CN1073615C - Impregnating solution useful for hydrogenating catalyst and its preparing process - Google Patents
Impregnating solution useful for hydrogenating catalyst and its preparing process Download PDFInfo
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- CN1073615C CN1073615C CN98114345A CN98114345A CN1073615C CN 1073615 C CN1073615 C CN 1073615C CN 98114345 A CN98114345 A CN 98114345A CN 98114345 A CN98114345 A CN 98114345A CN 1073615 C CN1073615 C CN 1073615C
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- citric acid
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Abstract
The present invention relates to a hydrogenation catalyst, particularly to immersion solution for the hydrotreating catalyst and a preparation method thereof. The solution contains 0.08 g/ml to 0.35 g/ml of metal oxides of the VIB group, 0.01 g/ml to 0.10 g/ml of metal oxides of the VIII group and 0.05 g/ml to 0.30 g/ml of citric acid. In the preparation method, a salt containing the metal of the VIB group or the VIII group or a mixture of the two kinds of metal is dissolved by ammonia water, and the citric acid is added for stabilizing the solution after the solution is completely dissolved. The solution has the advantages of good stability, fast and simple preparation process and energy saving, and can be used for preparing catalysts of hydrocracking, hydrotreatment, etc.
Description
The present invention relates to used dipping solution of a kind of hydrogenation catalyst and preparation method thereof.Solution of the present invention can be used for the preparation of hydrotreating catalyst, the preparation of especially residuum hydrodesulfurization, hydrodemetallation (HDM) and hydrodenitrogenation catalyst.
As everyone knows, industrial used hydrotreating catalyst is a carrier with inorganic oxide such as aluminum oxide normally at present, and load hydrogenation active metals (being generally VI B family and VIII family element, as Mo, W and Co, Ni etc.) is prepared from.Pickling process is a kind of hydrogenation activity component carrying method commonly used.
For some high-activity hydrogenation catalyst, require active metal component content very high, this brings certain degree of difficulty with regard to the load of giving the hydrogenation activity component.
Make solvent with the present industrial ammoniacal liquor that generally uses, the solution ratio of preparation single-activity component is easier to, but is difficult to obtain high density, stable Mo-Co (Ni) mixing solutions.If adopt segmentation dipping preparation catalyzer, formulations prepared from solutions does not have too big problem, but this method Catalyst Production cycle is long, the production cost height.
If adopt to mix and to pinch method supported active metal component, can shorten the Catalyst Production cycle, operate also easylier, but the pore structure of catalyzer and intensity are difficult to reach requirement.The also easy and support material generation strong interaction of active metal component generates inactive substance, is unfavorable for the raising of catalyst activity.
If can find out a kind of easy method prepares mixing solutions, prepare catalyzer with one section impregnation method, can overcome above-mentioned shortcoming.Useful quadrol used as stabilizers joins Mo-Co (Ni)-NH in the prior art
3-H
2In the O system so that solution-stabilized.But quadrol has severe toxicity, and is volatile, and its use is restricted.The citric acid of employing used as stabilizers is also arranged, and citric acid is a solid particulate, and nontoxicity is a kind of selection preferably.
USP4,409,131 and USP4, the formulations prepared from solutions process described in 483,942 all relates to the use of citric acid.
At USP4, in 409,131, the formulations prepared from solutions process is: (1) cobaltous carbonate mixes with citric acid and water, and stirring heating boils for some time, forms deep purple solution; (2) this solution is cooled to room temperature, part precipitation appears in solution, adds a certain amount of strong aqua and makes the throw out dissolving; (3) add a certain amount of ammonium molybdate and strong aqua,, finally form the Mo-Co mixing solutions through stirring and heating.
USP4,483,942 described solution manufacturing methods are: (1) is with ammonium molybdate and citric acid and the dissolving of water Hybrid Heating; (2) feed ammonia to (1) gained solution, adjust about pH value of solution value to 8.5, add the salt that contains Co or Ni, stir and make it dissolving; (3) feed ammonia to (2) gained solution, making the pH value is 9.5～10, promptly gets final solution.
In sum, these two kinds of methods all adopt the mode that adds citric acid earlier to prepare solution.Promptly, add ammoniacal liquor again and regulate earlier with citric acid lytic activity metal component.The shortcoming of this mode is: dissolution rate is slow; Be difficult for improving the meltage of active metal component.In order to overcome this class problem, can increase the consumption of citric acid, this can cause soltion viscosity excessive again, is unfavorable for that reactive metal is at catalyzer micropore internal surface uniform distribution.In addition, above-mentioned two kinds of methods are to adopt heating to improve dissolution rate, increase the content of active ingredient in the solution.Owing to adopt extra heating, not only increased energy consumption and facility investment, also increase operation steps, and operated trouble, preparation time is long, thereby the manufacturing cost of catalyzer is increased.Especially USP4,409,132 method is operated more complicatedly, and stability of solution is relatively poor, can not long storage time, this will make troubles to Catalyst Production.
The objective of the invention is at problems of the prior art, a kind of preparation method of quick, easy, energy-conservation Mo-Co (Ni) high-concentration stable solution is provided, a kind of Mo-Co (Ni) stabilizing solution of high density is provided simultaneously and reduces soltion viscosity, be convenient to metal and distribute better.The inventive method prepared solution can be used for high-activity hydrogenation catalyst, and especially hydrotreatment is as Preparation of catalysts such as weight, residuum hydrodesulfurization and hydrodenitrifications.
Characteristics of the present invention are that its preparation method is: take by weighing the salt that a certain amount of (at least a) contains VI B family metal, adding certain density proper ammonia stirring dissolves this salt fully, then add a certain amount of salt and citric acid that contains VIII family metal successively, be stirred to dissolving fully.Solution of the present invention also can adopt the ammoniacal liquor salt of dissolving VIII family metal earlier, or prepares with the method that ammoniacal liquor dissolves the salt of VI B family's metal and VIII family metal simultaneously.It is 0.08～0.35g/ml that prepared solution contains VI B family metal oxide component, contains VIII family metal oxide component 0.01～0.10g/ml, contains citric acid 0.05～0.30g/ml.
Wherein VI B family metal oxide component concentration is preferably 0.15～0.32g/ml.VIII family metal oxide component concentration is preferably 0.05～0.09g/ml.Citric acid adding amount is preferably 0.07～0.20g/ml.
Above-mentioned VI B family metal is Mo or W, preferably selects its ammonium salt for use, as ammonium molybdate; VIII family metal is Co or Ni, and its salt is carbonate, acetate or nitrate etc.
Advantage of the present invention is: method is simple, in the preparation process, owing to add ammoniacal liquor earlier, make the salt that contains active ingredient in dissolution process, produce a large amount of heat, but so do not need also accelerate dissolution of extra heating, promptly simplified operation steps, can save time again, save energy helps reducing the Catalyst Production cost.The inventive method prepared solution is as clear as crystal, and good stability can be deposited the long period, and SOLUTION PROPERTIES is constant.Soltion viscosity is lower, helps metal and moves and be evenly distributed on the micropore surface to the catalyzer micropore.
With solution impregnating carrier of the present invention (as Al
2O
3Or Al
2O
3-SiO
2), prepared catalyzer can be used for the hydrotreatment process of fraction oil of petroleum and heavy oil.
The invention is further illustrated by the following examples.
Embodiment 1
Take by weighing ammonium molybdate 66g, adding 200ml concentration is the ammoniacal liquor of 16m%, after stirring is dissolved ammonium molybdate fully, adds cobaltous carbonate 26g and citric acid 20g successively, continues to be stirred to dissolving fully, with ammoniacal liquor liquor capacity is transferred to 300ml, gets solution A.
Embodiment 2
Among the embodiment 1, the ammonium molybdate add-on changes 80.5g into, and the add-on of cobaltous carbonate changes 31g into, and promptly the cost example gets solution B.
Embodiment 3
Take by weighing cobaltous carbonate 31g, adding 200ml concentration is the ammoniacal liquor of 16m%, after stirring is dissolved cobaltous carbonate fully, adds ammonium molybdate 80.5g and citric acid 20g successively, continues to be stirred to dissolving fully, with ammoniacal liquor liquor capacity is transferred to 300ml, promptly gets solution C.
Embodiment 4
Take by weighing cobaltous carbonate 31g and ammonium molybdate 80.5g, adding 200ml concentration is the ammoniacal liquor of 16m%, is stirred to dissolving fully, adds citric acid 20g, continue to be stirred to dissolving fully after, with ammoniacal liquor liquor capacity is transferred to 300ml, promptly get solution D.
Embodiment 5
Among the embodiment 4, ammonium molybdate changes 91.5g into, and cobaltous carbonate changes 36.2g into, and promptly the cost example gets solution E.
Embodiment 6
Among the embodiment 4, ammonium molybdate changes 110g into, and cobaltous carbonate changes 47g into, and citric acid changes 60g into, and promptly the cost example gets solution F.
Embodiment 7
Among the embodiment 4, cobaltous carbonate changes nickelous carbonate into, and promptly the cost example gets solution G.
Comparative example 1
This example is by USP4, and 409,131 methods of describing prepare solution.
Take by weighing cobaltous carbonate 27g, water purification 130ml and citric acid 56g are mixed and heated to about 20 minutes of boiling, be cooled to room temperature then, add 200ml strong aqua (concentration is 30m%), add the 80.5g ammonium molybdate at last and continue heated and stirred, make it to dissolve fully, get Solution H (300ml).
Comparative example 2
This example is by USP4, and 483,942 described methods prepare solution.
Take by weighing ammonium molybdate 80.5g,, then add the 45g citric acid, feed after ammonia adjusts its pH value and be 8.5, slowly add the 27g cobaltous carbonate, regulate about its pH value to 10, promptly get this solution I of 300ml with ammonia again to this mixture with 200ml water purification Hybrid Heating.
Embodiment 8
This example is above-mentioned each routine solution comparing result, and is as shown in table 1 below.
The contrast situation strength of solution of the various different solutions of table 1, g/ml solution numbering MoO
3CoO citric acid pH value relative viscosity stability A 0.18 0.05 0.07 10 did not find later on that deposit B 0.22 0.06 0.07 11 do not find later on that precipitate C 0.22 0.06 0.07 11 found later on that precipitation D 0.22 0.06 0.07 10 found later on that precipitation E 0.25 0.07 0.07 11 found later on that precipitation F found later on that precipitation G 0.22 0.06# 0.07 10 found later on that precipitation H 0.22 0.06 0.18 9 14.1 occurred two days later precipitation I and found later on that precipitation annotated in 0.22 0.06 0.15 10 13.1 one month in 5.4 1 months in 0.30 0.09 0.20 11 10.2 one month in 8.6 1 months in 6.1 1 months in 6.0 1 months in 6.0 1 months in 4.1 1 months: # should count the content that represents NiO in the solution
The μ of relative viscosity shown in the table is calculated as follows:
K. μ in the formula
SolutionWith k. μ
GinsengRepresent the viscosity of solution of the present invention and reference solution respectively, μ
SolutionAnd μ
GinsengBe respectively the relevant viscosimetric analysis value with reference liquid of solution, k is the system compensation factor, and wherein reference solution is a water.
This is shown as can be seen, and the viscosity of solution of the present invention increases with the increase of citric acid adding amount; Solution A of the present invention, B, C, D, E, F, G and H relatively have satisfactory stability; Solution of the present invention and H and I compare, and soltion viscosity obviously reduces.
Claims (5)
1. the preparation method of the used dipping solution of hydrogenation catalyst, the preparation process that it is characterized in that this solution is: the salt of the salt of group VIB metal and/or group VIII metal is joined in the ammoniacal liquor stir, dissolve fully to this salt, add citric acid again so that solution-stabilized, wherein the add-on of each component makes prepared solution contain VI B family metal oxide 0.08～0.35g/ml, contain VIII family metal oxide 0.01～0.10g/ml, contain citric acid 0.05～0.30g/ml.
2. according to the described preparation method of claim 1, it is characterized in that VI B family metal is Mo and/or W, VIII family metal is Co and/or Ni.
3. preparation method according to claim 1 is characterized in that VI B family metal oxide content is 0.15～0.32g/ml in the described solution.
4. preparation method according to claim 1 is characterized in that VIII family metal oxide content is 0.05～0.09g/ml in the described solution.
5. preparation method according to claim 1 is characterized in that in the described solution that citric acid adding amount is 0.07～0.20g/ml.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN98114345A CN1073615C (en) | 1998-09-28 | 1998-09-28 | Impregnating solution useful for hydrogenating catalyst and its preparing process |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN98114345A CN1073615C (en) | 1998-09-28 | 1998-09-28 | Impregnating solution useful for hydrogenating catalyst and its preparing process |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1249327A CN1249327A (en) | 2000-04-05 |
| CN1073615C true CN1073615C (en) | 2001-10-24 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN98114345A Expired - Lifetime CN1073615C (en) | 1998-09-28 | 1998-09-28 | Impregnating solution useful for hydrogenating catalyst and its preparing process |
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| Country | Link |
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Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100513664B1 (en) | 2002-05-16 | 2005-09-07 | 주식회사 엘지화학 | Method for preparing a catalyst for partial oxidation of propylene |
| CN102600913B (en) * | 2011-01-20 | 2014-06-04 | 中国石油天然气股份有限公司 | Method for preparing molybdenum, nickel and phosphorus dipping aqueous solution |
| CN103801318B (en) * | 2012-11-08 | 2016-02-03 | 中国石油化工股份有限公司 | The preparation method of hydrotreating catalyst |
| CN107297223B (en) * | 2016-04-16 | 2019-08-06 | 中国石油化工股份有限公司 | Hydrocracking catalyst and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4409131A (en) * | 1982-02-22 | 1983-10-11 | Maine | Preparation of CoMo and NiMo catalyst using cobalt or nickel complexes that are stable in basic solution |
| US4483942A (en) * | 1982-10-15 | 1984-11-20 | Nippon Oil Co., Ltd. | Process of preparing hydrogenation catalysts |
-
1998
- 1998-09-28 CN CN98114345A patent/CN1073615C/en not_active Expired - Lifetime
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4409131A (en) * | 1982-02-22 | 1983-10-11 | Maine | Preparation of CoMo and NiMo catalyst using cobalt or nickel complexes that are stable in basic solution |
| US4483942A (en) * | 1982-10-15 | 1984-11-20 | Nippon Oil Co., Ltd. | Process of preparing hydrogenation catalysts |
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| Publication number | Publication date |
|---|---|
| CN1249327A (en) | 2000-04-05 |
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