CN100579652C - Paraffin hydrogenation refined catalyst and its preparing process and application - Google Patents

Paraffin hydrogenation refined catalyst and its preparing process and application Download PDF

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CN100579652C
CN100579652C CN200610047865A CN200610047865A CN100579652C CN 100579652 C CN100579652 C CN 100579652C CN 200610047865 A CN200610047865 A CN 200610047865A CN 200610047865 A CN200610047865 A CN 200610047865A CN 100579652 C CN100579652 C CN 100579652C
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CN101147866A (en
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何金海
刘平
罗锡辉
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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 present invention discloses a paraffin hydrogenation refining catalyst, its preparation method and application. It is characterized by that said preparation method includes the following steps: using chromic oxide and aluminium oxide as carrier, using nickel as main active metal component, adding chromium-containing compound in the course of preparing carrier so as to obtain chromium-containing catalyst, drying and calcining so as to obtain the invented paraffin hydrogenation refining catalyst.

Description

A kind of catalyst for hydrogen refining of paraffin wax and its production and application
Technical field
The present invention relates to a kind of catalyst for hydrogen refining of paraffin wax and its production and application, especially a kind of to contain the Al of auxiliary agent 2O 3For carrier, be used for hydrorefined nickel-containing catalyst of paraffin raw material and its production and application.
Background technology
Hydrofinishing is the main method of producing high-quality paraffin at present.The main purpose of hydrorefining paraffin wax be by hydrofinishing to remove contained coloured, unstability and harmful material in the starting paraffin, as condensed ring aromatic hydrocarbon, especially 3,4-BaP etc.
The wax hydrofining processing procedure comprises HDS (hydrodesulfurization), HDN (hydrodenitrogeneration), HDM (HDM), HDG (hydrogenation is saturated) etc.About the composition of wax hydrofining processing catalyst, generally adopting molybdenum is main metal component, and it is main metal component that the tungsten of employing is also arranged in addition.Except main metal component, hydrotreating catalyst also adopts second metal component such as nickel or cobalt.
Hydrorefining paraffin wax belongs to a kind of of hydrotreatment process, and therefore, catalyst for hydrogen refining of paraffin wax is close with hydrotreating catalyst aspect the metal composition.For example 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%, NiO3.6～5.3m%.Chinese patent CN 92111133.9 disclosed a kind of catalyst for hydrogen refining of paraffin wax contain MoO 318.0～24.0m%, NiO4.0～6.0m%.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%.(m% is a mass percent)
The cost of material of reactive metal accounts for the larger proportion of catalyst cost in the catalyst for hydrogen refining of paraffin wax, particularly the price continuous rise of molybdenum (also comprising tungsten) in recent years.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 with low cost and its production and application.The lower Cr materials of catalyst use cost of the present invention is prepared the catalyst for hydrogen refining of paraffin wax of function admirable by special method.
Catalyst for hydrogen refining of paraffin wax of the present invention is with CrO 3-Al 2O 3Being carrier, is the hydrogenation activity component with nickel.The content of chromium is with CrO in the carrier 3Quality counts 5%～8% (or be equivalent to catalyst gross mass 4%～7%).Nickel content in the catalyst counts 15%～25% with the NiO quality, is preferably 18%～20%.
The used CrO of catalyst of the present invention 3-Al 2O 3Carrier has following character: specific area is 250～300m 2/ g, pore volume are 0.65～0.75ml/g, can several apertures be 8.0～9.5nm.The specific area of catalyst is 200～250m 2/ g, pore volume are 0.45～0.55ml/g, can a few aperture 8.5～9.5nm.
Catalyst for hydrogen refining of paraffin wax of the present invention adopts immersion process for preparing: with nickeliferous solution impregnation CrO 3-Al 2O 3Carrier, dry then, roasting make final catalyst.CrO wherein 3-Al 2O 3The preparing carriers process is:
(1), with the boehmite powder with contain chromium compound and be mixed together, mediate, until becoming plastic shape;
(2), in banded extruder, be extruded into stripe shape or clover, bunge bedstraw herb type;
(3), the wet bar after the moulding was descended dry 1～3 hour at 60～70 ℃ and 105～115 ℃ respectively, then respectively at three temperature range constant temperature calcinings: 180～250 ℃ of constant temperature calcinings 0.5～3.0 hour, 370～450 ℃ of constant temperature calcinings 2.0～5.0 hours are at last 630～680 ℃ of roastings 1.0～3.0 hours.
Wherein contain chromium compound and can select CrO for use 3, Cr (NO 3) 3, CrF 3, CrPO 4, in chromium acetate or the chromium boride one or more.Preferably select CrO for use 3Or CrPO 4Consumption is by required chromium amount in the carrier.In mixing, kneading process, (for example mass concentration is 3% HNO can to use an amount of peptization acid 3) to increase plasticity.In order to further facilitate extruded moulding, also can add extrusion aid such as field mountain valley with clumps of trees and bamboo powder etc.
Catalyst of the present invention is suitable for the unifining process of paraffin raw material, as with 54 #～62 #Wax is raw material, and (hydrogen dividing potential drop 3.0～8.0MPa) is carried out hydrofinishing under medium reaction pressure condition.Other hydrofinishing condition: 220～310 ℃ of reaction temperatures, LHSV 0.5～3.0h -1, hydrogen/wax volume ratio is 100: 1～800: 1 (v/v).
The present invention contains chromium compound by adding in the preparing carriers process, to improve the surface nature of carrier, and then improve the dispersity of metal (nickel) at carrier surface, can keep and improve the hydrofinishing performance of catalyst fully without molybdenum to reach, thereby reduce the purpose of catalyst manufacturing cost significantly.The chromium alumina support that contains of the present invention has surface of good character: the aperture is bigger, does not have the center (being strong acid center) of high surface energy on the surface, and only containing medium surface can center and low-surface-energy center (strong acid and weak acid center promptly).Through experimental studies have found that, have an amount of active metal nickel of alumina support load of above-mentioned surface nature after, the hydrofinishing of paraffin is had particularly outstanding serviceability.
Catalyst for hydrogen refining of paraffin wax of the present invention has the following advantages:
(1), the present invention adds in by kneading process and contains chromium compound on a small quantity and control carrier roasting process (step) and roasting condition improve CrO 3-Al 2O 3Surface nature, improve the dispersity of reactive metal on catalyst surface, thereby reach the effect that fully keeps and improve the hydrorefining paraffin wax activity of catalyst without molybdenum.
(2), the prepared CrO of the present invention 3-Al 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 8.0～9.5nm.
(3), the present invention prepares solution containing nickel, 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/CrO of the present invention 3-Al 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 quite or be 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 18～20m%, CrO 34～7m%.Can not contain molybdenum or tungsten fully, can certainly contain a spot of molybdenum or tungsten.
(2), specific area is 200～250m 2/ g; Pore volume is 0.45～0.60ml/g; Can a few aperture 8.0～9.5nm.
(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 CrO 3-Al 2O 3Be carrier,, make catalyst precarsor with the solution containing nickel dipping.Catalyst precarsor (wet bar) at first descended dry 1～3 hour at 60～70 ℃ and 105～115 ℃, then respectively at 170～210 ℃ (first constant temperature zones), constant temperature calcining is carried out in 300～370 ℃ (second constant temperature zone) and 430～500 ℃ (the 3rd constant temperature zone) three different temperatures intervals, makes Ni/CrO 3-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.
Above-mentioned solution containing nickel has following character: every 100ml solution contains NiO 22～25g, and the pH value is 2.0～3.0.
The preparation process of this solution containing nickel 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.Also can suitably heat, 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, (mass content is 3%NH can under agitation to drip weak aqua ammonia in solution 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.The percentage composition that relates to is the quality percentage composition.
Embodiment 1
(1) .CrO 3-Al 2O 3The preparation of carrier
Take by weighing 360g boehmite powder, add 18.0g CrO 3With 3.0g field mountain valley with clumps of trees and bamboo powder, add 230ml 2.8%HNO after the mixing again 3With an amount of H 2O.Fully mix, mediate, after becoming plastic shape, adopt bar shaped orifice plate (φ 1.4mm) extrusion.The wet bar of extruding descended dry 2 hours respectively at 65 ℃ and 110 ℃ respectively.
Drying is crossed sample places high temperature furnace, be warming up to 230 ℃ with 3 ℃ of speed of per minute, and under this temperature constant temperature calcining 1.0 hours.Then be warming up to 420 ℃ with 3 ℃ of speed of per minute, and under this temperature constant temperature calcining 3.0 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). the preparation of solution containing nickel
The 58g nickel nitrate is dissolved in the 250ml water.Being stirred to solids dissolves fully.Under agitation drip 3% ammoniacal liquor, the pH value of solution value is transferred to 2.5.
(3) .Ni/CrO 3-Al 2O 3Preparation of Catalyst
Take by weighing 100g CrO 3-Al 2O 3, add the solution containing nickel of 150ml according to step (2) preparation.After at room temperature flooding 3 hours, leach redundant solution.The moist catalysis bar is respectively 65 ℃ and 110 ℃ each dry 2 hours.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 350 ℃ with 3 ℃ of/minute speed again, constant temperature calcining 1 hour.Be warming up to 460 ℃ with 3 ℃ of/minute speed at last, constant temperature calcining 3 hours.
Embodiment 2
(1) .CrO 3-Al 2O 3The preparation of carrier
Identical with embodiment 1 (1).But, CrO 3Addition be increased to 28.0g by 18.0g.Final calcination temperature is brought up to 670 ℃ by 650 ℃.
(2), the preparation of solution containing nickel
Identical with embodiment 1 (2).But the nickel nitrate addition is increased to 68g by 58g.
(3), Ni/CrO 3-Al 2O 3Preparation of Catalyst
With embodiment 1 (3).But final calcination temperature is brought up to 470 ℃ by 460 ℃.
Embodiment 3
(1), CrO 3-Al 2O 3The preparation of carrier
Identical with embodiment 2 (1).
(2), the preparation of solution containing nickel
With embodiment 2 (2).
(3), Ni/CrO 3-Al 2O 3Preparation of Catalyst
With embodiment 1 (3).But the catalyst final calcination temperature is 480 ℃.
Comparative example 1
(1), 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 the 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.Filter, 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, 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 A l 2O 3
(2), MoNi/Al 2O 3Preparation of Catalyst
Take by weighing by (1) prepared Al 2O 3Bead 100g 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). with the carrier (Al of comparative example 2O 3) compare CrO of the present invention 3-Al 2O 3Have bigger specific area, than large pore volume and bigger aperture; (2). CrO of the present invention 3-Al 2O 3Only contain moderate strength and weak interaction take place the same reactive metal of energy (nickel) medium surface energy and low-surface-energy center on the carrier surface, strong acid center and weak acid center promptly, do not contain the high surface energy center that strong interaction takes place the same reactive metal of energy (nickel) fully, i.e. strong acid center.And the Al in the reference example 2O 3, then contain a considerable amount of strong acid centers.
By table 2 as seen: (1). compare with the catalyst of comparative example, catalyst of the present invention does not contain molybdenum (or tungsten) fully; (2). catalyst of the present invention has bigger pore volume and aperture.
By table 3 as seen: (1). catalyst of the present invention has 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, is up to state standards to the quality requirement of food-grade paraffin wax.
The physicochemical property of each routine carrier of table 1
Figure C20061004786500111
[annotating 1]: 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.Adopt the PASCA technology can accurately determine the number at three class centers: " strong center " of high surface energy, " middle strong center " and " weak center " of low-surface-energy of medium surface energy.The PASCA test shows: this three classes center has corresponding relation with the three class acid sites that NH3-TPD measures.
The physico-chemical property of each routine catalyst of table 2 relatively
Each routine activity of such catalysts evaluation result of table 3
Figure C20061004786500122

Claims (9)

1, a kind of catalyst for hydrogen refining of paraffin wax is characterized in that with CrO 3-Al 2O 3Being carrier, is the hydrogenation activity component with nickel, and the content of chromium is with CrO in the carrier 3Quality counts 5%～8%, and the nickel content in the catalyst counts 15%～25% with the NiO quality; Described CrO 3-Al 2O 3The specific area of carrier is 250～300m 2/ g, pore volume are 0.65～0.75ml/g, can several apertures be 8.0～9.5nm.
2,, it is characterized in that nickel content counts 18%～20% with the NiO quality in the described catalyst according to the described catalyst of claim 1.
3, according to the described catalyst of claim 1, the specific area that it is characterized in that catalyst is 200～250m 2/ g, pore volume are 0.45～0.55ml/g.
4, the described Preparation of catalysts method of a kind of claim 1 adopts immersion process for preparing: with nickeliferous solution impregnation CrO 3-Al 2O 3Carrier, descended dry 1～3 hour respectively at 60～70 ℃ and 105～115 ℃ then, 170～210 ℃ of constant temperature calcinings 0.5～2 hour,, make final catalyst 300～370 ℃ of constant temperature calcinings 0.5～2 hour and 430～500 ℃ of constant temperature calcinings 2.0～5.0 hours;
CrO wherein 3-Al 2O 3The preparing carriers process is:
(1), with the boehmite powder with contain chromium compound and be mixed together, mediate, until becoming plastic shape;
(2), be extruded into stripe shape or clover, bunge bedstraw herb type;
(3), wet bar drying, roasting after the moulding are promptly got CrO 3-Al 2O 3Carrier;
Wherein the described roasting of step (3) is for respectively at three temperature range constant temperature calcinings: 180～250 ℃ of constant temperature calcinings 0.5～3.0 hour, 370～450 ℃ of constant temperature calcinings 2.0～5.0 hours are at last 630～680 ℃ of roastings 1.0～3.0 hours.
5, in accordance with the method for claim 4, it is characterized in that the described drying of step (3) is for descending dry 1～3 hour respectively at 60～70 ℃ and 105～115 ℃.
6, in accordance with the method for claim 4, it is characterized in that the described chromium compound that contains selects CrO for use 3, Cr (NO 3) 3, CrF 3, CrPO 4, in chromium acetate or the chromium boride one or more.
7, the application of the described catalyst of a kind of claim 1 in paraffin raw material hydrofinishing.
8,, it is characterized in that described paraffin raw material is 54 according to the described application of claim 7 #～62 #Paraffin raw material.
9,, it is characterized in that described hydrorefined hydrogen dividing potential drop is 3.0～8.0MPa, 220～310 ℃ of hydrofining reaction temperature, LHSV 0.5～3.0h according to the described application of claim 7 -1, hydrogen/wax volume ratio is 100: 1～800: 1.
CN200610047865A 2006-09-20 2006-09-20 Paraffin hydrogenation refined catalyst and its preparing process and application Expired - Fee Related CN100579652C (en)

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Publication number Priority date Publication date Assignee Title
CN102311804B (en) * 2010-07-07 2014-05-21 中国石油化工股份有限公司 Paraffin wax hydrogenation refining method
CN107597137A (en) * 2016-07-11 2018-01-19 中国石油天然气股份有限公司 Preparation method of distillate oil hydrofining catalyst
CN106475110B (en) * 2016-09-22 2019-02-12 中国石油大学(华东) The preparation method of superelevation content of metal hydrogenation catalyst
CN108855106B (en) * 2017-05-15 2021-03-30 中国石油天然气股份有限公司 Nickel-zinc series hydrogenation catalyst and preparation method thereof
CN108855127B (en) * 2017-05-15 2021-03-30 中国石油天然气股份有限公司 Hydrogenation catalyst and preparation method thereof
CN108855093B (en) * 2017-05-15 2021-03-30 中国石油天然气股份有限公司 Nickel-copper hydrogenation catalyst and preparation method thereof
CN108855114B (en) * 2017-05-15 2021-03-30 中国石油天然气股份有限公司 Hydrogenation protective agent and preparation method thereof

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