CN1286566C - Hydrofining catalyst containing molybdenum and/or tungsten and nickel and/or cobalt and its preparation process - Google Patents
Hydrofining catalyst containing molybdenum and/or tungsten and nickel and/or cobalt and its preparation process Download PDFInfo
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- CN1286566C CN1286566C CN 03147983 CN03147983A CN1286566C CN 1286566 C CN1286566 C CN 1286566C CN 03147983 CN03147983 CN 03147983 CN 03147983 A CN03147983 A CN 03147983A CN 1286566 C CN1286566 C CN 1286566C
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Abstract
The present invention relates to a hydrofining catalyst containing molybdenum and/or tungsten and nickel and/or cobalt, which contains a heat resisting inorganic oxide carrier, the molybdenum and/or the tungsten and the nickel and/or the cobalt, wherein the molybdenum and/or the tungsten and the nickel and/or the cobalt are loaded on the carrier. The catalyst is obtained by impregnating the heat resisting inorganic oxide carrier with an impregnating solution of a compound containing molybdenum and/or tungsten and nickel and/or cobalt and drying the heat resisting inorganic oxide carrier, wherein the impregnating process comprises a step that a mixture of the impregnating solution and the heat resisting inorganic oxide carrier are radiated by ultrasonic waves; microwave drying is adopted for drying the heat resisting inorganic oxide carrier. Due to the adoption of ultrasonic wave treatment and the microwave drying, the catalyst prepared with the method provided by the present invention has hydrodesulphurization activity higher than that of the existing catalyst.
Description
Technical field
The invention relates to a kind of Hydrobon Catalyst And Its Preparation Method, more specifically say so about containing the Hydrobon Catalyst And Its Preparation Method of molybdenum and/or tungsten and nickel and/or cobalt.
Background technology
In recent years, for satisfying environmental protection to pernicious gas NO in the motor vehicle emission tail gas
X, SO
XStrictness restriction, countries in the world have been issued and implemented strict vapour, diesel oil standard in succession.This impels the hydrofinishing technology that turns to purpose with the distillate high-quality to be developed rapidly, and Hydrobon catalyst is wherein important and one of The key factor.
Existing Hydrobon catalyst, the normally catalyst of load regulation group vib and group VIII non-noble metal components on the heat-resistant inorganic oxide carrier.Active metal component is incorporated on the carrier from solution or suspension by methods such as dipping, ion-exchange, co-precipitation or depositions, and to obtain catalyst be the common preparation method of this class catalyst for drying and roasting again.This is wherein general with preparation method's application of dipping, heat drying and roasting again.
CN1113829A discloses a kind of preparation method who contains the Hydrobon catalyst of molybdenum, nickel metal component, this method is that alumina support is immersed in the aqueous solution that contains molybdenum, nickel of preparation in advance, room temperature-80 ℃ following the immersion 1-4 hour, after filtering 80-150 ℃ dry 2-16 hour down, then in air in 300-580 ℃ of following roasting 2-16 hour.This catalyst consist of molybdenum oxide 10-24 weight %, nickel oxide 2.6-8.8 weight %, potassium 0.3-1.5 weight %, all the other are aluminium oxide.
CN1123310A discloses a kind of Hydrodevulcanizing catalyst for hydro-carbons and preparation method.This catalyst is with the γ-Al of modified zinc oxide
2O
3Being carrier, is active component with cobalt, molybdenum, adopts cobalt molybdenum co-impregnated solution single-steeping to be prepared from: with a certain amount of CoMo co-impregnated solution impregnated carrier 1-10 hour, dried 2-6 hour in 110-150 ℃, again in 480-600 ℃ of roasting 3-8 hour.Make catalyst and consist of molybdenum oxide 5-18 weight %, cobalt oxide 1-10 weight %, zinc oxide 1-15 weight %, all the other are aluminium oxide.
Among the CN1140748A, a kind of hydrogenization catalyst preparation method is disclosed.This method is to make MoO with infusion process or kneading method earlier
3Content be 6-13% contain the molybdenum carrier, the ammonia spirit with the Ni-Mo mixture floods then, in 80-160 ℃ of dry 4-16 hour, again under air atmosphere in 200-400 ℃ of roasting 2-6 hour.Catalyst consist of nickel oxide 5-30 weight %, molybdenum oxide 1-10 weight %, silica 0-15 weight and surplus Al
2O
3
CN1049800A discloses a kind of preparation method of nickel/aluminium oxide catalyst, this method is that alumina support immerses in the nickel amine aqueous solution, room temperature-60 ℃ following maintenance 1-5 hour, filter, in the time of also need flooding after the drying, and then repeated impregnations 0-6 time, twice of every dipping, must first roasting flood again, at last at 220-340 ℃ of following roasting 4-10 hour.
For active metal component such as nickel and/or cobalt, molybdenum and/or the tungsten of appointment, adopt said method to be difficult to make catalyst activity further to improve.Therefore, the new method of exploitation more and more is subject to people's attention with the preparation high-activity hydrofining catalyst.
Among the JP11033412, a kind of carried metal type Preparation of catalysts method is disclosed.This method is that the aqueous solution that will contain slaine and surfactant joins in the porous media material, places more than 1 hour under the room temperature, then uses ultrasonic generator (ultrasonic cleaner) to handle this maceration extract 2 hours.After the ultrasonic processing, with the porous media material behind this dipping in 120 ℃ of dryings 12 hours, roasting 2 hours in 500 ℃ of air atmospheres again.Porous media in the catalyst of this method preparation is a magnesia; Reactive metal is a platinum, and slaine is a chloroplatinic acid.
Though adopt existing method can produce the Hydrobon catalyst that satisfies some hydrofining technology requirements, hydrodesulfurization activity is still on the low side.
Summary of the invention
The objective of the invention is on the basis of existing technology, a kind of new more Hydrobon Catalyst And Its Preparation Method of high desulfurization activity that has is provided.
The preparation method of Hydrobon catalyst provided by the invention comprises with the dipping solution dipping heat-resistant inorganic oxide carrier that contains molybdenum and/or tungsten, nickel and/or cobalt compound and dry, wherein in dipping process, comprise a step, the described dry microwave ripple drying that adopts with the mixture of ultrasonic wave radiation impregnation solution and heat-resistant inorganic oxide carrier.
Hydrobon catalyst provided by the invention contains a kind of heat-resistant inorganic oxide carrier and the molybdenum and/or tungsten and nickel and/or the cobalt that load on this carrier, the method preparation that described catalyst is provided by the invention described above.
Owing to adopted ultrasonic wave radiation and microwave drying, the catalyst of the inventive method preparation has the hydrodesulfurization activity higher than existing catalyst.
For example, mixed solution with the n-hexane that contains the heavy % of thiophene 25 is a raw material, evaluation is by the hydrodesulfurization activity of forming same catalyst of distinct methods preparation, the result is: the hydrodesulfurization speed constant for preparing catalyst with dipping, oven drying, method of roasting is 1, then the relative speed constant by the catalyst of dipping, method for microwave drying preparation is 0.82, relative speed constant by the catalyst of dipping, ultrasonic wave radiation, oven drying, method of roasting preparation is 1.22, and is 2.1 according to the relative speed constant of the catalyst that the invention provides the method preparation.
Description of drawings
The schematic diagram of Fig. 1 probe type ultrasonic wave producer radiation impregnation.
The specific embodiment
According to method provided by the invention, in dipping process, the consumption of dipping solution is every gram heat-resistant inorganic oxide 1.5-10 milliliter, be the 2-7 milliliter under the preferable case, dip time is 1-6 hour, is preferably 2-5 hour, the time of ultrasonic wave radiation is 5-240 minute, preferred 10-120 minute, the volume ratio of ultrasonic wave radiant power and dipping solution was 0.05-20 watt/milliliter, is preferably 0.2-10 watt/milliliter.The dipping solution that carrier elimination after dipping and ultrasonic wave radiation is excessive is also used microwave drying.Catalyst was dried 4 hours down at 120 ℃, weightless less than 5 weight %.
According to method provided by the invention, the ultrasonic generator that wherein said ultrasonic wave radiation is used can be to adopt prior art for preparing or commercially available any supersonic generator, as washing trough formula supersonic generator or probe type ultrasonic wave producer.The microwave device that described microwave drying is used can be to adopt prior art for preparing or commercially available any micro-wave oven, as commercially available rotating disc type micro-wave oven.
According to method provided by the invention, described molybdenum and/or tungsten, nickel and/or the cobalt compound of containing, can be by in the soluble compound that is selected from nickeliferous and/or cobalt metal one or more, as the solution of one or more preparations in their nitrate, acetate, soluble carbon hydrochlorate, chloride, soluble complexes; Can be by being selected from the soluble compound that contains molybdenum and/or tungsten metal one or more, as the solution of one or more preparations in molybdate, tungstates, the ethyl metatungstate, can be mixed solution by the soluble compound preparation of the soluble compound of nickeliferous and/or cobalt metal and molybdenum and/or tungsten metal; Can also be by the heteropoly acid of nickeliferous and/or cobalt metal and molybdenum and/or tungsten metal or the aqueous solution of salt preparation.According to method provided by the invention, to the solvent in the solution without limits, can be organic solvent as alcohol, ether and acid, can be inorganic solvent such as water and their mixture.Preferably by the aqueous solution of nickel and/or cobalt metal soluble compound and/or molybdenum and/or the preparation of tungsten metal soluble compound.
By conciliation and control to concentration, consumption and the heat-resistant inorganic oxide consumption of dipping solution, the method for preparing specified metal content catalyst is conventionally known to one of skill in the art.In general, the consumption of the concentration of dipping solution, consumption and heat-resistant inorganic oxide should satisfy and makes in the final catalyst molybdenum and/or tungsten, nickel and/or cobalt reach desired content.Therefore, when adopting the high concentration dipping solution, described dipping can be finished in a step, when dipping solution concentration is low, described dipping can be twice or repeatedly so that in the final catalyst molybdenum and/or tungsten, nickel and/or cobalt reach desired content.
According to method provided by the invention,, wherein comprise the step of the mixture of once using ultrasonic wave radiation impregnation liquid and heat-resistant inorganic oxide carrier at least when described dipping is twice or repeatedly the time.
According to method provided by the invention, when described dipping is twice or repeatedly the time, the step that can comprise one or more dryings, to the drying means that drying steps adopted of centre without limits, it can be the conventional method drying, also can be microwave drying, the drying behind the last dipping be microwave drying.Catalyst was dried 4 hours down at 120 ℃, weightless less than 5 weight %.
According to method provided by the invention, wherein said heat-resistant inorganic oxide is selected from one or more in the various heat-resistant inorganic oxides that are commonly used for catalyst carrier and/or matrix.For example, in the optional self-alumina of described heat-resistingization thing, silica, titanium oxide, magnesia, aluminium oxide-magnesia, silica-alumina, silica-magnesia, silica-zirconia, silica-thorium oxide, silica-beryllium oxide, silica-titanium oxide, silica-zirconia, oxidation titania-zirconia, silica-alumina-thorium oxide, silica-alumina-titanium oxide, silica-alumina-magnesia, silica-alumina-zirconia, natural zeolite, the clay one or more, preferred aluminium oxide, further preferred gama-alumina.
According to method provided by the invention, being immersed in as shown in Figure 1 the device of catalyst carried out in embodiment preferred, and 1 among Fig. 1 is that transducer, 2 is reaction vessel for generator, 5 for probe, 4 for luffing bar, 3.Wherein said probe is the transmitting terminal by the sound luffing bar (also claiming speed converter) of ultrasonic transducer driving, and by the transducer ultrasonic waves transmitted, its emitting facet of process directly is radiated in the steeping liq.Porous refractory oxides and the solution that contains molybdenum and/or tungsten and nickel and/or cobalt were inserted in the reaction vessel 5 dipping 1-6 hour, in dipping process, will pop one's head in and 3 be inserted in the dipping solution that is impregnated with the porous refractory oxides, open generator 4, the volume ratio of reconciling ultrasonic wave radiant power and dipping solution is 0.2-10 watt/milliliter, radiation 10-120 minute, macerate after the ultrasonic radiation, the excessive solution of elimination and with obtaining catalyst after the micro-wave oven drying.Catalyst after microwave drying was dried 4 hours down at 120 ℃, and is weightless less than 5 weight %.
In the Hydrobon catalyst provided by the invention, molybdenum and/or tungsten and nickel and/or cobalt content are the content of hydrogenation catalyst routine, in general, according to the oxide meter and with the catalyst is benchmark, the content of molybdenum and/or tungsten is 5-40 weight %, is preferably 12-35 weight %, and the content of nickel and/or cobalt is 1-10 weight, be preferably 1-8 weight, the method preparation that described catalyst is provided by the invention described above.
The following examples will the present invention will be further described.
Example 1-3 describes and the invention provides Catalysts and its preparation method.
Example 1
Industrial gamma-aluminium oxide carrier (Chang Ling oil plant catalyst plant product) 50 grams are placed reaction vessel 5 (see figure 1)s, take by weighing ammonium metatungstate ((NH
4)
2W
4O
1318H
2O, Sichuan, chemical pure) 50 gram and nickel nitrate (Ni (NO
3)
26H
2O, Yixing, chemical pure) 23 grams are dissolved in water into 200 ml solns, solution was joined reaction vessel 5 (liquid-solid ratio of solution and gama-alumina be 4 milliliters/gram) dipping 3 hours, and will pop one's head in after 30 minutes at dipping 3 is inserted in the dipping solution that is impregnated with alumina support, opens generator 4, with ultrasonic wave radiation 30 minutes, the volume ratio of ultrasonic wave radiant power and dipping solution is 1.5 watts/milliliter, and cooling, filtration were put into micro-wave oven (trade mark Galanz WD900B) dry 15 minutes.Obtain catalyst B-1, catalyst B-1 was dried 4 hours down at 120 ℃, and weightless less than 3 weight %, its composition sees Table 1.
The hydrogenation activity constituent content adopts x-ray fluorescence spectrometry [Yang Cuiding etc., petrochemical industry analytical method (RIPP test method), Science Press, 1990, P380].
Comparative Examples 1-3 explanation Comparative Examples Catalysts and its preparation method.
Comparative Examples 1
Industrial gamma-aluminium oxide carrier (Chang Ling oil plant catalyst plant product) 50 grams are placed reaction vessel, take by weighing ammonium metatungstate (NH
4)
2W
4O
1318H
2O, Sichuan, chemical pure) 59 gram and nickel nitrate (Ni (NO
3)
26H
2O, Yixing, chemical pure) 29 grams are dissolved in water into 200 ml solns, and solution (liquid-solid ratio of solution and gama-alumina is 4 a milliliters/gram) is joined in the reaction vessel, at room temperature flood 3 hours, filter, micro-wave oven drying 15 minutes.Obtain catalyst D-1, its composition sees Table 1.
Comparative Examples 2
It is same with example 1 to feed intake, different is dipping 3 hours, to pop one's head in after 30 minutes at dipping and 3 to be inserted in the dipping solution that is impregnated with alumina support, open generator 4, with ultrasonic wave radiation 30 minutes, the volume ratio of ultrasonic wave radiant power and dipping solution is 1.5 watts/milliliter, cooling, puts into 120 ℃ of baking ovens dry 2 hours after filtering, roasting 3 hours under 450 ℃ of blowing airs then.Obtain catalyst D-2, its composition sees Table 1.
Comparative Examples 3
Feed intake with Comparative Examples 1 with, different is at room temperature to flood 3 hours, filters, the roasting 3 hours under 450 ℃ of blowing airs after 2 hours of 120 ℃ of dryings.Obtain catalyst D-3, its composition sees Table 1.
Example 2
Industrial gamma-aluminium oxide carrier (Chang Ling oil plant catalyst plant product) 50 grams are placed reaction vessel 5 (see figure 1)s, take by weighing ammonium metatungstate (NH
4)
2W
4O
1318H
2O, Sichuan, chemical pure) 26 gram and nickel nitrate (Ni (NO
3)
26H
2O, Xuan Xing, chemical pure) 9 grams are dissolved in water into 100 ml solns, solution was joined reaction vessel 5 (liquid-solid ratio of solution and gama-alumina be 2 milliliters/gram) dipping 2 hours, and will pop one's head in after 30 minutes at dipping 3 is inserted in the dipping solution that is impregnated with alumina support, opens generator 4, with ultrasonic wave radiation 60 minutes, the volume ratio of ultrasonic wave radiant power and dipping solution is 3 watts/milliliter, and cooling, filtration were put into micro-wave oven (trade mark Galanz WD900B) dry 20 minutes.Obtain catalyst B-2, catalyst B-2 was dried 4 hours down at 120 ℃, and weightless less than 2 weight %, its composition sees Table 1.
Example 3
Industrial gamma-aluminium oxide carrier (Chang Ling oil plant catalyst plant product) 50 grams are placed reaction vessel 5 (see figure 1)s, take by weighing ammonium metatungstate (NH
4)
2W
4O
1318H
2O, Sichuan, chemical pure) 35 gram and nickel nitrate (Ni (NO
3)
26H
2O, Yixing, chemical pure) 18 grams are dissolved in water into 300 ml solns, solution was joined reaction vessel 5 (liquid-solid ratio of solution and gama-alumina be 6 milliliters/gram) dipping 4 hours, and will pop one's head in after 30 minutes at dipping 3 is inserted in the dipping solution that is impregnated with alumina support, opens generator 4, with ultrasonic wave radiation 100 minutes, the volume ratio of ultrasonic wave radiant power and dipping solution is 1 watt/milliliter, and cooling, filtration were put into micro-wave oven (trade mark Galanz WD900B) dry 20 minutes.Obtain catalyst B-3, catalyst B-3 was dried 4 hours down at 120 ℃, and weightless less than 3 weight %, its composition sees Table 1.
Table 1 catalyst is formed
| Example | Numbering | WO 3, weight % | NiO, weight % |
| 1 | B-1 | 30.0 | 3.1 |
| Comparative Examples 1 | D-1 | 30.0 | 3.1 |
| Comparative Examples 2 | D-2 | 30.0 | 3.1 |
| Comparative Examples 3 | D-3 | 30.0 | 3.1 |
| 2 | B-2 | 20.8 | 2.2 |
| 3 | B-3 | 23.5 | 2.5 |
Example 4-6
The explanation of this example the invention provides the catalyst hydrogenation desulfurization performance.
Mixed solution with the n-hexane that contains the heavy % of thiophene 25 is a raw material, the hydrodesulfurization activity of evaluate catalysts B-1, B-2, B-3 on the normal pressure continuous-flow fixed-bed micro-devices of U.S. AutoclaveEngineers company, before formal charging, be that sulfurized oil carries out presulfurization to catalyst B-1, B-2, B-3 respectively with the mixed solution that contains 3% carbon disulfide and cyclohexane earlier, conditions of vulcanization is: 4.14MPa, 300 ℃, 2.5 hours, sulfurized oil feed rate 0.2 ml/min, H
2Flow velocity 400 ml/min.Cut raw material afterwards and react, reaction condition is: pressure 4MPa, and 275 ℃ of temperature, hydrogen flow rate 400 ml/min, feed rate 0.1 ml/min is reacted sample analysis after 3 hours.8000 serial gas-chromatographies with Britain Perkin-Elmer company are carried out on-line analysis.
Reaction conversion ratio is calculated as follows.
Thiophene HDS reaction is handled as pseudo first order reaction, and then reaction rate constant can be calculated as follows.
K is apparent reaction rate constant (a milliliter/gram minute) in the formula, and X is a conversion ratio, and W is catalyst weight (gram), V for obtain through correction volume flow rate (hydrogen flow rate * 0.005, ml/min).The results are shown in Table 2.
Comparative Examples 4-6
Adopt and example 4 identical reaction condition evaluate catalysts D-1, D-2, D-3 the results are shown in Table 2.
Table 2 catalyst activity evaluation result
| Example | Catalyst | Conversion ratio, % | K, milliliter/gram minute | The relative speed constant |
| 4 | B-1 | 37.99 | 0.1434 | 2.10 |
| Comparative Examples 4 | D-1 | 17.08 | 0.0563 | 0.82 |
| Comparative Examples 5 | D-2 | 24.19 | 0.0831 | 1.22 |
| Comparative Examples 6 | D-3 | 20.37 | 0.0683 | 1.00 |
| 5 | B-2 | 25.39 | 0.0879 | 1.29 |
| 6 | B-3 | 27.23 | 0.0954 | 1.40 |
Can show from the result of table 2, by the hydrodesulfurization activity activity of the catalyst that the invention provides method preparation catalyst apparently higher than existing method preparation.
Claims (13)
1, the preparation method who contains the Hydrobon catalyst of molybdenum and/or tungsten and nickel and/or cobalt, this method comprises with the dipping solution dipping heat-resistant inorganic oxide carrier that contains molybdenum and/or tungsten, nickel and/or cobalt compound and dry, it is characterized in that, comprise a step in the described dipping process, the described dry microwave drying of adopting with the mixture of ultrasonic wave radiation impregnation solution and heat-resistant inorganic oxide carrier.
According to the described method of claim 1, it is characterized in that 2, the consumption of described dipping solution is every gram heat-resistant inorganic oxide carrier 1.5-10 milliliter.
According to the described method of claim 2, it is characterized in that 3, the consumption of described dipping solution is every gram heat-resistant inorganic oxide carrier 2-7 milliliter.
According to the described method of claim 1, it is characterized in that 4, the time of described dipping is 1～6 hour, the time of ultrasonic wave radiation is 5-240 minute.
According to the described method of claim 4, it is characterized in that 5, the time of described dipping is 2-5 hour, the time of ultrasonic wave radiation is 10-120 minute.
According to the described method of claim 1, it is characterized in that 6, the ratio of described ultrasonic wave radiant power and dipping solution is 0.05-20 watt/milliliter.
According to the described method of claim 6, it is characterized in that 7, the ratio of described ultrasonic wave radiant power and dipping solution is 0.2-10 watt/milliliter.
8, according to the described method of claim 1, it is characterized in that, catalyst was dried 4 hours down at 120 ℃, weightless less than 5 weight %.
9, according to the described method of claim 1, it is characterized in that described heat-resistant inorganic oxide carrier is selected from aluminium oxide, silica, titanium oxide, magnesia, aluminium oxide-magnesia, silica-alumina, silica-magnesia, silica-thorium oxide, silica-beryllium oxide, silica-titanium oxide, silica-zirconia, the oxidation titania-zirconia, silica-alumina-thorium oxide, silica-alumina-titanium oxide, silica-alumina-magnesia, silica-alumina-zirconia, natural zeolite, synthesis zeolite, in non-zeolitic molecular sieves and the clay one or more.
10, according to the described method of claim 9, it is characterized in that described heat-resistant inorganic oxide carrier is selected from one or more in aluminium oxide, silica, aluminium oxide-magnesia, silica-alumina, silica-magnesia, synthesis zeolite, non-zeolite molecular sieve and the clay.
According to the described method of claim 10, it is characterized in that 11, described heat-resistant inorganic oxide carrier is an aluminium oxide.
According to the described method of claim 11, it is characterized in that 12, described aluminium oxide is a gama-alumina.
13, the Hydrobon catalyst that contains molybdenum and/or tungsten and nickel and/or cobalt, this catalyst contains a kind of heat-resistant inorganic oxide carrier and the molybdenum and/or tungsten and nickel and/or the cobalt that load on this carrier, it is characterized in that this catalyst is according to any described method preparation among the claim 1-12.
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| RU2807866C1 (en) * | 2023-04-17 | 2023-11-21 | ФЕДЕРАЛЬНОЕ ГОСУДАРСТВЕННОЕ БЮДЖЕТНОЕ УЧРЕЖДЕНИЕ НАУКИ ИНСТИТУТ ОРГАНИЧЕСКОЙ ХИМИИ им. Н.Д. ЗЕЛИНСКОГО РОССИЙСКОЙ АКАДЕМИИ НАУК (ИОХ РАН) | Method for producing nickel catalyst for liquid-phase selective hydrogenation of aromatic unsaturated hydrocarbons and nitro compounds |
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| CN109331832A (en) * | 2018-09-11 | 2019-02-15 | 中国石油天然气股份有限公司 | Hydrogenation catalyst and preparation method thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| RU2807866C1 (en) * | 2023-04-17 | 2023-11-21 | ФЕДЕРАЛЬНОЕ ГОСУДАРСТВЕННОЕ БЮДЖЕТНОЕ УЧРЕЖДЕНИЕ НАУКИ ИНСТИТУТ ОРГАНИЧЕСКОЙ ХИМИИ им. Н.Д. ЗЕЛИНСКОГО РОССИЙСКОЙ АКАДЕМИИ НАУК (ИОХ РАН) | Method for producing nickel catalyst for liquid-phase selective hydrogenation of aromatic unsaturated hydrocarbons and nitro compounds |
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