CN1006202B - A method for preparing supported hydroconversion catalyst and catalyst made by the method - Google Patents
A method for preparing supported hydroconversion catalyst and catalyst made by the method Download PDFInfo
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- CN1006202B CN1006202B CN85103891.3A CN85103891A CN1006202B CN 1006202 B CN1006202 B CN 1006202B CN 85103891 A CN85103891 A CN 85103891A CN 1006202 B CN1006202 B CN 1006202B
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Abstract
A process for preparing a supported hydroconversion catalyst comprising a support consisting essentially of alumina, silica or a mixture of both, at least one of molybdenum and tungsten, and at least one of cobalt and nickel, the process comprising: preparing a primary impregnation aqueous solution having a pH of 0.7 to 2.7, which comprises: mixing at least one of a molybdenum compound and a tungsten compound, at least one of a cobalt compound and a nickel compound, a stabilizing phosphorus compound in an amount of 0.2 to 1.0 mole per gram molecule of molybdenum or tungsten, and a suitable soluble amine compound selected from the group consisting of an alcohol amine, a polyamine and an amino acid in an amount of 2 to 6% by weight of the carrier, (b) impregnating the carrier with the above solution, and (c) drying and calcining the resulting composite.
Description
The present invention relates to a process for the preparation of supported hydroconversion catalysts, in particular catalysts having improved Hydrodenitrogenation (HDN) activity, and to catalysts prepared by such process.
Numerous studies have been conducted to develop and commercialize new, inexpensive, highly active hydrogen conversion catalysts that can be used in high volume first stage hydrocracking feed hydrotreaters and catalytic cracking feed hydrotreaters. The presence of significant amounts of residual components (including cracking feedstock) having boiling points greater than 535 ℃ in the hydrocarbon feed to the process creates serious activity and stability problems for the above-described utility catalysts currently used in industry.
Some hydrodenitrogenation catalysts for industrial use are well known. The best activity is currently Ni-No, ni-W, and Co-Mo catalysts attached to 7-alumina supports. The addition of phosphorus, which acts as a promoter, enhances the activity of these catalysts. For example, it is mentioned in British patent Specification 701,217 that the activity of hydrodesulfurization can be enhanced by the addition of phosphorus in the form of cobalt phosphomolybdate. In British patent Specification 807,583, phosphorus is mentioned to have a promoting effect on improving the hydrogenation activity of both Co-MO/Al 2O3 and Ni-W/Al 2O3 catalysts.
A one-step impregnation process is most desirable when the catalyst can be prepared by multiple impregnation processes. In order to achieve efficient impregnation and uniform distribution of metal on the support, the metallic elements must remain in solution during the impregnation process. Methods for maintaining a high concentration of metal in solution are well known. For example, in U.S. patent specification 3,629,146, a process is described for preparing supported catalysts containing metal molybdenum in an amount exceeding 12% by weight (concentration of pure metal) based on the catalyst prepared, which is prepared from a stabilized solution by one-step aqueous impregnation. In order to achieve efficient impregnation and a uniform portion of the metal on the support, the metal must remain in solution during the impregnation process. Precipitation of metal from the impregnation liquor may lead to non-uniformity of impregnation and reduced effectiveness of the deposited metal. The above-mentioned U.S. patent also teaches that a high concentration of active molybdenum can be immersed in the carrier by adding to the impregnating solution a quantity of stabilizing hydrogen peroxide and phosphoric acid. It has been found that hydrogen peroxide is not necessary for all impregnating solutions, as it is a solvent which increases the molybdenum content of the solution when used in a phosphorus-molybdenum solution.
In U.S. patent specification 2,946,739, a "conventional" method for preparing Co-Mo/Al 2O3 hydrocracking catalysts is described, which consists in impregnating the catalyst with an aqueous solution of (NH 4）Mo7O4·4H2 O in a 50/50 ethanolamine-water mixture) followed by drying and calcining the partially impregnated catalyst, and in the second step, re-using Co (NO 3）2 and Rh (NO 3）3 in aqueous solution. It has been found that the use of high concentrations of amine with phosphomolybdenum compounds results in unstable solutions, that is, in precipitation of metal compounds or uneven distribution of metal on the support.
In the course of studying various preparation methods of the catalyst, it was found that a stable impregnation liquid can be obtained by using a low concentration of certain amine compounds, such as alcohol amine, polyamine and amino acid, which are soluble in the impregnation liquid, together with at least one of molybdenum and tungsten compounds and at least one of nickel and cobalt compounds and a phosphorus compound. Typical alcohol amines are ethanolamine, propanolamine, butanolamine, diethanolamine 2, 2-diamino-1, 3-propanediol, 2, 3-triamino-1-propanol or triethanolamine. A common polyamine is ethylenediamine. Commonly used amino acids are glycine and nitrilotriacetic acid. Hydrogen peroxide may also be used as an adjuvant to formulate solutions in some cases. It was unexpectedly found that catalysts prepared with solutions containing both phosphorus and amine compounds had HDN activity 19% higher than catalysts prepared with solutions containing only phosphorus compounds. The amount of amine compound required is also much less than that used in the prior art (U.S. patent specification 2,946,739). The hydrodenitrogenation activity of the catalyst prepared with only the amine compound and not with the phosphorus compound is much less than that of the catalyst containing both phosphorus and amine.
The present invention thus relates to a process for the preparation of a supported hydroconversion catalyst comprising at least one of molybdenum and tungsten and at least one of cobalt and nickel bound to a suitable support, which comprises (a) preparing an aqueous impregnation solution (aqueous impregnation solutior) having a pH in the range of 0.7 to 2.7, which comprises mixing at least one of molybdenum compounds and tungsten compounds, at least one of cobalt compounds and nickel compounds, phosphorus compounds in an amount of 0.2 to 1.0 mole per mole of molybdenum or tungsten and a suitable soluble amine compound in an amount of 2 to 6% by weight of the support, impregnating the suitable catalyst support with the impregnation solution, and (c) drying and calcining the resulting composite.
In order to improve the HDN (hydrodenitrogenation) activity of the catalyst, the impregnation must not only be stable, but also allow a uniform distribution of the metal in the support. To prevent metal deposition on the support surface, the PH of the impregnation solution (at 38 ℃) must be lower than 2.7. However, if the pH is too low, i.e. below 0.7, moO 3 and phosphate form an adduct which is not uniformly distributed on the support. The pH is preferably maintained between 1.2 and 2.5 (at 38 ℃) and the support is impregnated with the solution so that it is loaded with the desired amount of catalytically active metal. The impregnated support (composite) is then dried and calcined. The process is particularly suitable for catalysts comprising 2.5 to 4% by weight of cobalt or nickel and 10 to 16% by weight of molybdenum or 10 to 32% by weight of tungsten on activated 7-alumina. Very high metal loadings can be obtained using a primary impregnation fluid (single impregnation so-lution) containing both phosphoric acid and soluble amine compounds.
It can be seen from the present invention that certain soluble amine compounds, when used in combination with certain phosphorus compounds, preferably phosphoric acid, not only effectively stabilize the impregnation solution, but also greatly enhance the catalytic activity of the finished catalyst. The reason for the enhanced catalyst activity is not clear, but it is believed that the use of certain phosphorus compounds in combination with amine compounds allows better metal dispersion.
As mentioned previously, the desired production conditions are critical in order to provide the hydrogenation metal on the catalyst support with the desired high concentration while maintaining high activity. We now feel that the most critical process conditions are the soluble amine compound/support weight ratio and the P/MoO 3 weight ratio. To achieve the above-described effect of the system described herein, the percentage of soluble amine/carrier should be in the range of 2% to 6% by weight. When this percentage is less than 2% by weight, the increase in catalyst activity seems to be unsatisfactory, whereas when it is more than 6% by weight, the activity does not appear to be higher than that when it contains 6% by weight of amine. Also, the amount of phosphorus should be 0.2 to 1.0 gram mole per gram mole of molybdenum or tungsten.
Many technical measures can be taken to maintain the pH of the impregnating solution at the desired value of 0.7 to 2.7, preferably in the range of 1.2 to 2.5. A suitable impregnation solution may be prepared by combining a molybdenum-containing solution comprising ammonia and/or ammonium hydroxide and a suitable soluble amine compound with a nickel-containing solution comprising phosphoric acid.
To stabilize MoO, the amount of ammonia and/or ammonium hydroxide added to the MoO slurry is typically 6 grams of NH or NHOH per 7 grams of MoO. Soluble amines may also be added to the solution, although some basic amines, such as monoethanolamine, propanolamine, ethylenediamine, may be substituted for ammonia and/or ammonium ions in a1 gram to 1 gram ratio. A preferred method of preparing the molybdenum-containing solution further comprises adding hydrogen peroxide to the impregnating solution in an amount of from 0.1 to 1 molar hydrogen peroxide per molar molybdenum.
Nickel-containing solutions contain a water-soluble nickel salt and phosphoric acid, and suitable nickel compounds are a wide range of such as nickel nitrate, nickel acetate, nickel formate, nickel oxide, nickel phosphate, nickel carbonate, nickel chloride and nickel hydroxide. Particularly useful are both nickel nitrate and nickel carbonate compounds. The final pH of the solution can be varied to within the desired range, especially 1.2 to 2.5 (at 38 ℃) by varying the amount of nickel salt, ammonia or ammonium hydroxide and the appropriate soluble amine compound, while achieving the desired nickel content.
The process of the present invention is particularly useful for supported hydroconversion catalysts comprising at least one of cobalt and nickel and at least one of molybdenum and tungsten bound to a support. The catalyst generally contains 1 to 5% by weight of cobalt and/or nickel, 2.5 to 4% by weight of special cobalt and/or nickel, and 10 to 16% by weight of molybdenum or 10 to 32% by weight of tungsten.
Any conventional catalyst support is considered suitable for use in the process of the present invention. Materials suitable as supports for the catalysts of the present invention include refractory oxides such as alumina, silica and mixtures thereof. Crystalline synthetic zeolites such as aluminosilicates, iron silicates, gallium silicates, magnesium oxide, titanium oxide and mixtures thereof may also be used as supports, but are preferably used in combination with refractory oxide supports. Activated 7-alumina is a particularly good support.
To commercialize a new hydroconversion catalyst, it is required that its HDN activity be greatly improved over existing commercial catalysts. In an effort to develop such improved catalysts, a number of experimental catalysts were prepared and their HDN activities were measured. The activity test in the test procedure was designed to determine denitrification using a standard hydrocarbon feed and a set of standard conditions including temperature, pressure, gas flow and liquid flow for each catalyst. A standard catalyst was tested under the same conditions as the experimental catalyst. The first order denitrification rate constant of the standard catalyst was set to 1.00, and the activity of all experimental catalysts was measured by this standard. This method was used to determine whether the HDN activity of the catalyst in the examples below was improved.
When the improved catalyst disclosed by the invention is used, suitable hydroconversion process conditions are that the temperature is 350-420 ℃, the total pressure is 75-200 bar, the hydrogen partial pressure is 60-200 bar, the space velocity is 0.4-1.5 kg of oil per liter of catalyst per hour, and the hydrogen feeding speed is 250-2500 nanoliters per kg of oil. According to the process, the hydrodenitrogenation treatment of heavy oil feed is preferably carried out at a temperature of 260-410 ℃, a total pressure of 100-150 bar, a hydrogen partial pressure of 80-150 bar, a space velocity of 0.4-1.0 kg oil/liter catalyst/hour, and a hydrogen feed rate of 500-1500 nanoliters/kg oil feed.
The hydrogen used may be pure hydrogen, or a hydrogen-containing gas, preferably having a hydrogen content of greater than 70%. The hydrogen-containing gas may also contain up to about 10% hydrogen sulfide.
The invention will now be illustrated by the following examples, which are intended to illustrate the invention and are not to be construed as limiting the invention.
Example 1
Catalyst A was prepared on a 7-alumina support at a concentration of 3.0% by weight of nickel, 13.0% by weight of molybdenum and 3.2% by weight of phosphorus. Because of the dry pore volume impregnation technique (drypore volume impregnation technique), the pores of the support are just filled with the various salt solutions. A solution suitable for impregnating 200 grams of alumina having a pore volume of 0.75 ml/gram may be formulated as follows:
nickel nitrate hexahydrate (26.0 grams) was dissolved in a sufficient amount of distilled water solution of 85% phosphoric acid (34.8 grams) to make up about 50 milliliters of the first solution. To this solution was added 6.9 g of nickel carbonate [ 51.2 wt% nickel-containing ]. The solution was stirred and heated slowly (to about 38 ℃) until the solids were completely dissolved, thus giving about 60 ml of solution No. 1. Solution number 2 was prepared by mixing 13.4 ml of 30% hydrogen peroxide, 50 ml of distilled water and 53.8 g of ammonium heptamolybdate and heating the mixture slowly (to about 38 ℃) until the solids were completely dissolved. To this solution 13.2 grams of molybdenum trioxide and 5.6 grams of 1-amino-2-propanol were added. Heating and stirring was continued until a clear yellow solution was obtained. While the two solutions are at or near room temperature, solution No.2 is slowly injected into solution No. 1 while stirring. The solution was cooled to about 32 ℃ and diluted with water to 150 ml and had a PH of about 2.2 (at 38 ℃). The solution was then added to the gamma-alumina support in small portions with moderate stirring. Stirring the impregnated carrier for 15-30 minutes, drying at 121 ℃ for 2 hours, and roasting at 482 ℃ and air for 2 hours.
Standard catalyst B was prepared in the same manner as catalyst A except that the molybdenum was derived entirely from ammonium heptamolybdate and no additional amine compound was added. The pH of the impregnation solution was about 1.8 (at 38 ℃). The catalytically cracked heavy diesel samples were hydrotreated with these two catalysts and the properties of the heavy diesel feedstock are shown in table 1. Both catalysts were sulfided with an H/HS gas mixture [5% HS (by volume) ] at 371℃for 2 hours before the start of the hydrotreatment.
The HDN activity of catalyst a containing 1-amino-2-propanol in the impregnation liquid was 19% higher than that of standard catalyst B.
Example 2
Catalyst C was prepared in the same manner as catalyst A except that the molybdate solution was prepared with 69.9 grams of ammonium heptamolybdate (without molybdenum trioxide) and 5.6 grams of 1-amino-2-propanol was replaced with 5.6 grams of nitrilotriacetic acid. The pH of the impregnation solution was 1.5 (at 38 ℃).
The HDN activity of catalyst C containing nitrilotriacetic acid was 22% increased relative to the activity of standard catalyst B.
Example 3
Catalyst D was prepared in the same manner as catalyst C except that nitrilotriacetic acid was replaced by 7.0 g of glycine. The pH of the impregnation solution was 2.3 (at 38 ℃).
The HDN activity of the glycine containing catalyst D was increased by 19% relative to the activity of the standard catalyst.
Example 4
To demonstrate the necessity of the presence of a suitable amine compound acting as a promoter, an alcohol functional group-containing water-soluble additive was tested. Catalyst E was prepared in the same manner as catalyst C except that 5.6 grams of ethylene glycol was substituted for nitrilotriacetic acid. The pH of the impregnation solution was 1.9 (at 38 ℃).
The activity of catalyst E containing ethylene glycol was the same as that of standard catalyst B in the experimental range.
Example 5
To demonstrate that very high metal loadings of catalyst were obtainable with a primary impregnation solution containing both phosphorus and soluble amine compounds, catalyst F was prepared with a metal loading of 3.5 wt% nickel, 15.0 wt% molybdenum, and 3.2 wt% phosphorus as follows:
Nickel nitrate hexahydrate (29.5 grams) was dissolved in a sufficient amount of distilled water solution of 85% phosphoric acid (36.8 grams) to make up about 50 milliliters of solution. 9.5 g of nickel carbonate [ 51.2 wt% nickel ] was added to the solution. The resulting slurry (to about 38 ℃) was stirred and heated slowly until the solids were completely dissolved, thus producing about 60 milliliters of the first solution.
The second solution (which had a volume of about 80 ml) was prepared by mixing 30% hydrogen peroxide (12.5 ml), 50 ml distilled water and ammonium heptamolybdate (65.3 g). The slurry was heated slowly (to about 38 ℃) until the solids were completely dissolved. 16.2 g of molybdenum trioxide and 5.6 g of monoethanolamine are additionally added. Heating and stirring was continued until a clear yellow solution was obtained.
When both solutions are at or near room temperature, the second solution is slowly injected into the first solution while stirring. The mixture was cooled to about 32 ℃ and diluted to 150 ml. This gives a clear stable solution with a pH of 2.0 (38 ℃). The solution was then poured into 7-alumina support in small batches with moderate stirring. And continuously stirring the impregnated carrier for 15-30 minutes, wherein the obtained catalyst particles are uniformly impregnated particles. The catalyst was dried at 121 ℃ for 2 hours and calcined at 482 ℃ for 2 hours. Catalyst F was measured in the same manner as catalyst B and was found to have a denitrification activity 23% higher than that of the standard catalyst B (Table 1).
Catalyst G had as high a loading of metal and phosphorus as catalyst F, but no soluble amine compound was added to the impregnation solution when preparing it. The metal in the solution partially settles on the outer surface of the support during impregnation, thus causing non-uniformity in the distribution of the metal. The catalyst particles are covered with "dust" which is mainly molybdenum oxide after calcination. This catalyst is not suitable for comparative tests.
TABLE 1
Test results
Under conditions of H58.2 bar, 330 ℃ H/oil 4.0
The feed parameters were C88.99%, H9.68%, S1.28%, N482ppm on support: ni3.0 wt.% to Mo13.0 wt.% to P3.2 wt.%
Relative denitrification Activity of catalyst additive (g/100 g support) solution pH (at 38 ℃)
B - 1.8 1.00±0.10
A1-amino-2-propanol (2.8) 2.2.1.19
C nitrilotriacetic acid (2.8) 1.5.1.22
D-aminoacetic acid (3.5) 2.3.1.19
E ethylene glycol (2.8) 1.9.1.08
F. monoethanolamine (2.8) 2.0.1.23
* The loading of the carrier (wt.%)
Ni3.5 Mo15 P3.2
Claims (10)
1. The method for preparing the supported hydroconversion catalyst by adopting an impregnation method comprises the steps of preparing a catalyst from a carrier mainly composed of alumina, silica or a mixture of the alumina and the silica, at least one of molybdenum and tungsten, at least one of cobalt and nickel and phosphorus; the method mainly comprises the steps of (a) preparing a primary soaking aqueous solution with a pH value of 0.7-2.7, wherein at least one of molybdenum compounds and tungsten compounds, at least one of cobalt compounds and nickel compounds, 0.2-1.0 mole of stabilizing phosphorus compound for each mole of molybdenum or tungsten and 2-6 weight percent of carrier, and proper soluble amine compound selected from alcohol amine, polyamine and amino acid are mixed, (b) soaking the carrier by the solution, and (c) drying and roasting the obtained compound.
2. The method of claim 1, wherein an immersion liquid is used having a pH in the range of 1.2 to 2.5 (at 38 ℃).
3. The process as claimed in claim 1, wherein the support used further comprises crystalline silicate zeolite.
4. The process of claim 1, wherein an activated gamma-alumina support is used.
5. The method according to claim 1, wherein 0.1 to 1.0 molar hydrogen peroxide per one molar molybdenum is additionally added when preparing the molybdenum-containing aqueous impregnation solution.
6. The process as claimed in claim 1 to 5, wherein the amine compound used is selected from the group consisting of monoethanolamine, 1-amino-2-propanol, 3-amino-1-propanol, glycine and nitrilotriacetic acid.
7. A hydroconversion catalyst consisting essentially of a carrier consisting essentially of alumina, silica or a mixture of both and at least one of 1 to 5 weight percent cobalt and nickel, at least one of 10 to 16 weight percent molybdenum and 10 to 32 weight percent tungsten, and the balance phosphorus, the catalyst being prepared by a process consisting essentially of:
(a) Preparing a primary soaking water solution with a pH value of 0.7-2.7, wherein at least one of molybdenum compound and tungsten compound, at least one of cobalt compound and nickel compound, 0.2-10 mol of phosphorus compound which has stabilizing effect for each mol of molybdenum or tungsten and 2-6 wt% of carrier and proper soluble amine compound selected from alcohol amine, polyamine and amino acid are mixed;
(b) Impregnating the above-mentioned carrier with the above-mentioned solution, and
(C) The resulting composite is dried and calcined.
8. The catalyst of claim 7, which is prepared by impregnating alumina, silica or a mixture of both with an aqueous impregnation solution having a pH of 1.2 to 2.5 (at 38 ℃) and containing nickel and molybdenum or cobalt and molybdenum.
9. The catalyst according to claim 7, wherein 0.1 to 1 molar hydrogen peroxide per one molar molybdenum is additionally added in preparing the molybdenum-containing impregnating aqueous solution.
10. The catalyst according to one or more of claims 7 to 9, which is prepared by using an amine compound selected from the group consisting of ethanolamine, 1-amino-2-propanol, 3-amino-1-propanol, glycine and nitrilotriacetic acid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN85103891.3A CN1006202B (en) | 1984-05-18 | 1985-05-10 | A method for preparing supported hydroconversion catalyst and catalyst made by the method |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US06/611,574 US4530911A (en) | 1984-05-18 | 1984-05-18 | Hydrodenitrification catalyst |
| CN85103891.3A CN1006202B (en) | 1984-05-18 | 1985-05-10 | A method for preparing supported hydroconversion catalyst and catalyst made by the method |
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| Publication Number | Publication Date |
|---|---|
| CN85103891A CN85103891A (en) | 1986-11-12 |
| CN1006202B true CN1006202B (en) | 1989-12-27 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN85103891.3A Expired CN1006202B (en) | 1984-05-18 | 1985-05-10 | A method for preparing supported hydroconversion catalyst and catalyst made by the method |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101279278B (en) * | 2007-04-04 | 2010-12-01 | 中国石油化工股份有限公司 | Molybdenum, nickel, phosphorus soaking solution and preparation thereof |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1051479C (en) * | 1994-12-07 | 2000-04-19 | 中国石油化工总公司石油化工科学研究院 | Carbon carrier hydrogenation catalyst |
| CN1063104C (en) * | 1996-09-04 | 2001-03-14 | 中国石油化工集团公司抚顺石油化工研究院 | Co-impregnation liquid for preparing hydrocracking catalyst |
| CN1060097C (en) * | 1996-12-11 | 2001-01-03 | 中国石油化工总公司 | Catalyst for hydrogenation of fraction oil, and method for preparing same |
| CN100425676C (en) * | 2005-04-29 | 2008-10-15 | 中国石油化工股份有限公司 | Hydrogenation cracking catalyst composition |
| CN101434861B (en) * | 2007-11-15 | 2013-03-20 | 中国石油化工股份有限公司 | Preparation method of hydrogenation catalyst |
| CN102989493B (en) * | 2011-09-15 | 2015-05-20 | 中国石油天然气股份有限公司 | A kind of preparation method of composite catalyst for heavy oil hydrotreating |
| EP3041604A4 (en) * | 2013-09-06 | 2017-04-26 | Reliance Industries Limited | A catalyst composition and a catalytic process for conversion of biomass to crude bio oil |
| CN105778979B (en) * | 2014-12-22 | 2017-11-07 | 中国石油天然气股份有限公司 | Catalyst for reducing sulfur content of catalytic cracking gasoline and preparation method thereof |
-
1985
- 1985-05-10 CN CN85103891.3A patent/CN1006202B/en not_active Expired
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101279278B (en) * | 2007-04-04 | 2010-12-01 | 中国石油化工股份有限公司 | Molybdenum, nickel, phosphorus soaking solution and preparation thereof |
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