CN100467576C - Refining catalyst with low molybdenum content for paraffin-hydrogenating and its preparing process - Google Patents

Refining catalyst with low molybdenum content for paraffin-hydrogenating and its preparing process Download PDF

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CN100467576C
CN100467576C CNB2005100475302A CN200510047530A CN100467576C CN 100467576 C CN100467576 C CN 100467576C CN B2005100475302 A CNB2005100475302 A CN B2005100475302A CN 200510047530 A CN200510047530 A CN 200510047530A CN 100467576 C CN100467576 C CN 100467576C
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CN1952079A (en
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罗锡辉
何金海
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China Petroleum and Chemical Corp
Sinopec Fushun Research Institute of Petroleum and Petrochemicals
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China Petroleum and Chemical Corp
Sinopec Fushun Research Institute of Petroleum and Petrochemicals
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Abstract

The invention disclosed a kind of ozocerite hydrogenation refining catalyst with low molybdenum content as well as its preparing method. During the process of preparing the carrier, add nickel compound to get Ni-Al2O3, the surface of which contains only weak acid center. Using the Ni-Al2O3 as the carrier, dip the material into the Mo-Ni-P solution and calcinate by the third-stage incubating technology to get the MoNiP/Ni-Al2O3 ozocerite hydrogenation refinement catalyst. The molybdenum content of the invention is only 60-75m% of the present technology; the invention has very simple preparing procedure and less wastage of raw materials; besides, the activity of the catalyst is higher than the present ozocerite hydrogenation refinement catalyst.

Description

A kind of refining catalyst with low molybdenum content for paraffin-hydrogenating and preparation method thereof
Technical field
The present invention relates to a kind of catalyst for hydrogen refining of paraffin wax and preparation method thereof, especially is the hydrorefined Catalysts and its preparation method of paraffin raw material of active ingredient with molybdenum and nickel.
Background technology
Paraffin raw material originates from decompression two in the crude oil distillation process, three-way cut (VGO) reduces pressure.The main purpose of hydrorefining paraffin wax is to remove contained coloured, destabilization and harmful material (as condensed ring aromatic hydrocarbon such as benzo pyrroles) in the starting paraffin by hydrofining.Hydrorefining paraffin wax requires the saturated and very strong decoloration performance of the existing high hydrogenation of catalyzer, and the strong ability that removes aromatic organic compounds is arranged again.
Catalyst for hydrogen refining of paraffin wax is close with hydrotreating catalyst aspect composition.The major metal component is molybdenum or tungsten, and the promoter metal component is nickel or cobalt, with γ-Al 2O 3Be carrier.It is main metal component that the most widely used at present catalyst for hydrogen refining of paraffin wax adopts molybdenum, and molybdenum content accounts for 15～28m% of catalyzer total mass (with MoO 3Meter); With nickel is promoter metal, accounts for the 3.6～6.0m% (in NiO) of catalyzer total mass.For example U.S. Pat P 4,186, and 078 discloses a kind of catalyst for hydrogen refining of paraffin wax, and this catalyzer contains MoO 315.1～19.1m%, NiO 3.6～5.3m%.Chinese patent CN 92111133.9 disclosed a kind of catalyst for hydrogen refining of paraffin wax contain MoO 318.0～24.0m%, NiO 4.0～6.0m%.Chinese patent CN 98114346.6 disclosed a kind of catalyst for hydrogen refining of paraffin wax contain MoO 323～28m%, NiO 4.5～6.0m%.
The raw materials cost of reactive metal accounts for the larger proportion of catalyzer cost in the catalyst for hydrogen refining of paraffin wax, the price continuous rise of molybdenum in recent years particularly, and between in recent years, MoO 3Price rise to 530,000 yuan/ton by 80,000 yuan/ton, increased more than 6 times.Molybdenum has been MoNi/Al 2O 3The main part of type catalyst for hydrogen refining of paraffin wax price structure.Therefore, the cost that how to reduce catalyst for hydrogen refining of paraffin wax is one of important topic of this area.
Summary of the invention
At the deficiencies in the prior art, the invention provides a kind of catalyst for hydrogen refining of paraffin wax of with low cost, excellent property.
Catalyst for hydrogen refining of paraffin wax of the present invention adopts conventional immersion process for preparing: with the solution impregnation Ni-Al that contains Mo-Ni-P 2O 3, dry then, roasting make final catalyzer.Ni-Al wherein 2O 3The preparing carriers process is:
(1), pseudo-boehmite powder and nickel compound containing (powder) are mixed together, mediate, until becoming plastic shape;
(2), extruded moulding in banded extruder.The shape of bar and thickness are by the shape and the pore size decision of banded extruder orifice bore;
(3), with the wet bar drying after the moulding, adopt three sections constant temperature method roastings then: 150～270 ℃ of roastings 0.5～3.0 hour, 350～450 ℃ of warm roastings 2.0～5.0 hours, at last 650～700 ℃ of roastings 1.0～3.0 hours.
Wherein nickel compound containing is preferably selected NiCO for use 32Ni (OH) 24H 2O (basic nickel carbonate).Certainly, also can adopt Ni (NO 3) 26H 2O (nickelous nitrate).Consumption is by required nickel amount in the carrier, generally in the mass percent carrier of NiO nickeliferous 2.0%～4.0%.In mixing, kneading process, can use an amount of peptization acid (for example rare nitric acid) to increase plasticity-.
The Ni-Al of method for preparing 2O 3Carrier has following character: specific surface area is 200～300m 2/ g; Pore volume is 0.60～0.70ml/g; Average pore diameter is 8.0～10.0nm, and wherein 4.0～10.0nm hole accounts for 80%～90% of whole pore volume.Carrier surface only contains the weak acid center, does not contain middle strong acid center, does not especially contain strong acid center.Contain nickel 2.0%～4.0% (in the mass percent of NiO) in the carrier.
Above-mentioned Ni-Al 2O 3Carrier adopts conventional pickling process to become catalyst for hydrogen refining of paraffin wax, and specific nature is as follows:
(1), metal content is MoO 38～10m%, NiO 6～8m%.
(2), specific surface area is 180～250m 2/ g; Pore volume is 0.45～0.55ml/g; Average pore diameter 8.0～10.0nm.Pore distribution concentration, bore dia be the hole of 4.0～10.0nm account for whole pore volume 80%～90%.
Catalyzer of the present invention is suitable for 54 #～62 #Paraffin raw material, (hydrogen pressure 3～10MPa) carries out hydrofining under medium reaction pressure condition.The hydrofining condition adopts this area usual terms: 220～310 ℃ of temperature of reaction, LHSV (volume space velocity during liquid) 0.5～2.0h -1, hydrogen/wax volume ratio is 200～1000.
The present invention by the suitable alumina carrier containing Ni of processability, improve the dispersion state of metal on carrier surface, thereby can reduce the content of molybdenum significantly and keep the hydrofining performance of catalyzer, reach the purpose that reduces the catalyzer manufacturing cost.Alumina carrier containing Ni of the present invention has surface of good character: pore distribution is quite concentrated, only contains the weak acid center on the surface, strong acid center and strong acid center in not containing.These character have outstanding effect for the hydrofining of paraffin raw material.The present invention reduces MoO greatly because of the content of reactive metal molybdenum in the catalyzer 3Content is than existing MoNi/Al 2O 3Catalyzer is low by about 60%～75%, so the cost of catalyzer obviously reduces.
Catalyst for hydrogen refining of paraffin wax of the present invention has the following advantages:
(1), the present invention is simple and easy to do.Control Ni-Al by adding a small amount of nickel compound containing in the kneading process with control carrier calcination steps, maturing temperature 2O 3Surface properties, improve the dispersion state of reactive metal on catalyst surface.Thereby reach the molybdenum content that reduces catalyzer significantly and keep or improve the active purpose of hydrorefining paraffin wax of catalyzer.
(2), the prepared Ni-Al of the present invention 2O 3The general catalyst for hydrogen refining of paraffin wax carrier of aperture ratio want big, average pore diameter 8.0～10.0nm.Pore distribution concentration, bore dia be the hole of 4.0～10.0nm account for whole pore volume 80～90%.
(3), the made Mo-Ni-P solution of the present invention, form rationally, concentration can be adjusted arbitrarily, and can maintain a long-term stability.Because the metal content of catalyzer of the present invention is lower, only need the Mo-Ni-P solution of lower concentration, so the formulations prepared from solutions process is simpler.
(4), the manufacturing cost of catalyst for hydrogen refining of paraffin wax of the present invention is comparatively cheap, and the hydrorefining paraffin wax activity of catalyzer is equal to or slightly better in existing catalyzer.
Embodiment
The character of catalyst for hydrogen refining of paraffin wax of the present invention is as follows: (forming in mass)
(1), metal content is MoO 38%～10%, NiO 6%～8%.P content 1%～3%.
(2), specific surface area is 180～250m 2/ g; Pore volume is 0.45～0.55ml/g; Average pore diameter 8.0～10.0nm.Pore distribution concentration, bore dia be the hole of 4.0～10.0nm account for whole pore volume 80%～90%;
(3), active metal component molybdenum, nickel have preferable dispersion state on catalyst surface, thereby the hydrofining activity is higher.
It is as follows that catalyst for hydrogen refining of paraffin wax of the present invention prepares main points: with prepared Ni-Al 2O 3Being carrier, is steeping fluid with Mo-Ni-P, takes step pickling process (soaking a method altogether) preparation catalyst precursor.Adopt three sections constant temperature calcining technology to prepare catalyzer then: respectively at 160～205 ℃, 280～350 ℃ and 400～550 ℃ of three temperature ranges are carried out constant temperature calcining, make MoNiP/Ni-Al with catalyst precursor 2O 3Catalyst for hydrogen refining of paraffin wax.
In the above-mentioned roasting process, the heat-up rate between initial heat-up rate and per two the constant temperature calcining temperature is 2～5 ℃/minute.First and second constant temperature zone roasting time is 0.5～2.0 hour, and the 3rd constant temperature zone is 2.0～5.0 hours.
Above-mentioned Mo-Ni-P solution has following character: 1, every 100ml solution contains MoO 310～12g, NiO5～7g.P/MoO 3Mass ratio is 0.1～0.3; 2, if desired, this solution can continue to heat and is concentrated into arbitrarily high concentration, also can be diluted to any lower concentration; 3, this solution (even under high density) at room temperature can maintain a long-term stability, and 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, be made into phosphate aqueous solution.Above-mentioned phosphate aqueous solution is joined the MoO of aequum 3In.With this system under agitation heat temperature raising and be heated to MoO to little boiling 3Most of dissolving.When system temperature is reduced to 60～70 ℃, add the basic nickel carbonate (NiCO of requirement 32Ni (OH) 24H 2O), stir and heat up once more and is heated to little boiling, and be heated to basic nickel carbonate and all dissolve.Last slowly heating evaporation is removed redundant moisture and is made solution concentration, makes the Mo-Ni-P solution of suitable concn.
The step that the present invention prepares Mo-Ni-P solution is as follows:
(1), under agitation phosphate aqueous solution is added MoO 3In, be warming up to and littlely boil and be heated to MoO 3Whole or most of dissolvings;
(2), above-mentioned solution is cooled to 60～70 ℃, the adding basic nickel carbonate.Place be warming up to again after 15 minutes little boil and be heated to basic nickel carbonate and the residue MoO 3All dissolvings.Reduce to the room temperature after-filtration to remove insoluble impurities;
(3), above-mentioned solution heating is concentrated into needed concentration.Also can be concentrated into any concentration, be diluted with water to desired concn before the use again.
For further specifying all main points of the present invention, enumerate following examples and comparative example.Wherein m%, % are mass percent.
Embodiment 1
(1), Ni-Al 2O 3The preparation of carrier
Get 200g pseudo-boehmite powder and (contain Al (OH) 3＜3m%), add the 7.5g basic nickel carbonate, add 150ml 3% HNO after the mixing again 3With an amount of H 2O.Thorough mixing, kneading are until becoming plastic shape.Adopt trifolium orifice plate (φ 1.4mm) extrusion.Wet bar was dried 2 hours down at 115 ℃ after drying in air and spending the night.
Drying is crossed sample places High Temperature Furnaces Heating Apparatus, be warming up to 210 ℃ with 3 ℃ of speed of per minute, and under this temperature constant temperature calcining 1.0 hours.Then be warming up to 380 ℃ with 3 ℃ of speed of per minute, and under this temperature constant temperature calcining 3.0 hours.Be warming up to 660 ℃ with 3 ℃ of speed of per minute again, and under this temperature constant temperature calcining 2.0 hours.
(2), the preparation of Mo-Ni-P solution
With 9.0ml H 3PO 4(contain H 3PO 485%) is dissolved in the 250ml water.Under agitation solution is joined 18g MoO 3In.Be warming up to and littlely boil and heat 2 hours to MoO 3Most of dissolving.Be cooled to 60～70 ℃, under agitation slowly add basic nickel carbonate 10.3g, be warming up to again and littlely boil and heated 2 hours, all dissolve to throw out.Filter then, filtrate is concentrated into 200ml.
(3), MoNiP/Ni-Al 2O 3Preparation of Catalyst
Take by weighing 100g Ni-Al 2O 3, add the Mo-Ni-P solution of 150ml according to embodiment 1 (2) preparation.After at room temperature flooding 4 hours, leach redundant solution.The moist catalysis bar was dried 2 hours down at 115 ℃ after air drying spends the night.Dried sample is warming up to 180 ℃ with 3 ℃ of/minute speed, constant temperature calcining 1 hour.Be warming up to 350 ℃ with 3 ℃ of/minute speed again, constant temperature calcining 1 hour.Be warming up to 450 ℃ with 3 ℃ of/minute speed at last, constant temperature calcining 3 hours.
Embodiment 2
(1), Ni-Al 2O 3The preparation of carrier
Identical with embodiment 1 (1).But the basic nickel carbonate add-on is increased to 9.5g by 7.5g.Final calcination temperature is brought up to 680 ℃ by 660 ℃.
(2), the preparation of Mo-Ni-P solution
Identical with embodiment 1 (2).But filtrate finally is concentrated into 180ml.
(3), MoNiP/Ni-Al 2O 3Preparation of Catalyst
With embodiment 1 (3).
Embodiment 3
(1), Ni-Al 2O 3The preparation of carrier
Identical with embodiment 2 (1).
(2), the preparation of Mo-Ni-P solution
With embodiment 2 (2).
(3), MoNiP/Ni-Al 2O 3Preparation of Catalyst
With embodiment 1 (3).But the catalyzer final calcination temperature is 470 ℃.
Comparative example 1
(1), γ-Al 2O 3The preparation of carrier
To contain Al 2O 3The AlCl of 5g/100ml 3Solution 5L with contain SiO 2The acidified sodium silicate 250ml of 5g/100ml mixes, and pH value is transferred to 2.8, keeps 15 ℃, leaves standstill 2 hours.Be 15 ℃ with temperature then, concentration is in 9% the ammoniacal liquor and above-mentioned solution.Control ammoniacal liquor flow, making reaction contact time is 10 minutes, and total reaction time is 90 minutes, and material PH is 7.8.Filtration under diminished pressure.Filter cake distilled water wash 3 times.Wash temperature is 25 ℃, and washing time is 40 minutes.Corresponding to 500g Al 2O 3The wet gel amount of butt, the H of adding 40g 53% 3PO 4Solution and 10ml 33% HNO 3, stirred 2 hours under the room temperature, make colloidal sol.Colloidal sol is dripped by water dropper, by oil ammonia column balling-up (room temperature).The wet bulb of making soaked 3 hours in 5% ammoniacal liquor.Then wet bulb was dried 3 hours down at 90 ℃, 620 ℃ of following roastings 4 hours.Make carrier γ-Al 2O 3
(2), MoNi/Al 2O 3Preparation of Catalyst
Take by weighing by (1) prepared γ-Al 2O 3Bead 100g added after bleeding in filter flask 1 hour and contains MoO 330g/100ml, the ammonium molybdate of NiO 6.0g/100ml and nickelous nitrate ammonia soln 200ml flood 1 hour after-filtration.Catalyst precursor was dried 3 hours down at 120 ℃, 530 ℃ of following roastings 3 hours.
Comparative example 2
Step is identical with comparative example 1.53% H 3PO 4Solution usage changes 60g into.
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 60 #Wax material (Daqing crude oil).Reaction process condition is: LHSV0.8h -1, reaction pressure (hydrogen pressure) 6.0MPa, 260 ℃ of temperature of reaction, hydrogen/wax volume ratio are 300:1 (v/v).
By table 1 as seen: (1), compare Ni-Al of the present invention with the carrier of comparative example 2O 3Have bigger pore volume, bigger aperture, pore distribution concentration; (2), Ni-Al of the present invention 2O 3Only contain the weak acid center on the carrier surface, do not contain strong acid center and middle strong acid center.And the γ-Al in the reference example 2O 3, (the two accounts for γ-Al then to contain a considerable amount of strong acid and middle strong acid center 2O 3Total acid content 55～58%).
By table 2 as seen: (1), compare the molybdenum (MoO of catalyzer of the present invention with the catalyzer of comparative example 3) content will hang down more than the 50m%; (2), catalyzer of the present invention has bigger aperture and concentrated characteristics such as pore distribution.
By table 3 as seen: (1), catalyzer of the present invention have excellent results to hydrorefining paraffin wax.Compare with the comparative example catalyzer, the light stability of refining wax is suitable, all is No. 3.Refining wax (embodiment 1,2,3) is all low than comparative example (comparative example 1,2) at the ultraviolet absorption value (height of aromatic hydrocarbon content in corresponding to paraffin) at 280～289nm and 290～299nm place.Illustrate that catalyzer of the present invention has the saturated performance of aromatic hydrocarbon preferably and to the refining performance of paraffin; (2), the color (Sai Shi) of refining wax is+No. 30 all, be up to state standards to the specification of quality of food-grade paraffin wax.
The physico-chemical property of each routine carrier of table 1
Figure C200510047530D00121
[notes]: adopt ammonia absorption-TPD method to measure.150～250 ℃, 250～400 ℃, 400～500 ℃ corresponding to ammonia at the weak acid center, the desorption temperature of middle strong acid center and strong acid center.
The physico-chemical property of each routine catalyzer of table 2 relatively
Figure C200510047530D00131
Each routine activity rating of catalyst result of table 3
Figure C200510047530D00132

Claims (6)

1, a kind of preparation method of catalyst for hydrogen refining of paraffin wax adopts conventional immersion process for preparing: with the solution impregnation Ni-Al that contains Mo-Ni-P 2O 3Carrier, dry then, roasting make final catalyzer; Ni-Al wherein 2O 3The preparing carriers process is:
(1), pseudo-boehmite powder and nickel compound containing are mixed together, mediate, until becoming plastic shape;
(2), extruded moulding in banded extruder;
(3), with the wet bar drying after the moulding, adopt three sections constant temperature method roastings then: 150～270 ℃ of roastings 0.5～3.0 hour, 350～450 ℃ of warm roastings 2.0～5.0 hours, at last 650～700 ℃ of roastings 1.0～3.0 hours;
The described nickel compound containing of step (1) is selected basic nickel carbonate or nickelous nitrate for use, and consumption contains 2.0%～4.0% in the mass percent of NiO in carrier.
2, in accordance with the method for claim 1, it is characterized in that described Mo-Ni-P solution has following character: every 100ml solution contains MoO 310～12g, NiO5～7g, P/MoO 3Mass ratio is 0.1～0.3.
3, in accordance with the method for claim 1, it is characterized in that described employing Mo-Ni-P solution impregnation Ni-Al 2O 3Three sections constant temperature calcinings are adopted in roasting behind the carrier, respectively 160～205 ℃ of first constant temperature zones, 280～350 ℃ of second constant temperature zones and 400～550 ℃ of three temperature ranges of the 3rd constant temperature zone are carried out constant temperature calcining, first and second constant temperature zone roasting time is 0.5～2.0 hour, and the 3rd constant temperature zone is 2.0～5.0 hours.
4, in accordance with the method for claim 1, it is characterized in that described Ni-Al 2O 3Carrier has following character: specific surface area is 200～300m 2/ g; Pore volume is 0.60～0.70ml/g; Average pore diameter is 8.0～10.0nm, and 4.0～10.0nm hole accounts for 80%～90% of whole pore volume.
5, the catalyst for hydrogen refining of paraffin wax of the described method preparation of the arbitrary claim of a kind of claim 1～4 has following character, forms in mass:
(1), metal content is MoO 38%～10%, NiO6%～8%, P content 1%～3%;
(2), specific surface area is 180～250m 2/ g, pore volume are 0.45～0.55ml/g, average pore diameter 8.0～10.0nm.
6,, it is characterized in that the catalyst pores diameter is that the hole of 4.0～10.0nm accounts for 80%～90% of whole pore volume according to the described catalyzer of claim 5.
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US4186078A (en) * 1977-09-12 1980-01-29 Toa Nenryo Kogyo Kabushiki Kaisha Catalyst and process for hydrofining petroleum wax

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4186078A (en) * 1977-09-12 1980-01-29 Toa Nenryo Kogyo Kabushiki Kaisha Catalyst and process for hydrofining petroleum wax

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