CN1072616A - The preparation method of hydrogen refining cobalt molybdenum catalyzer - Google Patents
The preparation method of hydrogen refining cobalt molybdenum catalyzer Download PDFInfo
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- CN1072616A CN1072616A CN 91110935 CN91110935A CN1072616A CN 1072616 A CN1072616 A CN 1072616A CN 91110935 CN91110935 CN 91110935 CN 91110935 A CN91110935 A CN 91110935A CN 1072616 A CN1072616 A CN 1072616A
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Abstract
The present invention relates to a kind of preparation method of hydrogen refining cobalt molybdenum catalyzer.This method is that the water-soluble back of cobalt acetate is added ethylenediamine, makes it form the mixed solution of cobalt ethylenediamine, add ammonium molybdate at last and make the co-impregnated solution that contains the cobalt molybdenum, with porous carrier with this solution impregnation after in anaerobic or little oxygen atmosphere roasting get product.This method device therefor is simple, and the preparation time is short, can not produce temperature runaway during roasting, thereby guarantee the high activity of catalyst.The catalyst of the same type that the catalyst hydrodesulfurization active of this method preparation is produced far above Uop Inc..
Description
The invention belongs to catalyst, be specifically related to a kind of organic complex of cobalt and molybdenum salt of making and be dipped in the method for preparing hydrogenation catalyst on the porous carrier altogether.
The cobalt molybdenum is supported on the cobaltmolybdate catalyst of (the normally mixture of aluminium oxide or aluminium oxide and silica) on the porous carrier, is widely used in hydrodesulfurization, denitrogenation, the demetalization of gasoline, kerosene, diesel oil, to obtain high-quality purified product.Prepare above-mentioned catalyst, cobalt molybdenum salt need be dissolved in the same solution, this point is made very difficulty.The common practice is these two kinds of metal step impregnations of cobalt molybdenum, promptly earlier catalyst carrier is immersed in molybdenum salt (or cobalt salt) solution, semi-finished product behind the drying and roasting immerse in cobalt salt (or the molybdenum salt) solution dry again again, roasting obtains product, and the method for this dipping in two steps and roasting is very loaded down with trivial details.U.S. USP4409131 discloses a kind of " using the cobalt molybdenum to soak the method that legal system is equipped with cobalt molybdenum or nickel molybdenum catalyst altogether ", this method with water-fast cobalt carbonate as the cobalt source, be dissolved in organic acid (as citric acid, tartaric acid, ethylenediamine tetra-acetic acid) back ebuillition of heated, drive the carbon dioxide that reaction generates away, be placed to room temperature, form cobalt and organic acid mixture this moment, add concentrated ammonia liquor more respectively, ammonium molybdate is mixed with and soaks solution altogether, with the back roasting of catalyst carrier dipping, said method equipment complexity, the time is long, owing to use organic acid in the co-impregnated solution, so contain a large amount of organic carbons in the catalyst semi-finished product before the roasting, in this high oxygen-containing atmosphere of air, can emit a large amount of combustions heat during roasting, temperature is with uncontrollable, the temperature runaway phenomenon is serious, even activation furnace can be burnt, and the cobaltmolybdate catalyst sintering temperature is if surpass 550 ℃, activity will descend even non-activity.Above-mentioned patent does not relate to the implementation method of this committed step of roasting.
The object of the present invention is to provide a kind of improved method for preparing cobaltmolybdate catalyst, this method is promptly simple, save time again, and the product quality height.
The method that the present invention prepares cobaltmolybdate catalyst is such: adopt the method for porous carrier in the co-impregnated solution dipping back roasting that contains cobalt molybdenum salt, co-impregnated solution makes as follows:
It is a. cobalt acetate is water-soluble,
B. in molar ratio 1: 1.5-3 adds ethylenediamine,
C. add concentrated ammonia liquor adjusting pH value again and reach 12-14, last
D. add ammonium molybdate it fully dissolved,
Roasting is to be the 0-1%(volume in oxygen content) inert atmosphere in, in 460-500 ℃ of following roasting 2-10 hour.
Said inert atmosphere can be water vapour or nitrogen.
The preparation method of hydrogen refining cobalt molybdenum catalyzer of the present invention mainly is the preparation of common dipping solution, and the preparation of solution is carried out at normal temperatures, selects for use cobalt acetate, ammonium molybdate to do the source of cobalt, molybdenum respectively.At first cobalt acetate is dissolved in low amounts of water, added ethylenediamine then in 1: 2 in molar ratio, it is cobalt ethylenediamine mixture solution that the brownish red that form this moment does not have precipitation liquid, in this solution, add concentrated ammonia liquor and regulate pH value and behind 12-14, add ammonium molybdate again it is fully dissolved, promptly be mixed with stable cobalt molybdenum and soak solution altogether.Use this impregnating porous carrier solution, soak the enforcement of spray method, be the catalyst semi-finished product of not roasting after the drying by general full closing.Dried semi-finished product are gone into roaster, are the 0-1%(volume in oxygen content) inert atmosphere in be warming up to 460-500 ℃ of roasting 2-10 hour, be finished catalyst.
Method device therefor of the present invention is simple, and the preparation time is short, is convenient to implement.Because the preparation of co-impregnated solution does not adopt organic acid to make the coke on regenerated catalyst behind the dipping reduce, and the roasting of catalyst is to carry out in the inert atmosphere of anaerobic or micro amount of oxygen, thereby easy control of temperature, can not produce overheating problem, thereby guarantee the high activity of catalyst.
Embodiment 1:
Get 224.0g cobalt acetate (Co(CH
3COO)
24H
2O), add suitable quantity of water, make into pasty state, slowly add anhydrous ethylenediamine 120ml(density 0.9 while stirring), solution becomes brown.Be diluted to about 850ml with concentrated ammonia liquor, this moment, pH value should take by weighing 388.2g ammonium molybdate [(NH greater than 12
4)
6Mo
7O
44H
2O] add in the solution, stirring is diluted to 1000ml with ammoniacal liquor after making its dissolving.This moment, the pH value of solution approximated 9, was the stable cobalt molybdenum of a kind of brown nothing precipitation maceration extract altogether.
Getting water absorption rate is 0.58mlH
2Industrial γ-AL of O/g
2O
3Carrier (specific surface 230m
2/ g, pore volume 0.48ml/g, φ 1.6mm cloverleaf pattern) 1000g, implement by the full dipping method that closes, promptly add the above-mentioned cobalt molybdenum of 580ml maceration extract and stirring altogether, the carrier pinkiness.Drying is 3 hours under 120 ℃, is the dried bar of half-finished red cobaltmolybdate catalyst.
Embodiment 2:
Get dried bar 150 grams of embodiment 1 cobaltmolybdate catalyst, in the tubular type of packing into the roaster, with the 120ml/min bubbling air, speed with 1 ℃/min heats up simultaneously, when being raised to 210 ℃, get the heat-clearing source, because a large amount of heat is emitted in the oxidation meeting of organic carbon on the catalyst, catalyst still rises to more than 700 ℃ at a terrific speed.The catalyst that takes out carries out the hydrodesulfurization activity test in fixed-bed tube reactor, what use is the naphtha of sulfur-bearing as 27.5ppm, reaction gross pressure 30 atmospheric pressure, hydrogen-oil ratio is the 70(volume), air speed 6hr
1(air speed=raw material weight/unit interval.The Unit Weight catalyst), 350 ℃ of temperature are before use with the DMDS (C that contains 0.125% sulphur
2H
6S
2) naphtha 290-310 ℃ of sulfuration, refining back product sulfur content is 2.5ppm, can not satisfy reformation to the refining requirement of naphtha sulphur below 0.5ppm.
Embodiment 3:
Get the dried bar of embodiment 1 cobaltmolybdate catalyst 150 grams, in the tubular type of packing into the roaster, be warming up to 100 ℃ with 1 ℃/min after, feed water vapour with 200ml/min, and be warming up to 480 ℃, kept 4 hours with the speed of 1 ℃/min, after being cooled to below 150 ℃, stop water flowing steam, tube furnace is reduced to room temperature.The finished catalyst that takes out is a black.Wherein metal and carbon content to be respectively CoO3.1%(heavy), MoO
3The 15.0%(weight), C0.5%(is heavy).
The industrial CoO-MoO-ALO[CoO3.6%(that gets embodiment 3 finished catalysts and American UOP company of the same type is heavy), MoO
315.5(heavy)] catalyst, under the reaction condition of embodiment 2, do contrast test, reaction result sees Table 1
Table 1: embodiment 3 catalyst and UoP catalyst comparative test result
S(ppm) N(ppm) As(ppb) Pb(ppb) Cu(ppb)
Raw material 27.5 2.5 2.1 5.2 10.9
UOP catalyst 0.4＜0.5 0.4 0.4 0.3
As can be seen from Table 1, embodiment 3 catalyst hydrogenation desulfurization, metal removal activity all are higher than the catalyst of American UOP company.
For further comparison, get embodiment 3 catalyst and Uop Inc.'s catalyst, at 150hr
-1Under the high-speed (other condition is with embodiment 2), carry out hydrodesulfurization activity contrast in 100 hours, the results are shown in Figure 1, show that from Fig. 1 result embodiment 3 catalyst are active catalyst apparently higher than Uop Inc. under high-speed, stable indifference.
Embodiment 4:
Get dried bar 150 grams of embodiment 1 cobaltmolybdate catalyst, in the tubular type of packing into the roaster, rise to 150 ℃ with the heating rate of 1 ℃/min after, with 200ml/min, feed water vapour, be warming up to 300 ℃ with 1 ℃/min again, feed in the water vapour and sneak into the 0.2%(volume) oxygen, rise to 480 ℃ with 1 ℃/min, kept 4 hours, be cooled to 150 ℃ and stop water flowing steam, reduce to room temperature again, the finished catalyst of taking-up is blue look.Tenor is that CoO3.2%(is heavy), MoO
315.0%(is heavy), carbon containing not.
The catalyst of getting embodiment 4 finished catalysts and American UOP company carries out hydrodesulfurization, denitrogenation, demetalization test in fixed-bed tube reactor, reaction condition is with embodiment 3, and reaction result sees Table 2.
Table 2: embodiment 4 catalyst and UOP catalyst comparative test result
S N As Pb Cu
Raw material 27.5 2.5 2.1 5.2 10.9
Embodiment 4 catalyst 0.3＜0.5 0.1 0.2 0.2
UOP catalyst 0.4＜0.5 0.4 0.4 0.3
As seen from Table 2, embodiment 4 catalyst hydrogenation desulfurization metal removal activities all are higher than the catalyst of the same type of Uop Inc..
Get embodiment 4 finished catalysts, at 150hr
-1High-speed under (other condition is with embodiment 2), carry out hydrodesulfurization activity contrast in 100 hours with the catalyst of the same type of U.S. Uop company, the results are shown in Figure 2, show from Fig. 2 result and find out that embodiment 4 catalyst hydrodesulfurization actives are far above the CoO-MoO of U.S. Uop company
3-Al
2O
3Catalyst.
Fig. 1 is embodiment 3 catalyst and the hydrodesulfurization activity contrast in 100 hours of Uop catalyst.
Fig. 2 is embodiment 4 catalyst and the hydrodesulfurization activity contrast in 100 hours of Uop catalyst.
Above-mentioned analysis data are that the analytical of the U.S. AP Oil company that adopts with Tianjin Petrochemical Company obtains, and each data analysis standard is as follows:
S American UOP company 727
N D-3421
Ab Uop-296
Pb Uop-350
Cu Uop-144
American UOP company catalyst is obtained by import.
Claims (2)
1, a kind of preparation method of hydrogen refining cobalt molybdenum catalyzer is that porous carrier is obtained in the co-impregnated solution dipping back roasting that contains the cobalt molybdenum, it is characterized in that the said solution that soaks altogether makes with the following method:
It is a. cobalt acetate is water-soluble,
B. 1:1.5-3 adds ethylenediamine in molar ratio,
C. add concentrated ammonia liquor again and regulate pH value to 12-14, last
D. adding ammonium molybdate fully dissolves it
Said roasting was to be in the inert atmosphere of 0-1% (volume) in oxygen content, in 460-500 ℃ of following roasting 2-10 hour.
2, method for preparing catalyst as claimed in claim 1 is characterized in that said inert atmosphere can be water vapour or nitrogen.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 91110935 CN1029510C (en) | 1991-11-22 | 1991-11-22 | Preparing method for hydrogen refining cobalt molybdenum catalyzer. |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 91110935 CN1029510C (en) | 1991-11-22 | 1991-11-22 | Preparing method for hydrogen refining cobalt molybdenum catalyzer. |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1072616A true CN1072616A (en) | 1993-06-02 |
| CN1029510C CN1029510C (en) | 1995-08-16 |
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ID=4910349
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 91110935 Expired - Fee Related CN1029510C (en) | 1991-11-22 | 1991-11-22 | Preparing method for hydrogen refining cobalt molybdenum catalyzer. |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1049608C (en) * | 1996-12-02 | 2000-02-23 | 南京大学 | Nanometre grade cobalt-manganese spinel and its manufacturing method and use |
| CN102166520A (en) * | 2010-02-25 | 2011-08-31 | 中国石油天然气股份有限公司 | Hydrorefining catalyst |
| CN102166521A (en) * | 2010-02-25 | 2011-08-31 | 中国石油天然气股份有限公司 | Preparation method of hydrofining catalyst |
| CN108568305A (en) * | 2017-03-08 | 2018-09-25 | 中国石油化工股份有限公司 | A kind of Hydrobon catalyst and its preparation method and application |
-
1991
- 1991-11-22 CN CN 91110935 patent/CN1029510C/en not_active Expired - Fee Related
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1049608C (en) * | 1996-12-02 | 2000-02-23 | 南京大学 | Nanometre grade cobalt-manganese spinel and its manufacturing method and use |
| CN102166520A (en) * | 2010-02-25 | 2011-08-31 | 中国石油天然气股份有限公司 | Hydrorefining catalyst |
| CN102166521A (en) * | 2010-02-25 | 2011-08-31 | 中国石油天然气股份有限公司 | Preparation method of hydrofining catalyst |
| WO2011103698A1 (en) * | 2010-02-25 | 2011-09-01 | 中国石油天然气股份有限公司 | Hydro refining catalyst |
| CN102166520B (en) * | 2010-02-25 | 2013-03-27 | 中国石油天然气股份有限公司 | Hydrorefining catalyst |
| CN102166521B (en) * | 2010-02-25 | 2013-03-27 | 中国石油天然气股份有限公司 | Preparation method of hydrofining catalyst |
| US8785345B2 (en) | 2010-02-25 | 2014-07-22 | Petrochina Company Limited | Method for preparing hydrorefining catalyst |
| CN108568305A (en) * | 2017-03-08 | 2018-09-25 | 中国石油化工股份有限公司 | A kind of Hydrobon catalyst and its preparation method and application |
| CN108568305B (en) * | 2017-03-08 | 2019-12-27 | 中国石油化工股份有限公司 | Hydrofining catalyst and preparation method and application thereof |
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| Publication number | Publication date |
|---|---|
| CN1029510C (en) | 1995-08-16 |
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