CN1211460C - Hydrogenation catalyst preparing method - Google Patents
Hydrogenation catalyst preparing method Download PDFInfo
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- CN1211460C CN1211460C CN 02133124 CN02133124A CN1211460C CN 1211460 C CN1211460 C CN 1211460C CN 02133124 CN02133124 CN 02133124 CN 02133124 A CN02133124 A CN 02133124A CN 1211460 C CN1211460 C CN 1211460C
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Abstract
The present invention relates to a preparation method of a hydrodemetalization catalyst for heavy oil and residual oil, which is characterized in that a weak acid solution or a weakly alkaline solution containing organic acid, volatile ammonium salt and active metal is adopted as a peptizing agent mixed with an alumina monohydrate, the constant temperature of the mixture is maintained for a certain time after the mixture is heated at the temperature of 50DEG C to 130DEG C, then, the mixture is kneaded into a mouldable body formed, dried and calcined to obtain the final catalyst. Compared with the prior art, the method of the present invention has the advantages of larger catalyst product pore volume, concentrated pore distribution and simple catalyst preparing technology. The method of the present invention reduces the damage of peptizing acid to the pore structure of a catalyst carrier. The catalyst prepared with the method of the present invention, which is suitable for the hydrodemetalization process of the heavy oil and the hydrodemetalization process of the residual oil, has superior activity and superior activity stability.
Description
1, technical field
The present invention relates to a kind of preparation method of hydrotreatment catalyst, especially heavy, residuum hydrogenating and metal-eliminating catalyst preparation method.
2, background technology
Now, it is heavy that world's crude oil becomes gradually, and deep processing and utilization very fast, heavy, residual oil are worldwide especially paid attention to and market increases the light-end products demand.One of key of heavy Oil Hydrotreating Processes is to develop the catalyzer of excellent performance.Its performance not only depends on the chemical state of kind, content and the active specy of reactive metal, and it is closely related with catalyst pores structure and preparation method thereof, for heavy oil hydrogenation demetal, having large pore volume is that catalyzer keeps long-life important assurance.
U.S. Pat 4411824 discloses a kind of Preparation of catalysts method, and the key step of preparation catalyzer is: (1) adds Al to gelatinizing agent at 20～100 ℃
2O
3In, obtain the pulpous state liquid of pH3～6; (2), contain the VIII family metallic compound of solubility in gelatinizing agent and the alkali lye with in the nitrogenous alkaline solution and slurries; (3) moulding; (4) at 100～260 ℃ of dry 1-5 hours; (5) 450 ℃～825 ℃ roastings 1～6 hour.The problem that the catalyzer for preparing by above-mentioned openly method exists is that the gelatinizing agent acidity that (1) adds is stronger, to the pore structure formation destruction of aluminum oxide monohydrate, the pore volume of catalyzer is reduced easily; (2) complicated operating process.The catalyzer of being introduced among USP4448896 and the JP57-123820 adopts physics expanding agent carbon black to carry out reaming and increase pore volume, its peptizing agent also uses acid stronger acidic solution, owing to need to use more carbon black, cause prepared catalyzer aperture distribution disperse, bad mechanical strength, the catalyzer aperture is also less.
3, summary of the invention
The object of the present invention is to provide the big and simple Catalysts and its preparation method of preparation method of a kind of pore volume.This catalyzer is particularly useful for removing the organic impuritys such as nickel, vanadium heavy metal and sulphur in the heavy hydrocarbon.
The process of method for preparing catalyst of the present invention is: (1) will contain water-soluble aqueous acid and volatile ammonium salt alkaline aqueous solution fully earlier and nitrogenous alkaline solution mixes, add the active metallic compound that contains solubility then, be mixed with peptizing agent, the pH value of solution is reached between 6～9; (2) peptizing agent mixes with the aluminum oxide monohydrate, and the pH value is reached more than 7.0, better is more than 7.5, and preferably 7.5～9.0.Constant temperature is 0.5～1.5 hour after being heated to 50 ℃～130 ℃.(3) the mixed plastic, moulding pinched into; (4) dry, roasting.Drying temperature is 50 ℃～150 ℃, and maturing temperature is more than 800 ℃.
It is described that to contain water-soluble aqueous acid generally be organic acid, as citric acid, formic acid, acetate etc., described can complete volatile ammonium salt alkaline aqueous solution generally be volatile salt, and the alkaline aqueous solution of bicarbonate of ammonia etc., described nitrogenous alkaline solution generally are the alkaline aqueous solutions of ammoniacal liquor etc.
The per 1000 gram butt aluminum oxide of described aqueous acid consumption are 550ml～800ml, and acid concentration is 5.0g/100ml～9.0g/100ml.
The consumption of described ammonium salt is described aluminum oxide (butt) 2.5%～4.0% of the weight that feeds intake.
The consumption of described nitrogenous thing is described aluminum oxide (butt) 3.0%～5.0% of the weight that feeds intake.
Described catalyzer drying conditions generally is: drying is 1～10 hour under 50～150 ℃ of temperature;
Described catalyzer roasting method is: rise to 800 ℃～1000 ℃ with 200～300 ℃/hour, constant temperature carried out roasting in 1～6 hour.
Described catalyst metal components is the compound of group vib molybdenum element and group VIII nickel element, and its catalyzer compositing range (weight percent) is: MoO
37%～15%, NiO 1%～3%, and all the other are Al
2O
3The catalyzer pore volume is at least 0.65ml/g, generally at 0.70-0.80ml/g; Specific surface is 130～230m
2/ g is preferably 140-180m
2/ g.
The shape of catalyzer of the present invention can change by changing mould according to different requirements.
The mineral compound that can add boron, silicon, phosphorus, titanium etc. in the catalyzer of the present invention; Also can roasting in different temperature ranges, to obtain different zones and to contain the catalyzer of different added ingredientss.
Compare with prior art, the advantage of the inventive method is:
(1) avoids using strong acid to make peptizing agent merely.Therefore eliminated thus that the class material directly acts on the aluminum oxide monohydrate and to the catalyst pores structural damage.
(2) method for preparing catalyst is simple.
(3) the inventive method adopts the volatile ammonium salt as the pore structure conditioning agent, and material is heated for some time before moulding, makes catalyzer have characteristics such as pore volume is big, pore distribution concentration, is suitable for the hydrodemetallation (HDM) process of heavy hydrocarbon.
4, embodiment
Below further specify Preparation of catalysts method of the present invention with example.
Example 1
The acidic aqueous solution that 800ml is contained the 72g citric acid join 700ml contain mix in the basic solution of 27.5g volatile salt and 33g ammonia after, add industrial Ammonium Heptamolybdate 55g and industrial nitric acid nickel 45g then, stir, till the no insolubles, the pH value of solution is 9.
Peptizing agent joins in the aluminum oxide monohydrate dry glue powder that takes by weighing 1100g together.Mixed 25 minutes, pH value 9 is heated to 130 ℃, after the time is 1.5 hours.Mixed 30 minutes, and made material become plastic.Be that the 1.0mm circle is leant on pattern tool extrusion with F-26 type banded extruder and diameter then.After extrusion finished, 150 ℃ of dryings 1 hour, the speed with 300 ℃/hour rose to 800 ℃ under air atmosphere then, and constant temperature calcining 6 hours obtains catalyst A.
Example 2
The acidic aqueous solution that 620ml is contained 31g acetate joins 670ml and contains in the basic solution of 35g bicarbonate of ammonia and 35g ammonia and mix, and adds industrial Ammonium Heptamolybdate 55g and industrial nitric acid nickel 45g then, stirs, and till the no insolubles, the pH value of solution is 8;
Peptizing agent joins in the aluminum oxide monohydrate dry glue powder of the 1000g that takes by weighing together.Mixed 20 minutes, pH value 8 is heated to 120 ℃, and the time is 1.0 hours.Mixed 30 minutes, and made material blend together plastic.Be that the 1.0mm circle is leant on pattern tool extrusion with F-26 type banded extruder and diameter then.After extrusion finishes, 50 ℃ of dryings 3 hours, 105 ℃ of dryings 6 hours.Speed with 230 ℃/hour rises to 900 ℃ under air atmosphere then, and constant temperature calcining 3 hours obtains catalyst B.
Example 3
The acidic aqueous solution that 550ml is contained 49g formic acid joins 600ml and contains in the basic solution of 40g volatile salt and 50g ammonia and mix, and adds industrial Ammonium Heptamolybdate 55g and industrial nitric acid nickel 45g then, stir, and till the no insolubles, the pH value 7 of solution;
Peptizing agent joins in the aluminum oxide monohydrate dry glue powder that takes by weighing 1000g together.Mixed 20 minutes, pH value 7.5 is heated to 50 ℃, and the time is 0.5 hour.Mixed 30 minutes, and mixed to pinch making material become plastic.Be that the 1.0mm circle is leant on pattern tool extrusion with F-26 type banded extruder and diameter then.After extrusion finishes, 90 ℃ of dryings 10 hours.Speed with 200 ℃/hour rises to 1000 ℃ under air atmosphere then, and constant temperature calcining 1 hour obtains catalyzer C.
Comparative example 1
Preparation of catalysts method according in U.S. Pat 4411824 examples makes catalyzer D.
Table one catalyzer physical data
| The catalyzer numbering | A | B | C | D |
| Pore volume, ml/g | 0.70 | 0.77 | 0.80 | 0.65 |
| Specific surface, m 2/g | 156 | 160 | 157 | 162 |
| Can several diameters, nm | 17 | 15.5 | 16.8 | 14.5 |
| Pore distribution, % (10～20) nm | 80 | 85 | 81 | 75 |
| MoO 3，w％ | 8.00 | 7.95 | 8.03 | 8.01 |
| NiO，w％ | 2.00 | 2.01 | 1.98 | 2.00 |
Example 4
On 200ml fixed bed hydrogenation testing apparatus catalyst A, D have been carried out the activity stability test, stock oil character, test conditions and result are shown in table two, three, four.
Table two stock oil character
Table three test conditions
| Temperature of reaction, ℃ | 385 |
| Reaction pressure, MPa | 15.7 |
| Volume space velocity, h -1 | 1.0 |
| Hydrogen-oil ratio, V/V | 758 |
Table four catalyst activity stability test result
| Catalyzer | A | D | ||
| Runtime, h | Desulfurization degree, % | Take off (nickel+vanadium) rate, % | Desulfurization degree, % | Take off (nickel+vanadium) rate, % |
| ～1000 | 50.0 | 72.0 | 49.7 | 70.4 |
| 1000～2000 | 48.1 | 71.0 | 47.1 | 67.9 |
| 2000～3000 | 47.4 | 69.7 | 45.0 | 66.0 |
From table four, find out, when device running to 1200 hours～2000 hours, catalyzer D takes off percentage of admixture, and to take off percentage of admixture than catalyst A low, illustrates that catalyst A is bigger than the molten impurity ability of catalyzer D.
By above result as can be seen, by the catalyzer of the present invention's preparation, pore volume is apparently higher than the pore volume of comparative example catalyzer.This shows the pore volume that adopts the inventive method can effectively improve catalyzer.
Claims (8)
1, a kind of hydrogenization catalyst preparation method, it is characterized in that adopting following process: (1) will contain water-soluble aqueous acid and volatile ammonium salt alkaline aqueous solution fully and nitrogenous alkaline solution mixes, the molybdate compound and the nickel compound containing that add solubility then, be mixed with peptizing agent, the pH value of solution is reached between 6～9; (2) peptizing agent mixes with the aluminum oxide monohydrate, and the pH value is reached more than 7.0, be heated to 50 ℃～130 ℃ after constant temperature 0.5～1.5 hour; (3) the mixed plastic, moulding pinched into; (4) dry, roast; Described drying temperature is 50 ℃～150 ℃, and be 1～10 hour time of drying, and maturing temperature is 800～1000 ℃, and roasting time is 1～6 hour.
2,, it is characterized in that the mixture pH value of described peptizing agent and aluminum oxide monohydrate is more than 7.5 according to the described preparation method of claim 1.
3,, it is characterized in that the mixture pH value of described peptizing agent and aluminum oxide monohydrate is 7.5～9.0 according to the described preparation method of claim 1.
4,, it is characterized in that described water soluble acid is selected from citric acid, formic acid or acetate according to the described preparation method of claim 1.
5, according to the described preparation method of claim 1, it is characterized in that described can complete volatile ammonium salt alkaline aqueous solution the alkaline aqueous solution that is volatile salt or bicarbonate of ammonia, described nitrogenous alkaline solution is an ammoniacal liquor.
6, according to the described preparation method of claim 1, it is characterized in that described aqueous acid consumption is 1000 gram butt aluminum oxide 550ml～800ml, acid concentration is 5.0g/100ml～9.0g/100ml.
7, according to the described preparation method of claim 1, the consumption that it is characterized in that described ammonium salt is described aluminum oxide 2.5%～4.0% of the weight that feeds intake, and the consumption of described nitrogenous thing is described aluminum oxide 3.0%～5.0% of the weight that feeds intake.
8, according to the described preparation method of claim 1, the consumption that it is characterized in that described catalyst activity metal molybdenum and nickel accounts for final catalyst weight per-cent and is: MoO
37%～15%, NiO 1%～3%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 02133124 CN1211460C (en) | 2002-10-10 | 2002-10-10 | Hydrogenation catalyst preparing method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 02133124 CN1211460C (en) | 2002-10-10 | 2002-10-10 | Hydrogenation catalyst preparing method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1488717A CN1488717A (en) | 2004-04-14 |
| CN1211460C true CN1211460C (en) | 2005-07-20 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 02133124 Expired - Lifetime CN1211460C (en) | 2002-10-10 | 2002-10-10 | Hydrogenation catalyst preparing method |
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Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104588108B (en) * | 2013-11-03 | 2016-08-17 | 中国石油化工股份有限公司 | Heavy-oil hydrogenation catalyst and its preparation method and application |
| CN106807419B (en) * | 2017-03-09 | 2019-07-02 | 武汉凯迪工程技术研究总院有限公司 | The method that infusion process prepares hydrotreating catalyst |
| CN106807418B (en) * | 2017-03-09 | 2019-07-02 | 武汉凯迪工程技术研究总院有限公司 | Hydrotreating catalyst dipping solution and preparation method thereof |
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