CN1868590A - Catalyst for hydrogen refining of paraffin wax, prepn. method and application thereof - Google Patents
Catalyst for hydrogen refining of paraffin wax, prepn. method and application thereof Download PDFInfo
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- CN1868590A CN1868590A CN 200610046914 CN200610046914A CN1868590A CN 1868590 A CN1868590 A CN 1868590A CN 200610046914 CN200610046914 CN 200610046914 CN 200610046914 A CN200610046914 A CN 200610046914A CN 1868590 A CN1868590 A CN 1868590A
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- paraffin wax
- wax
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- 239000003054 catalyst Substances 0.000 title claims abstract description 70
- 239000012188 paraffin wax Substances 0.000 title claims abstract description 34
- 238000000034 method Methods 0.000 title claims abstract description 18
- 229910052739 hydrogen Inorganic materials 0.000 title claims description 26
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims description 25
- 239000001257 hydrogen Substances 0.000 title claims description 25
- 238000007670 refining Methods 0.000 title claims description 23
- 238000001354 calcination Methods 0.000 claims abstract description 15
- 238000001035 drying Methods 0.000 claims abstract description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 39
- 229910007570 Zn-Al Inorganic materials 0.000 claims description 24
- 238000002360 preparation method Methods 0.000 claims description 19
- 239000011701 zinc Substances 0.000 claims description 14
- 229910052759 nickel Inorganic materials 0.000 claims description 12
- 239000001993 wax Substances 0.000 claims description 11
- 239000011148 porous material Substances 0.000 claims description 10
- 230000000694 effects Effects 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 239000002994 raw material Substances 0.000 claims description 7
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 229910052725 zinc Inorganic materials 0.000 claims description 6
- 150000003752 zinc compounds Chemical class 0.000 claims description 6
- 238000005984 hydrogenation reaction Methods 0.000 claims description 4
- 239000000843 powder Substances 0.000 claims description 4
- 229910001593 boehmite Inorganic materials 0.000 claims description 3
- 239000000969 carrier Substances 0.000 claims description 3
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims description 3
- 240000005702 Galium aparine Species 0.000 claims description 2
- 235000014820 Galium aparine Nutrition 0.000 claims description 2
- 241000612118 Samolus valerandi Species 0.000 claims description 2
- 241000219793 Trifolium Species 0.000 claims description 2
- 238000007654 immersion Methods 0.000 claims description 2
- 238000000465 moulding Methods 0.000 claims description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract description 8
- 229910052593 corundum Inorganic materials 0.000 abstract 2
- 229910001845 yogo sapphire Inorganic materials 0.000 abstract 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 26
- 239000000243 solution Substances 0.000 description 25
- 230000000052 comparative effect Effects 0.000 description 15
- 239000011787 zinc oxide Substances 0.000 description 13
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 11
- 229910052750 molybdenum Inorganic materials 0.000 description 11
- 239000011733 molybdenum Substances 0.000 description 11
- 229910052751 metal Inorganic materials 0.000 description 10
- 239000002184 metal Substances 0.000 description 10
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 6
- 235000011114 ammonium hydroxide Nutrition 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 238000010792 warming Methods 0.000 description 6
- 239000002253 acid Substances 0.000 description 4
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 229910015338 MoNi Inorganic materials 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 3
- 230000003993 interaction Effects 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 230000001603 reducing effect Effects 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 2
- WURBVZBTWMNKQT-UHFFFAOYSA-N 1-(4-chlorophenoxy)-3,3-dimethyl-1-(1,2,4-triazol-1-yl)butan-2-one Chemical compound C1=NC=NN1C(C(=O)C(C)(C)C)OC1=CC=C(Cl)C=C1 WURBVZBTWMNKQT-UHFFFAOYSA-N 0.000 description 1
- 235000017166 Bambusa arundinacea Nutrition 0.000 description 1
- 235000017491 Bambusa tulda Nutrition 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 229910017318 Mo—Ni Inorganic materials 0.000 description 1
- 229910018104 Ni-P Inorganic materials 0.000 description 1
- 229910018536 Ni—P Inorganic materials 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 244000082204 Phyllostachys viridis Species 0.000 description 1
- 235000015334 Phyllostachys viridis Nutrition 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- 229910000611 Zinc aluminium Inorganic materials 0.000 description 1
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 1
- 239000011609 ammonium molybdate Substances 0.000 description 1
- 235000018660 ammonium molybdate Nutrition 0.000 description 1
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 1
- 229940010552 ammonium molybdate Drugs 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- GBVHZBMVFWLGMT-UHFFFAOYSA-N azane nickel(2+) dinitrate Chemical compound [N+](=O)([O-])[O-].[Ni+2].N.[N+](=O)([O-])[O-] GBVHZBMVFWLGMT-UHFFFAOYSA-N 0.000 description 1
- 239000011425 bamboo Substances 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 230000000740 bleeding effect Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 230000003292 diminished effect Effects 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 150000002816 nickel compounds Chemical class 0.000 description 1
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 description 1
- ZULUUIKRFGGGTL-UHFFFAOYSA-L nickel(ii) carbonate Chemical compound [Ni+2].[O-]C([O-])=O ZULUUIKRFGGGTL-UHFFFAOYSA-L 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 238000001935 peptisation Methods 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 239000011240 wet gel Substances 0.000 description 1
- 239000004246 zinc acetate Substances 0.000 description 1
- LRXTYHSAJDENHV-UHFFFAOYSA-H zinc phosphate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LRXTYHSAJDENHV-UHFFFAOYSA-H 0.000 description 1
- 229910000165 zinc phosphate Inorganic materials 0.000 description 1
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- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Catalysts (AREA)
Abstract
A catalyst for hydrorefining paraffin wax is composed of Zn-Al2O3 as carrier and Ni as main active component. Its preparing process includes such steps as preparing Zn-Al2O3, immersing it in the Ni contained solution, drying and calcining.
Description
Technical field
The present invention relates to a kind of Hydrobon Catalyst And Its Preparation Method, especially a kind of paraffin raw material Hydrobon Catalyst And Its Preparation Method and application that contains zinc.
Background technology
Hydrofinishing is the main method of producing products such as high-quality oil product, food-grade paraffin wax and food packing wax at present.The main purpose of hydrorefining paraffin wax be by hydrofinishing with remove in the starting paraffin contained have colour substance, store, unstability and some harmful material in the transportation, as condensed ring aromatic hydrocarbon, especially 3,4-BaP etc.
Hydrotreatment comprises HDS (hydrodesulfurization), HDN (hydrodenitrogeneration), HDM (HDM), HDG processes such as (hydrogenation are saturated).The most widely used catalyst for hydrogen refining of paraffin wax in the present prior art, basic identical with other hydrotreating catalyst aspect composition: adopting molybdenum is main metal component, and content accounts for 15～28m% of catalyst gross mass (with MoO
3Meter); With nickel is promoter metal, and content accounts for the 3.6～6.0m% (in NiO) of catalyst gross mass.
U.S. Pat P 4,186, and 078 discloses a kind of catalyst for hydrogen refining of paraffin wax, and this catalyst 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 cost of material of reactive metal accounts for the larger proportion of catalyst 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 rises 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 is carrier to contain the zinc aluminium oxide, is reactive metal with nickel, can not contain molybdenum fully or contains catalyst for hydrogen refining of paraffin wax of a small amount of molybdenum and its production and application.
Catalyst for hydrogen refining of paraffin wax of the present invention is with Zn-Al
2O
3Being carrier, is the hydrogenation activity component with the lower nickel of price.Its content is the 3～5m% (in the ZnO quality) of carrier quality, or is equivalent to the 2～4m% (in the ZnO quality) of catalyst gross mass.Nickel content is 10～20m% (in the NiO quality) in the catalyst, preferred 16～18m%.The specific area of catalyst is 200～250m
2/ g; Pore volume is 0.45～0.60ml/g; Can a few aperture 8.0～10.0nm.
The use of zinc is in order to improve the surface nature of aluminium oxide.Catalyst used carrier of the present invention has following character: specific area is 250～350m
2/ g; Pore volume is 0.65～0.75ml/g; Can a few aperture 8.0～10.0nm.Contain zinc 3～5m% (in the ZnO quality) in the carrier.
One or more conventional auxiliary agents can be contained simultaneously in the catalyst,, also a small amount of molybdenum can be contained as phosphorus, silicon, boron etc.
Catalyst for hydrogen refining of paraffin wax of the present invention adopts immersion process for preparing: flood Zn-Al with solution containing nickel
2O
3Carrier, dry then, roasting make final catalyst.Zn-Al wherein
2O
3The preparing carriers process is:
(1), boehmite powder and zinc compound are mixed together, mediate, until becoming plastic shape;
(2), in banded extruder, be extruded into stripe shape or clover, bunge bedstraw herb type;
(3), with the wet bar after the moulding respectively 60～70 ℃ and 105～115 ℃ dry 1～3 hour down, make dry sample.
(3), with drying sample respectively 180～250 ℃ of constant temperature calcinings 0.5～3.0 hour, 370～450 ℃ of warm roastings 2.0～5.0 hours are at last 630～680 ℃ of roastings 1.0～3.0 hours.
Wherein zinc compound can be selected ZnO (zinc oxide), Zn (C for use
2H
3O
2)
2(zinc acetate), Zn (NO
3)
2(zinc nitrate), Zn
3(PO
4)
2In (trbasic zinc phosphate) etc. one or more.Preferably select ZnO or Zn for use
3(PO
4)
2Consumption is by required zinc amount in the carrier.Mixing, in the kneading process, can use an amount of peptization acid (3m%HNO for example
3) to increase plasticity.(above-mentioned m% is the quality percentage composition, down together)
Catalyst of the present invention is suitable for the hydrofinishing of various pertroleum wax class raw materials.As 54～62
#Paraffin raw material etc.Handle 54～62
#During paraffin raw material, (hydrogen pressure 3～8MPa) carries out hydrofinishing, and other hydrofinishing condition is as follows: 220～310 ℃ of reaction temperatures, LHSV 0.5～3.0h under medium reaction pressure condition
-1, hydrogen/wax volume ratio is 100～800.
The present invention is by adding zinc compound in the preparing carriers process, to improve the surface nature of carrier, and then improve the dispersity of metal (nickel) at carrier surface, reach and can keep and improve the hydrofinishing performance of catalyst fully without molybdenum, reduce the purpose of catalyst manufacturing cost significantly.The zinc alumina support that contains of the present invention has surface of good character: the aperture is bigger, does not have strong acid center and middle strong acid center on the surface, only contains the weak acid center.These character can reduce the interaction between metal-carrier greatly, thereby improve the reducing property and the hydrogenation activity of reactive metal (nickel).
Catalyst for hydrogen refining of paraffin wax of the present invention has the following advantages:
(1), the present invention is by adding a small amount of zinc compound in the kneading process, control carrier calcination steps and sintering temperature improve Zn-Al
2O
3Surface nature, improve the dispersity of reactive metal on catalyst surface, thereby reach the active purpose of the hydrorefining paraffin wax that can keep and improve catalyst fully without molybdenum;
(2), the prepared Zn-Al of the present invention
2O
3The specific area of carrier, pore volume and aperture are bigger than general catalyst for hydrogen refining of paraffin wax carrier, can several apertures be 8.0～10.0nm;
(3), the present invention preparation contains Ni solution, process is simply, easily and fast.Will be easily and fast than other dipping solution of preparation (as Mo-Ni and Mo-Ni-P solution) many;
(4), Ni/Zn-Al of the present invention
2O
3Catalyst is than existing MoNi/Al
2O
3It is much cheap that the manufacturing cost of catalyst for hydrogen refining of paraffin wax is wanted, and the hydrorefining paraffin wax activity of catalyst is better than existing similar catalyst.
The specific embodiment
The character of catalyst for hydrogen refining of paraffin wax of the present invention is as follows:
(1), tenor is NiO 16～18m%, ZnO 3～5m%.Do not contain molybdenum fully, or contain a small amount of molybdenum (with MoO
3Meter 5m% is following);
(2), specific area is 200～250m
2/ g; Pore volume is 0.45～0.60ml/g; Can a few aperture 8.0～10.0nm;
(3), active metal component nickel has preferable dispersity on catalyst surface, higher reducing property, thereby higher hydrofinishing activity is arranged.
It is as follows that catalyst for hydrogen refining of paraffin wax of the present invention prepares main points: with prepared Zn-Al
2O
3Be carrier,, make catalyst precarsor to contain the Ni solution impregnation.Catalyst precarsor (wet bar) at first descended dry 1～3 hour at 60～70 ℃ and 105～115 ℃.Then respectively at 170～210 ℃, 300～370 ℃ and 410～480 ℃) three different temperatures sections carry out constant temperature calcining, make Ni/Zn-Al
2O
3Catalyst for hydrogen refining of paraffin wax.
In the above-mentioned roasting process, the programming rate between initial programming 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.
The above-mentioned Ni of containing solution has following character: 1, every 100ml solution contains NiO 18～22g; 2, the pH value of this solution is 2.0～3.0.
These preparation main points that contain Ni solution are: by the solution concentration requirement required nickel compound is added in the entry, be made into the nickeliferous aqueous solution, and adjust the pH value of solution with weak aqua ammonia.
The preparation process of Ni solution of the present invention is as follows:
(1), a certain amount of nickel nitrate or basic nickel carbonate are added in the entry, at room temperature be stirred to solids and dissolve fully.Can suitably heat in the process, with the accelerate dissolution process.As insoluble impurities is arranged in the solution, can be by removing by filter;
(2), using under the situation of nickel nitrate as solute, can under agitation in solution, drip weak aqua ammonia and (contain 5%NH
4OH), the pH value of solution value is transferred to 2.0～3.0.
For further specifying all main points of the present invention, enumerate following examples and comparative example.(% and m% are the quality percentage composition in the example)
Embodiment 1
(1), Zn-Al
2O
3The preparation of carrier
Weigh 200g boehmite powder, add 5.9g ZnO (zinc oxide) and 2.0g field mountain valley with clumps of trees and bamboo powder, add 145ml 3%HNO after the mixing again
3With an amount of H
2O.Fully mix, mediate, until becoming plastic shape.Adopt bar shaped orifice plate (φ 1.4mm) extrusion.The wet bar of extruding descended dry 2 hours at 65 ℃ and 110 ℃ respectively.It is rectangular to be shaped as 3～5mm then.
Drying is crossed sample places high temperature furnace, be warming up to 210 ℃ with 3 ℃ of/minute speed, and under this temperature constant temperature calcining 1.0 hours.Then be warming up to 410 ℃ with 3 ℃ of/minute speed, and under this temperature constant temperature calcining 3.0 hours.Be warming up to 640 ℃ with 3 ℃ of/minute speed again, and under this temperature constant temperature calcining 2.0 hours.
(2), contain the preparation of Ni solution
The 42g nickel nitrate is dissolved in the 200ml water.Being stirred to solids dissolves fully.Under agitation Dropwise 5 % ammoniacal liquor transfers to 2.5 with the pH value of solution value.
(3), Ni/Zn-Al
2O
3Preparation of Catalyst
Take by weighing 100g Zn-Al
2O
3, add 150ml and contain Ni solution according to embodiment 1 (2) preparation.After at room temperature flooding 4 hours, leach redundant solution.The moist catalysis bar was dried 2 hours at 65 ℃ and 110 ℃ respectively.The sample that drying is crossed is warming up to 190 ℃ with 3 ℃ of/minute speed then, 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 430 ℃ with 3 ℃ of/minute speed at last, constant temperature calcining 3 hours.
Embodiment 2
(1), Zn-Al
2O
3The preparation of carrier
Identical with embodiment 1 (1).But ZnO (zinc oxide) changes Zn into
3(PO
4)
2, addition is 9.0g.Final calcination temperature is brought up to 660 ℃ by 640 ℃.
(2), contain the preparation of Ni solution
Identical with embodiment 1 (2).But the nickel nitrate addition is increased to 46g by 42g.
(3), Ni/Zn-Al
2O
3Preparation of Catalyst
With embodiment 1 (3).But final calcination temperature is brought up to 460 ℃ by 430 ℃.
Embodiment 3
(1), Zn-Al
2O
3The preparation of carrier
Identical with embodiment 2 (1).
(2), contain the preparation of Ni solution
With embodiment 2 (2).
(3), Ni/Zn-Al
2O
3Preparation of Catalyst
With embodiment 1 (3).But the catalyst final calcination temperature is 470 ℃.
Comparative example 1
(1), γ-Al
2O
3The preparation of carrier
Every 100ml is contained 5g Al
2O
3AlCl
3Solution 5L and 250ml acidified sodium silicate (contain SiO
25g/100ml) mix, the pH value is transferred to 2.8, keep 15 ℃, left standstill 2 hours.Above-mentioned solution neutralizes to use ammoniacal liquor (temperature is 15 ℃, and concentration is 9%) then.Control ammoniacal liquor flow, making reaction contact time is 10 minutes, and total reaction time is 90 minutes, and material pH value is 7.8.Filtration under diminished pressure.Filter cake washs 3 times with distilled water.Wash temperature is 25 ℃, and wash time is 40 minutes.Corresponding to 500g Al
2O
3The wet gel amount of butt adds 40g H
3PO
4Solution (contains H
3PO
453%) 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 100g by (1) prepared γ-Al
2O
3Bead added after bleeding in bottle,suction 1 hour and contains MoO
332g/100ml, the ammonium molybdate of NiO 6.2g/100ml and nickel nitrate ammonia spirit 200ml flood after 1 hour and filter.Catalyst precarsor 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 physicochemical property of each routine carrier and catalyst 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.Reaction process condition is: LHSV 1.0h
-1, reaction pressure (hydrogen pressure) 6.0MPa, 260 ℃ of reaction temperatures, hydrogen/wax volume ratio are 300: 1 (v/v).
By table 1 as seen: (1), compare Zn-Al of the present invention with the carrier of comparative example
2O
3Have bigger specific area, than large pore volume and bigger aperture; (2), Zn-Al of the present invention
2O
3Only contain the low-surface-energy center that weak interaction takes place the same reactive metal of energy (nickel) on the carrier surface, promptly the weak acid center does not contain the high surface energy center that strong interaction takes place the same reactive metal of energy (nickel), i.e. strong acid center fully.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 with the catalyst of comparative example, catalyst of the present invention do not contain molybdenum fully; (2), catalyst of the present invention has bigger pore volume and aperture.
By table 3 as seen: (1), catalyst of the present invention have excellent results to hydrorefining paraffin wax.Compare with the comparative example catalyst, the light stability of refining wax is better, reaches No. 3.The refining ultraviolet absorption value (corresponding to paraffin in the height of aromatic hydrocarbon content) of wax (embodiment 1,2,3) at 280～289nm and 290～299nm place all is starkly lower than comparative example (comparative example 1,2).Illustrate that catalyst of the present invention has the saturated performance of higher aromatic hydrocarbon and to the hydrofinishing performance of paraffin; (2), the color (Sai Shi) of refining wax is+No. 30 all, be up to state standards to the quality requirement of food-grade paraffin wax.
The physicochemical property of each routine carrier of table 1
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Comparative example 1 | Comparative example 2 | |
| Zn-Al 2O 3 | Zn-Al 2O 3 | Zn-Al 2O 3 | γ-Al 2O 3 | γ-Al 2O 3 | |
| The crystalline phase specific surface, m 2/ g pore volume, ml/g can several apertures, nm ZnO, m% | γ-Al 2O 3 286 0.65 8.6 4.0 | γ-Al 2O 3 278 0.63 8.8 4.1 | γ-Al 2O 3 270 0.63 9.0 4.1 | γ-Al 2O 3 243 0.49 7.5 --- | γ-Al 2O 3 250 0.50 7.4 --- |
| Acid distributes [notes]The weak acid center, strong acid center among the mmol/g, mmol/g strong acid center, mmol/g | 0.56 0 0 | 0.44 0 0 | 0.0.43 0 0 | 0.18 0.12 0.10 | 0.17 0.12 0.11 |
[notes]: adopt ammonia absorption-TPD method to measure.150～250 ℃, 250～400 ℃, 400～500 ℃ respectively 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 catalyst of table 2 relatively
| Chemical composition, m% | Embodiment 1 | Embodiment 2 | Embodiment 3 | Comparative example 1 | Comparative example 2 |
| MoO 3NiO P ZnO specific surface, m 2/ g pore volume, m1/g can several apertures, nm | --- 17.2 --- 3.1 240 0.52 8.6 | --- 17.3 0.9 3.5 230 0.50 8.7 | --- 17.3 0.9 3.5 220 0.50 8.9 | 19.7 4.7 1.3 --- 235 0.46 7.6 | 20.4 4.7 1.9 --- 239 0.45 7.3 |
The hydrofinishing activity rating result of each routine catalyst of table 3
| Paraffin | Refining wax product character | |||||
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Comparative example 1 | Comparative example 2 | ||
| Fusing point, ℃ oil content, m% Sai Shi color, number light stability, number readily carbonizable substance | 60.3 0.50 17 is defective | 60.3 0.50+30 3 is qualified | 60.3 0.50+30 is qualified | 60.3 0.50+30 3 is qualified | 60.2 0.52+30 3～4 is qualified | 60.1 0.52+30 3～4 is qualified |
| Simple and easy FDA (aromatic hydrocarbon ultraviolet absorption value) | ||||||
| 280～289nm 290～299nm | 0.387 0.250 | 0.036 0.011 | 0.034 0.011 | 0.033 0.010 | 0.074 0.046 | 0.077 0.049 |
Claims (10)
1, a kind of catalyst for hydrogen refining of paraffin wax is characterized in that with Zn-Al
2O
3Being carrier, is the hydrogenation activity component with nickel; Is 2m%～4m% in the ZnO quality at catalyst content, is 10m%～20m% in NiO quality content in catalyst.
2, according to the described catalyst of claim 1, the specific area that it is characterized in that described catalyst is 200～250m
2/ g; Pore volume is 0.45～0.60ml/g; Can a few aperture 8.0～10.0nm.
3, according to the described catalyst of claim 1, it is characterized in that described Zn-Al
2O
3For the carrier specific area is 250～350m
2/ g; Pore volume is 0.65～0.75ml/g; Can a few aperture 8.0～10.0nm; Contain zinc in the carrier and count 3m%～5m% with the ZnO quality.
4, the described Preparation of catalysts method of a kind of claim 1 adopts immersion process for preparing: flood Zn-Al with solution containing nickel
2O
3Carrier, dry then, roasting make final catalyst.
5, in accordance with the method for claim 4, it is characterized in that described Zn-Al
2O
3The preparing carriers process is:
(1), boehmite powder and zinc compound are mixed together, mediate, until becoming plastic shape;
(2), in banded extruder, be extruded into stripe shape or clover, bunge bedstraw herb type;
(3), with the wet bar after the moulding respectively 60～70 ℃ and 105～115 ℃ dry 1～3 hour down, make dry sample;
(3), drying sample is respectively 180～250 ℃ of constant temperature calcinings 0.5～3.0 hour, 370～450 ℃ of warm roastings 2.0～5.0 hours are at last 630～680 ℃ of roastings 1.0～3.0 hours.
6, in accordance with the method for claim 5, it is characterized in that described zinc compound can select ZnO, Zn (C for use
2H
3O
2)
2, Zn (NO
3)
2And Zn
3(PO
4)
2In one or more.
7, in accordance with the method for claim 4, it is characterized in that the described Ni of containing SOLUTION PROPERTIES is: every 100ml solution contains NiO 18～22g, and the pH value of solution is 2.0～3.0.
8, the application of the described catalyst of a kind of claim 1 in the hydrofinishing of pertroleum wax class raw material.
9, the described catalyst of a kind of claim 1 is 54～62
#Application in the paraffin raw material hydrofinishing.
10, according to the described application of claim 8, it is characterized in that the hydrofinishing condition is: hydrogen pressure 3～8MPa, 220～310 ℃ of reaction temperatures, LHSV 0.5～3.0h
-1, hydrogen/wax volume ratio is 100～800.
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|---|---|
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