CN1221632C - Dipping solution and preparing method thereof - Google Patents
Dipping solution and preparing method thereof Download PDFInfo
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- CN1221632C CN1221632C CN 03133555 CN03133555A CN1221632C CN 1221632 C CN1221632 C CN 1221632C CN 03133555 CN03133555 CN 03133555 CN 03133555 A CN03133555 A CN 03133555A CN 1221632 C CN1221632 C CN 1221632C
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Abstract
The present invention relates to a dipping solution and a preparation method thereof for hydrogenation catalysts. The solution of the present invention contains at least one metal component of the VIB group and at least one metal component of the VIII group. The present invention is characterized in that the solution contains at least three metal components, and is a water solution without volatile substances and odor. In the process of preparing the solution, a water soluble compound containing molybdenum is firstly dissolves by water, then organic carboxylic acid substances are added so that the molybdenum forms a substance for stabilizing complexes, the other compound containing the metal of the VIB group is added, at least one salt of the metal of the VIII group, and the mixture is completely dissolved. The solution preparation method has simple preparation process and no irritant and volatile substances; the solution has good stability, and can be used for hydrofining petroleum distillate oil, heavy oil, etc. and preparing hydrotreating catalysts.
Description
Technical field
The present invention relates to a kind of dipping solution and preparation method thereof, specifically prepare hydrofining and the used dipping solution of hydrotreating catalyst and preparation method thereof, particularly tungsten, molybdenum, nickel (or cobalt) hybrid infusion solution and preparation method thereof.Solution of the present invention can be used for preparation, the especially hydrorefining paraffin wax of hydrotreating catalysts such as petroleum fractions and heavy oil and the preparation of residual oil hydrocatalyst.
Background technology
As everyone knows, industrial used hydrofining at present and hydrotreating catalyst are carrier with inorganic oxide such as aluminum oxide normally, and load hydrogenation active metals (being generally group vib 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 often to reach more than three kinds or three kinds, and require metal content very high, this brings certain degree of difficulty with regard to the load of giving the hydrogenation activity component.The method that solves often has following several: the one, prepare two or more solution, and dip loading is on support of the catalyst respectively; The 2nd, set of dispense more than three kinds or three kinds is made a kind of solution one or many dip loading on support of the catalyst.First kind of carrying method promptly prepared a component or two component solutions, and step impregnation prepares three component catalysts, operate complicatedly, preparation cycle is long, and the catalyzer yield is low, physico-chemical property to catalyzer also has certain influence, and activity of such catalysts also is subjected to certain influence.Prepare the above co-impregnated solution of three components or three composition activity metals, when adopting the one or many dipping, under normal conditions, because the restriction of strength of solution, single-steeping is only applicable to light ends oil hydrofining or the hydrotreating catalyst lower to the metal content requirement, the hydrofining of mink cell focus of having relatively high expectations for metal content or residual oil etc. or hydrotreating catalyst generally need adopt repeatedly dipping, and this makes Preparation of catalysts process complexity, and cost increases.
ZL89109140 is with tungsten, molybdenum, three kinds of active ingredients of nickel and auxiliary agent boron, and the mode of loading of reactive metal adopts two kinds of solution step impregnations, and the siliceous alumina supporter of solution impregnation of the first step preparation tungstenic and nickel is stand-by after drying and the roasting; Second step was prepared the work in-process of the tungstenic nickel of the basic solution dipping the first step that contains molybdenum and boron, and finished catalyst is made in drying and roasting again.The method of such two kinds of solution step impregnations makes that the Preparation of Catalyst flow process is complicated, catalyst breakage rate height, thereby yield is low, Preparation of Catalyst cost height.
ZL99113281.5 also is with tungsten, molybdenum, nickel three components are active ingredient, add phosphate builder, this patent relates to a kind of preparation of tungsten nickel phosphorus solution, and the technology of taking segmentation to soak altogether, the catalyst activity metal component is uniformly dispersed on catalyzer, activity of such catalysts is improved, adopt twice or twice above steeping process in catalyst preparation process equally, the preparation process complexity, and tungsten nickel phosphorus three component solutions are tungstate and the nickel salts that add processable on the basis of traditional molybdenum nickel phosphorus solution, make solution acidic stronger, viscosity is big, and is big to the catalyst pores structure influence, make the metal component content of catalyzer reach requirement if adopt this solution single-steeping, then very difficult, because metal component content height, bonding is agglomerating easily for moist catalysis in steeping process, cause the metal component catalyzer to disperse inhomogeneous at catalyst surface, influence activity of such catalysts, therefore, this patent haves no alternative but adopt lower concentration, the method that low viscous solution repeatedly floods prepares catalyzer.
Same ZL86107828 relates to the preparation of a kind of tungsten, molybdenum, nickel phosphorus solution solution, and the same with ZL99113281.5, this solution acidic is strong, viscosity is big, and the concentration of nickel is low in this patent solution, utilizes that NiO content does not belong to optimum range less than 3.0m% on the catalyzer of this formulations prepared from solutions.The preparation of solution all is to adopt the mode of 90 ℃～120 ℃ of heating to dissolve its metal component in two patents, dissolution time 0.5 hour did not wait by 6.0 hours, owing to adopt extra heating, energy consumption and facility investment have not only been increased, also increased operation steps, and operate trouble, preparation time is long, thereby the manufacturing cost of catalyzer is increased.
If can find out a kind of easy method prepares mixing solutions, a little less than the solution acidic of preparation, viscosity is low, and process for preparation is simple, and can adopt this solution to prepare catalyzer with one section impregnation method, can overcome above-mentioned shortcoming.
Summary of the invention
At problems of the prior art, the invention provides W-Mo-Ni (or Co) dipping solution of a kind of high density, low acidity and low-viscosity stable, a kind of quick, easy, energy-conservation W-Mo-Ni (or Co) is provided solution manufacturing method simultaneously.
W-Mo-Ni of the present invention (Co) each material concentration of dipping solution (metal concentration is in oxide compound) is: molybdenum 0.05g/ml～0.35g/ml, be preferably 0.10g/ml～0.25g/ml, tungsten 0.05g/ml～0.50g/ml, be preferably 0.20g/ml～0.40g/ml, Ni (or Co) 0.01～0.15g/ml, be preferably 0.06g/ml～0.12g/ml, the carboxylic-acid substance is 0.03～0.30g/ml, is preferably 0.05～0.15g/ml.
The preparation method of dipping solution of the present invention is: earlier contain a kind of salt in molybdenum and the tungsten with water dissolution, add organic carboxyl acid class material then and make it to form stable complex compound, add another kind of metal-salt again, add nickeliferous (or cobalt) salt at last, make it to dissolve fully, this process can heat to be dissolved various metal-salts as early as possible and reaches stable.The organic carboxyl acid class material that the present invention selects is one or more of citric acid, tartrate, oxalic acid etc., and the present invention is preferably citric acid.Solution of the present invention can also adopt preparation process such as following: (1) dissolves molybdate compound earlier with the aqueous solution that contains organic carboxylic-acid substance, dissolves Tungstenic compound and nickel salt (or cobalt salt) again; (2) with water dissolution molybdate compound and tungsten compound, add organic carboxyl acid class material then, add nickel salt or cobalt salt at last; (3) water dissolves organic carboxylic-acid substance, dissolves a kind of molybdenum solution that contains of molybdate compound preparation again; Tungstenic compound and nickeliferous or cobalt compound added in the entry dissolve, be prepared into a kind of tungstenic nickel or cobalt liquor, then two kinds of solution are carried out mixing and stirring.(4) water dissolves nickel salt or cobalt salt earlier, dissolves molybdate compound and Tungstenic compound then, adds organic carboxyl acid class material then.Preferred version (3).
Nickel salt (or cobalt salt) is nitrate, acetate or the muriate etc. of nickel (or cobalt).Molybdate compound is a kind of ammonium salt that is dissolvable in water the molybdenum of water, mainly is a kind of Ammonium Heptamolybdate.Tungstenic compound is an ammonium metawolframate.
The inventive method prepared solution is as clear as crystal, and good stability can be deposited the long period, and is especially more stable at 30 ℃～70 ℃ following solution, 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.Solution compound method of the present invention is simple and easy to do, in the preparation process, because selected compounds is water miscible metallic salt, so also solubilized had at normal temperatures both been simplified operation steps, can save time again, and save energy helps reducing the Catalyst Production cost.
Embodiment
The invention is further illustrated by the following examples.
Embodiment 1
Take by weighing water miscible technical grade Ammonium Heptamolybdate (solubleness of this kind ammonium molybdate in water is 50.0g/100g water) 90g, add the 150ml deionized water, stirring adds the 60.0g citric acid after ammonium molybdate is dissolved fully again, fully dissolving, then with the ammonium metawolframate 180g and the nickelous nitrate 140g of technical grade, join the 150ml deionized water, stirring and dissolving is mixed two kinds of different solutions then, with deionized water liquor capacity is transferred to 500ml, get solution A.
Embodiment 2
Compare with embodiment 1, change water miscible technical grade Ammonium Heptamolybdate add-on into 180g, the ammonium metawolframate add-on changes 270.0g into, and correspondingly the add-on of citric acid changes 90.0g into, and all the other are identical with embodiment 1, and promptly the cost example gets solution B.
Embodiment 3
Compare with embodiment 1, change the ammonium metawolframate add-on into 90.0g, correspondingly the add-on of citric acid changes 30.0g into, and all the other are identical with embodiment 1, and promptly the cost example gets solution C.
Embodiment 4
Compare with embodiment 1, change water miscible technical grade Ammonium Heptamolybdate add-on into 45g, the ammonium metawolframate add-on changes 45.0g into, nickelous nitrate changes 70.0g into, and correspondingly the add-on of citric acid changes 10.0g into, and all the other are identical with embodiment 1, be the cost example, get solution D.
Embodiment 5
Compare with embodiment 1, earlier the 45.0g citric acid is dissolved in the deionized water, add the metal-salt identical then, promptly get solution E with embodiment 1.
Embodiment 6
Compare with embodiment 1, change the ammonium molybdate add-on into 45.0g, correspondingly the add-on of citric acid changes 20.0g into, and all the other are identical with embodiment 1, and promptly the cost example promptly gets solution F.
Embodiment 7
Compare with embodiment 6, change the ammonium metawolframate add-on into 100.0g, correspondingly the add-on of citric acid changes 15.0g into, and promptly the cost example promptly gets solution G.
Comparative example 1
This example is to prepare solution by the method that ZL86107828 describes.
With technical grade ammonium metawolframate 180g, industry molybdenum trioxide 75g, basic nickel carbonate 30.0g, phosphoric acid 30.0g and 350ml deionized water mix, then under whipped state and 100 ℃ of reactions 1.5 hours down, after the filtration with solution dilution to 500ml, Solution H.
Embodiment 7
This example is above-mentioned each routine solution comparing result, and is as shown in table 1 below.
Each embodiment solution contrast situation of table 1
| The solution numbering | Strength of solution, g/ml | The pH value | Relative viscosity | Stability | |||
| MoO 3 | WO 3 | NiO | Citric acid | ||||
| A | 0.148 | 0.296 | 0.07 | 0.12 | 3.0 | 6.0 | Stable |
| B C D E F G H | 0.296 0.148 0.074 0.148 0.074 0.074 0.15 | 0.444 0.148 0.074 0.296 0.296 0.164 0.30 | 0.07 | 0.18 | 2.5 3.5 3.8 3.2 3.5 3.6 1.0 | 8.2 4.2 3.0 4.5 4.0 3.2 12.5 | Stable stable stable |
| 0.07 | 0.06 | ||||||
| 0.035 | 0.02 | ||||||
| 0.07 | 0.09 | ||||||
| 0.07 | 0.040 | ||||||
| 0.07 | 0.030 | ||||||
| 0.035 | / | ||||||
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.
This is shown as can be seen, and the viscosity of solution of the present invention increases with the increase of ammonium metawolframate and citric acid adding amount; Solution A of the present invention, B, C, D, E, F, G have satisfactory stability; Solution of the present invention and H compare, and soltion viscosity obviously reduces, and the solution pH value is also higher.
Claims (10)
1, a kind of dipping solution, solvent are water, and solute is tungsten compound, molybdenum compound, nickel compound or cobalt compound and organic carboxyl acid; Wherein the concentration of each solute in solution is: in the molybdenum 0.05g/ml～0.35g/ml of oxide compound, in the tungsten 0.05g/ml～0.50g/ml of oxide compound, in the nickel or the cobalt 0.01～0.15g/ml of oxide compound, organic carboxyl acid is 0.03～0.30g/ml.
2, according to the described dipping solution of claim 1, it is characterized in that each material concentration of described dipping solution is: in the molybdenum 0.10g/ml～0.25g/ml of oxide compound, tungsten 0.20g/ml～0.40g/ml in oxide compound, in the nickel or the cobalt 0.06g/ml～0.12g/ml of oxide compound, organic carboxyl acid 0.05～0.15g/ml.
3, according to claim 1 or 2 described dipping solutions, it is characterized in that described organic carboxyl acid be in citric acid, tartrate, the oxalic acid one or more.
4, the preparation method of the described dipping solution of a kind of claim 1, it is characterized in that its process is as follows: earlier contain a kind of compound in molybdenum and the tungsten with water dissolution, add organic carboxyl acid then, add the another kind of metallic compound that contains in molybdenum and the tungsten again, add nickel salt or cobalt salt at last, make it to dissolve fully, the add-on of various materials is in content in the claim 1.
5, in accordance with the method for claim 4, it is characterized in that described organic carboxyl acid is one or more in citric acid, tartrate, the oxalic acid.
6, in accordance with the method for claim 4, it is characterized in that described nickel salt or cobalt salt are nitrate, acetate or the muriate of nickel or cobalt, molybdate compound is an Ammonium Heptamolybdate, and Tungstenic compound is an ammonium metawolframate.
7, the preparation method of the described dipping solution of a kind of claim 1, it is characterized in that adopting following process: dissolve molybdate compound earlier with the aqueous solution that contains organic carboxylic acid, dissolve Tungstenic compound and nickel salt or cobalt salt again, the add-on of various materials is in content in the claim 1.
8, the preparation method of the described dipping solution of a kind of claim 1, it is characterized in that adopting following process: with water dissolution molybdate compound and tungsten compound, add organic carboxyl acid then, stir last nickel salt or the cobalt salt of adding in dissolving back fully, the add-on of various materials is in content in the claim 1.
9, the preparation method of the described dipping solution of a kind of claim 1 is characterized in that adopting following process: water dissolving organic carboxyl acid, dissolve a kind of molybdenum solution that contains of molybdate compound preparation again; Tungstenic compound and nickeliferous or cobalt compound added in the entry dissolve, be prepared into a kind of tungstenic, nickel solution, or tungstenic, cobalt liquor; Then two kinds of solution are carried out mixing and stirring, the add-on of various materials is in content in the claim 1.
10, the preparation method of the described dipping solution of a kind of claim 1, it is characterized in that adopting following process: water is dissolving nickel salt or cobalt salt earlier, dissolve molybdate compound and Tungstenic compound then, add organic carboxyl acid then, the add-on of various materials is in content in the claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03133555 CN1221632C (en) | 2003-05-31 | 2003-05-31 | Dipping solution and preparing method thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03133555 CN1221632C (en) | 2003-05-31 | 2003-05-31 | Dipping solution and preparing method thereof |
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| CN1552794A CN1552794A (en) | 2004-12-08 |
| CN1221632C true CN1221632C (en) | 2005-10-05 |
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Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2603317A4 (en) | 2010-08-13 | 2014-08-06 | Shell Oil Co | A hydroprocessing catalyst prepared with waste catalyst fines and its use |
| CN103100400B (en) * | 2011-11-09 | 2015-07-22 | 中国石油化工股份有限公司 | Preparation method of hydrocracking catalyst |
| CN102658208B (en) * | 2012-04-28 | 2015-10-07 | 重庆紫光天化蛋氨酸有限责任公司 | Mercaptan catalyst agent and its preparation method and application |
| CN103627425B (en) * | 2012-08-23 | 2016-02-10 | 中国石油天然气股份有限公司 | Residual oil hydrodesulfurization method |
| CN103785448B (en) * | 2012-11-03 | 2016-04-13 | 中国石油化工股份有限公司 | A kind of clean method for preparing of hydrogenation catalyst |
| CN104549430B (en) * | 2013-10-23 | 2017-05-17 | 中国石油化工股份有限公司 | Hydrogenation catalyst as well as preparation method and application thereof |
| CN104998696B (en) * | 2014-04-24 | 2018-01-05 | 中国石油化工股份有限公司 | A kind of dipping solution and its preparation and application |
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