existing high hydrofining activity has high decoloration performance again concurrently.
Catalyst for hydrogen refining of paraffin wax of the present invention and other petroleum fractions hydrotreating catalyst have much in common: be active ingredient with group VIII and group vib metallic element mainly, with γ-Al
2O
3Be carrier.Catalyst for hydrogen refining of paraffin wax of the present invention has following character:
(1), γ-Al
2O
3Contain auxiliary agent boron in the carrier;
(2), be benchmark with the weight of catalyzer, the content of active ingredient is as follows: MoO
317%～20%, NiO3.0%～4.0%, P 2.0%～3.0%, B
2O
33.0%～10.0%, be preferably 4.0%～8.0%.
(3), specific surface area is 180m
2/ g～250m
2/ g, pore volume are 0.30ml/g～0.35ml/g, and average pore diameter is 7.8nm～9.0nm, and wherein the pore volume of 4.0nm～12.0nm accounts for the 85.0v%～93.0v% of whole pore volume.
Boracic γ-Al that the present invention is used
2O
3Carrier has following character:
(1), specific surface area is 280m
2/ g～350m
2/ g, pore volume are 0.60ml/g～0.80ml/g, and average pore diameter is 7.8nm～8.8nm;
(2), pore distribution is more concentrated, the pore volume of 4.0nm～12.0nm accounts for the 85.0v%～90.0v% of whole pore volume.
It is as follows that catalyst for hydrogen refining of paraffin wax of the present invention prepares main points: with B
2O
3-Al
2O
3Being carrier, is steeping fluid with Mo-Ni-P solution, adopts co-impregnation to prepare Mo-Ni-P/B
2O
3-Al
2O
3Catalyst precursor adopts " three sections constant temperature calcinings " preparation catalyzer then, promptly after dipping and drying, catalyst precursor respectively at 160～205 ℃, is carried out constant temperature calcining under 282～360 ℃ and 380～450 ℃, makes catalyst for hydrogen refining of paraffin wax.
In the roasting process of above-mentioned catalyst precursor, three preceding heat-up rates of constant temperature calcining section are 2 ℃～5 ℃/minute.The first constant temperature zone roasting time is that 0.5 hour～2.0 hours, the second constant temperature zone roasting time are 0.5 hour～2.0 hours, and the 3rd constant temperature zone roasting time is 3.0～6.0 hours.
Above-mentioned B
2O
3-Al
2O
3The preparation process of carrier is as follows: a water aluminum oxide mixes with the halogen compounds of boron-containing compound or boracic and pinches, and through extrusion, drying, roasting, makes B
2O
3-Al
2O
3Carrier.
B of the present invention
2O
3-Al
2O
3The concrete preparation process of carrier is:
(1). take by weighing an a certain amount of water aluminum oxide and (contain the dry glue powder of alumina trihydrate≤2w%), add additive and peptization acid solution, fully mix and pinch until becoming plastic shape; (2). extruded moulding on banded extruder; (3). the wet bar after the moulding is following dry 2 hours～4 hours at 105 ℃～115 ℃; (4). place High Temperature Furnaces Heating Apparatus then, 150 ℃～270 ℃ following constant temperature calcinings 0.5 hour～3.0 hours; Then 400 ℃～520 ℃ following constant temperature calcinings 2.0 hours～5.0 hours; At last 580 ℃～700 ℃ following constant temperature calcinings 1.0 hours～3.0 hours.
Said additive is the halogen compounds of boron-containing compound or boracic in the step (1).Said boron-containing compound is H preferably
3BO
3Or B
2O
3, the halogen compounds of said boracic is BCl preferably
3, BBr
3Or BF
3
The peptization acid solution that is added in the step (1), preferably nitric acid and/or acetate.
Temperature rise rate in the step (4) before each constant temperature zone is 2 ℃～5 ℃/minute.
Above-mentioned Mo-Ni-P solution has following character: (1). and every 100ml solution contains MoO
325g～50g contains NiO 6g～10g.P/MoO
3Weight ratio is 0.08～0.18; (2). if desired, this solution can continue to heat and is concentrated into higher concentration; (3). this solution at room temperature can be steady in a long-term, and the preservation several years does not produce muddiness or precipitation.
The preparation main points of this Mo-Ni-P solution are: by the strength of solution requirement required phosphoric acid is added in the entry, make phosphate aqueous solution.Above-mentioned phosphate aqueous solution is joined in the molybdenum oxide of aequum.With this system under agitation heat temperature raising and be heated to molybdenum oxide all or most of dissolving to little boiling.System temperature is reduced to 60 ℃～70 ℃, add the basic nickel carbonate of requirement.Heat up once more and be heated to little boiling, and be heated to basic nickel carbonate and all dissolve.Last slowly heating evaporation removes redundant moisture and makes solution concentration, makes the concentration that requires, the Mo-Ni-P solution of high stability.
The step that the present invention prepares Mo-Ni-P solution is as follows:
(1). under agitation phosphate aqueous solution is added in the molybdenum oxide.Heat temperature raising boils and is heated to molybdenum oxide all or most of dissolving to little.
(2). after above-mentioned solution is cooled to 60 ℃～70 ℃, add basic nickel carbonate.Be warming up to again little boil and be heated to basic nickel carbonate and the residue molybdenum oxide all dissolve.Reduce to the room temperature after-filtration to remove insoluble impurities.
(3). above-mentioned solution heating is concentrated into needed concentration.
Advantage of the present invention is:
(1). the present invention is simple and easy to do.By introducing boron-containing additive, control calcination steps and maturing temperature are controlled the surface properties of carrier, increase the specific surface area and the aperture of carrier (thereby also being catalyzer), improve reactive metal at Mo-Ni-P/B
2O
3-Al
2O
3Dispersion state on the catalyst surface improves its reducing property, thereby has improved the hydrorefining paraffin wax activity and the decoloration performance of catalyzer;
(2). the made Mo-Ni-P solution of the present invention, form rationally, can be steady in a long-term, and concentration can be as required with time modulation.Therefore, reactive metal is at made Mo-Ni-P/B
2O
3-Al
2O
3Higher dispersity and good dispersion state can be arranged on the catalyst surface, and it is active and to the decoloration performance of paraffin to help improving the hydrofining of this catalyzer;
(3). Mo-Ni-P/B of the present invention
2O
3-Al
2O
3Catalyst for hydrogen refining of paraffin wax, active metallic content can reduce 20w%, but still keeps higher hydrorefining paraffin wax reactive behavior;
(4). Mo-Ni-P/B of the present invention
2O
3-Al
2O
3Catalyst for hydrogen refining of paraffin wax has superpower paraffin decoloration performance.
Embodiment
For further specifying all main points of the present invention, enumerate following examples and comparative example.
Embodiment 1
(1) .B
2O
3-Al
2O
3The preparation of carrier
Weigh a water aluminum oxide dry glue powder (containing the 2w% alumina trihydrate) 200g, add 6.5g B
2O
3, 150ml3wt%HNO
3With 5ml H
2O.Thorough mixing, be extruded into the trifolium strip after being kneaded into plastic shape.Dry in the air spend the night after, 110 ℃ of down oven dry 2 hours.
Dry sample is placed High Temperature Furnaces Heating Apparatus, is warming up to 200 ℃ with 3 ℃ of speed of per minute, and under this temperature constant temperature calcining 1.0 hours.Then be warming up to 460 ℃ with 3 ℃ of speed of per minute, and under this temperature constant temperature calcining 2.0 hours, be warming up to 650 ℃ with 3 ℃ of speed of per minute again, and under this temperature constant temperature calcining 2.0 hours.
(2) preparation of .Mo-Ni-P solution
14ml phosphoric acid (concentration is 85v%) is dissolved in the 600ml water.Under agitation solution is joined in the 80g molybdenum oxide.Be warming up to and littlely boil and heat 3 hours to the most of dissolving of molybdenum oxide.Be cooled to 65 ℃, under agitation slowly add basic nickel carbonate 47g, be warming up to again and littlely boil and heated 3 hours, all dissolve to throw out, filter.Filtrate is concentrated into 285ml.
(3) .Mo-Ni-P/B
2O
3-Al
2O
3Preparation of catalysts
150ml is joined the B of 100g embodiment 1 (2) preparation according to the Mo-Ni-P solution of embodiment 1 (2) preparation
2O
3-Al
2O
3In, at room temperature flood 4 hours after, leach redundant solution.After moist catalysis dries in air and spends the night, dried 2 hours down at 120 ℃.Dried sample is warming up to 190 ℃ with 3 ℃ of/minute speed, constant temperature calcining 1 hour.Be warming up to 330 ℃ with 3 ℃ of/minute speed again, constant temperature calcining 1 hour.Be warming up to 420 ℃ with 3 ℃ of/minute speed at last, constant temperature calcining 4 hours.
Embodiment 2
(1) .B
2O
3-Al
2O
3The preparation of carrier
Identical with embodiment 1 (1) step, but B
2O
3Add-on changes 9.5g into.
(2) preparation of Mo-Ni-P solution
Identical with embodiment 1 (2) step.
(3) .Mo-Ni-P/B
2O
3-Al
2O
3Preparation of Catalyst
Identical with embodiment 1 (3) step.
Embodiment 3
(1) .B
2O
3-Al
2O
3The preparation of carrier
Identical with embodiment 1 (1) step, but B
2O
3Change BF into
3BF
3Add-on is 23.5g.
(2) preparation of .Mo-Ni-P solution
Identical with embodiment 1 (2) step, but filtrate is concentrated into 260ml.
(3) .Mo-Ni-P/B
2O
3-Al
2O
3Preparation of Catalyst
Identical with embodiment 1 (3) step, but the 3rd section maturing temperature changes 390 ℃ into.
Comparative example 1
(1). γ-Al
2O
3The preparation of carrier
Weigh a water aluminum oxide dry glue powder (containing the 2wt% alumina trihydrate) 200g, 160ml 3wt%HNO
3With 5ml H
2O.Thorough mixing, be extruded into the trifolium strip after being kneaded into plastic shape.After air drying spends the night, be that 110 ℃ dried 2 hours down.
Dry sample is placed High Temperature Furnaces Heating Apparatus, is warming up to 200 ℃ with 3 ℃ of speed of per minute, and under this temperature constant temperature calcining 1.0 hours.Then be warming up to 488 ℃ with 3 ℃ of speed of per minute, and under this temperature constant temperature calcining 2.0 hours, again with 3 ℃ of speed of per minute be warming up to 600 ℃ and under this temperature constant temperature calcining 2.0 hours.
(2) preparation of .Mo-Ni-P solution
15ml phosphoric acid (concentration is 85v%) is dissolved in the 600ml water.Under agitation solution is joined in the 100g molybdenum oxide.Be warming up to and littlely boil and heat 3 hours to the most of dissolving of molybdenum oxide.Be cooled to 65 ℃, under agitation slowly add basic nickel carbonate 60g, be warming up to again and littlely boil and heated 3 hours, all dissolve to throw out, filter.Filtrate is concentrated into 285ml.
(3) .Mo-Ni-P/Al
2O
3Preparation of Catalyst
150ml is joined the γ-Al of this example (1) preparation according to the Mo-Ni-P solution of this example (2) preparation
2O
3In, at room temperature soak 4 hours after, leach redundant solution.Moist catalysis was dried 2 hours down at 120 ℃ after air drying spends the night.Dried sample was warming up to 190 ℃ of constant temperature calcinings 1 hour with 3 ℃ of/minute speed.Be warming up to 368 ℃ with 3 ℃ of/minute speed again, constant temperature calcining 1 hour.Be warming up to 490 ℃ with 3 ℃ of/minute speed at last, constant temperature calcining 4 hours.
Comparative example 2
(1). γ-Al
2O
3The preparation of carrier
Identical with comparative example 1 (1).
(2) preparation of .Mo-Ni-P solution
Identical with comparative example 1 (2), but solution is concentrated into 260ml at last.
(3) .MoNiP/Al
2O
3Preparation of Catalyst
Identical with comparative example 1 (3).
More than the physico-chemical property of each routine carrier and catalyzer list in table 1 and the table 2 respectively.Each routine catalyst activity evaluation result is as shown in table 3.Evaluation of catalyst activity is raw materials used to be No. 58 wax materials (Daqing crude oil).Reaction process condition is: LHSV 0.8h
-1, reaction pressure (hydrogen pressure) 6.0MPa, 260 ℃ of temperature of reaction, hydrogen/wax volume ratio is 300: 1.
Table 2 data show: the catalyst pores diameter of present embodiment obviously increases, pore distribution more concentrated (comparing with comparative example).
The physico-chemical property of each routine carrier of table 1
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Comparative example 1 | Comparative example 2 | |
| B 2O 3，wt％ | 4.5 | 6.3 | 7.9 | - | - |
| Al 2O 3，wt％ | Surplus | Surplus | Surplus | 100 | 100 |
| Specific surface, m 2/g | 323 | 318 | 316 | 300 | 302 |
| Pore volume, ml/g | 0.730 | 0.725 | 0.727 | 0.668 | 0.670 |
| Average pore diameter, nm | 8.39 | 8.40 | 8.27 | 7.77 | 7.75 |
| Pore size distribution, v%＜4.0nm 4.0-12.0nm＞12.0nm | 5.00 86.8 8.20 | 4.80 87.0 8.20 | 5.10 86.9 8.00 | 11.3 82.1 6.60 | 11.5 82.0 6.50 |
The physico-chemical property of each routine catalyzer of table 2 relatively
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Comparative example 1 | Comparative example 2 | |
| Chemical constitution, wt% MoO 3 NiO P B 2O 3 Al 2O 3 | 17.3 3.55 2.44 3.00 surpluses | 17.2 3.53 2.43 5.87 surpluses | 19.0 3.95 2.41 7.00 surpluses | 17.3 3.57 2.45-surpluses | 20.7 4.26 2.60-surpluses |
| Specific surface, m 2/ g pore volume, ml/g average pore diameter, nm | 223 0.316 8.85 | 219 0.310 8.76 | 219 0.301 8.78 | 196 0.305 8.00 | 193 0.293 7.98 |
| Pore size distribution, v%＜4.0nm 4.0-12.0nm＞12.0nm | 3.9 88.8 7.3 | 3.9 88.6 7.5 | 5.0 89.0 6.0 | 10.8 80.0 9.2 | 10.7 80.0 9.3 |
Table 3 data show: (1). under the identical situation of metal (Mo and Ni) content, owing to contain the B of 3.0w% in the catalyzer
2O
3(embodiment 1), the light stability of refining wax product is identical with comparative example 1, and simple and easy FDA value (index of aromatic hydrocarbon content height in the refining wax product) then is lower than (being better than) comparative example 1.The color (+No. 30) of especially refining wax product obviously is better than comparative example 1, has reached the requirement of national standard to the food-grade paraffin wax color; (2). at the low approximately 20w% of metal (Mo and Ni) content, and B
2O
3Content reaches under the situation of 5.87w% (embodiment 2), and the light stability of refining wax product is brought up to No. 3, and color is further improved (＞+No. 30), and simple and easy FDA value obviously reduces (comparing with embodiment 1); (3). B in catalyzer
2O
3When content reached the 7.00w% left and right sides, metal content further improved (with comparative example 1,2 comparisons, MoO
3Improve 10w% and 12w% respectively with NiO content), the light stability of refining wax product, simple and easy FDA value and color are all further improved, and are better than comparative example greatly.All indexs all obviously are better than the requirement of national standard to the food-grade paraffin wax color.
Each routine activity rating of catalyst result of table 3
| Paraffin | Refining wax product | |||||
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Comparative example 1 | Comparative example 2 | ||
| Fusing point, ℃ | 58.2 | 58.2 | 58.2 | 58.2 | 58.2 | 58.2 |
| Oleaginousness, wt% | 0.33 | 0.33 | 0.33 | 0.33 | 0.33 | 0.33 |
| Color, number | -7 | +30 | ＞+30 | ＞+30 | +27 | +28 |
| Light stability, number | 7 | 3～4 | 3 | 3 | 3～4 | 3～4 |
| Ultraviolet extinction value (simple and easy FDA) 280～289nm, 290～299nm | 0.356 0.230 | 0.050 0.029 | 0.032 0.022 | 0.021 0.010 | 0.064 0.039 | 0.051 0.029 |
Claims (7)
1, a kind of preparation method of catalyst for hydrogen refining of paraffin wax comprises the steps: with Mo-Ni-P solution to be the γ-Al of steeping fluid dipping boracic
2O
3Carrier, drying, roasting, make this catalyzer, wherein said roasting is " three sections constant temperature calcinings ", be about to catalyst precursor respectively 160 ℃～205 ℃ constant temperature calcinings 0.5～2.0 hour, 282 ℃～360 ℃ constant temperature calcinings 0.5～2.0 hour and 380 ℃～450 ℃ constant temperature calcinings 3.0～6.0 hours, the heat-up rate before each constant temperature calcining section is 2～5 ℃/minute; Weight with described catalyzer is benchmark, and it consists of: MoO
3Content be 17%～20%, the content of NiO is 3.0%～4.0%, the content of P is 2.0%～3.0%, B
2O
3Content be 3.0%～10.0%.
2,, it is characterized in that the γ-Al of boracic according to the described Preparation of catalysts method of claim 1
2O
3The preparation process of carrier is as follows: a water aluminum oxide is mixed with the halogen compounds of additive boron-containing compound or boracic pinch, through extrusion, drying, roasting, make B again
2O
3-Al
2O
3Carrier.
3,, it is characterized in that said boron-containing compound is H according to the described Preparation of catalysts method of claim 2
3BO
3Or B
2O
3, the halogen compounds of boracic is BCl
3, BBr
3Or BF
3
4, according to the described Preparation of catalysts method of claim 2, it is characterized in that said B
2O
3-Al
2O
3Precursor carrier adopts " three sections constant temperature calcinings ", promptly successively 150 ℃～270 ℃ following constant temperature calcinings 0.5～3.0 hour; Then 400 ℃～520 ℃ following constant temperature calcinings 2.0～5.0 hours; At last 580 ℃～700 ℃ following constant temperature calcinings 1.0～3.0 hours; Temperature rise rate before each constant temperature zone is 2～5 ℃/minute.
5,, it is characterized in that every 100ml solution contains MoO in the above-mentioned Mo-Ni-P solution according to the described Preparation of catalysts method of claim 1
325g～50g contains NiO 6g～10g, P/MoO
3Weight ratio is 0.08～0.18.
6,, it is characterized in that the weight with catalyzer is benchmark, B according to the described Preparation of catalysts method of claim 1
2O
3Content be 4.0%～8.0%.
7, according to the described Preparation of catalysts method of claim 1, the specific surface area that it is characterized in that described catalyzer is 180m
2/ g～250m
2/ g, pore volume are 0.30ml/g～0.35ml/g, and average pore diameter is 7.8nm～9.0nm, and wherein the pore volume of 4.0nm～12.0nm accounts for the 85.0v%～93.0v% of whole pore volume.
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|---|---|---|---|
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|---|---|---|---|
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|---|---|
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP4082657A4 (en) * | 2019-12-27 | 2024-04-03 | Petroleo Brasileiro S.A. - PETROBRAS | Method for obtaining a support for hydrofining catalysts, support for hydrofining catalysts, hydrofining catalysts, process for obtaining hydrofining catalysts, and use of support in hydrofining catalysts |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100446856C (en) * | 2006-07-26 | 2008-12-31 | 中国石油大庆石化公司研究院 | Petroleum wax hydrofining catalyst and its prepn process |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP4082657A4 (en) * | 2019-12-27 | 2024-04-03 | Petroleo Brasileiro S.A. - PETROBRAS | Method for obtaining a support for hydrofining catalysts, support for hydrofining catalysts, hydrofining catalysts, process for obtaining hydrofining catalysts, and use of support in hydrofining catalysts |
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