CN101722039A - Hydrogenation catalyst and preparation method thereof - Google Patents
Hydrogenation catalyst and preparation method thereof Download PDFInfo
- Publication number
- CN101722039A CN101722039A CN200810224593A CN200810224593A CN101722039A CN 101722039 A CN101722039 A CN 101722039A CN 200810224593 A CN200810224593 A CN 200810224593A CN 200810224593 A CN200810224593 A CN 200810224593A CN 101722039 A CN101722039 A CN 101722039A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- carrier
- acid
- metal
- inorganic assistant
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Abstract
The invention discloses a hydrogenation catalyst, which comprises a carrier as well as a hydrogenation active component and an organic addictive carried on the carrier, wherein the catalyst also comprises an inorganic assistant carried on the carrier. The inorganic assisting agent is selected from one or more of an III group metal, an IIB group metal, an IVB group metal, a rare-earth metal and gallium in an element periodic table. The invention also provides a preparation method of the hydrogenation catalyst. Compared with the traditional hydrogenation catalyst, the activity of the hydrogenation catalyst provided by the invention is obviously improved.
Description
Technical field
The invention relates to a kind of hydrogenation catalyst and preparation method thereof.
Background technology
In recent years, for satisfying environmental protection to pernicious gas NO in the vehicle exhaust
X, SO
XThe strictness restriction of discharging impels the developing rapidly of correlation techniques such as hydrotreating catalyst that turns to purpose with the fraction oil of petroleum high-quality.In addition, because petroleum resources day by day reduce, the coal liquefaction technology is developed, and wherein contains more nitrogen-containing compound, oxygenatedchemicals and aromatic hydrocarbons, olefinic material in the coal direct liquefaction oil, need carry out hydrotreatment equally before using; The alkene and the oxygenatedchemicals that contain in other artificial artificial oil such as coal-based and the natural gas base Fischer-Tropsch synthesis oil also need carry out hydrotreatment before carrying out upgrading.
Hydrobon catalyst is formed by alumina support supported V IB family and group VIII metal component usually.Generally speaking, for the course of reaction based on desulphurization reaction, the preferred Co of hydrogenation active metals component (Ni) of catalyst-Mo combination is main course of reaction for hydrogenation reactions such as aromatic hydrocarbons are saturated, preferred Ni-W combination.
CN1085934A discloses a kind of catalyst that is used for hydrorefining petroleum waxes, this catalyst is made up of magnesia, nickel oxide, tungsten oxide and aluminium oxide, weight with catalyst is benchmark, each components contents is: magnesia 0.1-1.9 weight %, nickel oxide 2.5-6 weight %, tungsten oxide 24-34 weight % and surplus aluminium oxide.
CN1626279A discloses a kind of preparation method of catalyst for hydrorefining distillate oil, this method comprises with carrying out drying behind the solution impregnation of alumina carrier of molybdate compound, with the solution impregnation of nickeliferous, tungsten compound and carry out drying and roasting, obtain a kind of Mo modification NiW/Al again
2O
3Catalyst.
Though said method provides the activity of hydrogenation catalyst to a certain extent, the activity of the hydrogenation catalyst that is provided by prior art is still lower.
Summary of the invention
The objective of the invention is to overcome the lower defective of catalytic activity of the hydrogenation catalyst of prior art, higher hydrogenation catalyst of a kind of catalytic activity and preparation method thereof is provided.
The invention provides a kind of hydrogenation catalyst, this catalyst contains carrier and the hydrogenation activity component and the organic additive that load on this carrier, wherein, this catalyst also contains the inorganic assistant that loads on the described carrier, and this inorganic assistant is selected from one or more in IIA family metal in the periodic table of elements, IIB family metal, IVB family metal, rare earth metal and the gallium.
The present invention also provides described hydrogenization catalyst preparation method, and this method comprises:
The aqueous solution of the presoma of inorganic assistant is contacted with described carrier, dry also roasting, so that inorganic assistant is loaded on the carrier, wherein, the presoma of described inorganic assistant is one or more in the soluble compound of IIA family metallic element, IIB family metallic element, IVB family metallic element, lanthanide element and gallium; And, the aqueous solution that will contain hydrogenation activity component predecessor and organic additive contacts with carrier, dry, roasting or not roasting, hydrogenation activity component and organic additive are incorporated on the carrier, perhaps, the aqueous solution that will contain hydrogenation activity component predecessor contacts with carrier, drying, roasting or not roasting are incorporated into the hydrogenation activity component on the carrier, the aqueous solution that will contain organic additive then contacts with catalyst carrier, drying, roasting or not roasting are incorporated into organic additive on the catalyst carrier.
Compare with existing hydrogenation catalyst, the activity of hydrogenation catalyst provided by the invention is significantly improved.For example, 360 ℃ of reaction temperatures, hydrogen dividing potential drop 6.0MPa, hydrogen to oil volume ratio 300, volume space velocity 2.0h
-1Under the condition, to a kind of refractive power (/n
D 20) be 1.5315, sulfur content is that 0.68 weight %, nitrogen content are the catalytic diesel oil of 842 μ g/g when carrying out hydrotreatment, when adopting the catalyst that the embodiment of the invention 10 provided, generates the refractive power (/n of oil
D 20) be 1.5011 (refractive power is more little, and the arene content in the oil is low more), sulfur content is reduced to 478.7 μ g/g, and nitrogen content is reduced to 146.1 μ g/g.And under same reaction condition, use the reference agent 4 according to the preparation of CN1085934A provider's method, the refractive power (/n of product
D 20) be 1.5034, sulfur content is reduced to 633.7 μ g/g, and nitrogen content is reduced to 257.0 μ g/g.
The specific embodiment
According to the present invention, described hydrogenation catalyst contains carrier and the hydrogenation activity component and the organic additive that load on this carrier, wherein, this catalyst also contains the inorganic assistant that loads on the described carrier, and this inorganic assistant is selected from one or more in IIA family metal in the periodic table of elements, IIB family metal, IVB family metal, rare earth metal and the gallium.
Total amount with described catalyst is a benchmark, and the content of described carrier can be 30-85 weight %, is preferably 40-80 weight %; The content of described organic additive can be 0.5-20 weight %, is preferably 1-15 weight %; In oxide, the content of described inorganic assistant can be 0.5-10 weight %, is preferably 0.5-6 weight %; Described hydrogenation activity components contents can be 5-60 weight %, is preferably 10-50 weight %.
Described inorganic assistant can be selected from one or more in IIA family metal in the periodic table of elements, IIB family metal, IVB family metal, rare earth metal and the gallium.Inorganic assistant can with the oxide of metal and or the form of sulfide exist.
Inorganic assistant is preferably one or more in the oxide of Mg, Zn, La, Ce, Ga and Zr.
Described inorganic assistant is two or more in the oxide of Mg, Zn, La, Ce, Ga and Zr more preferably.When containing two or more inorganic assistant, the weight ratio of any two kinds of inorganic assistants is 1: 0.1-10.According to this embodiment, can further improve the hydrogenation activity of hydrogenation catalyst.
Described inorganic assistant also is preferably one or more in the oxide of Zn, La, Ce, Ga and Zr; Two or more in the oxide of Zn, La, Ce, Ga and Zr more preferably, the weight ratio of any two kinds of inorganic assistants is 1: 0.1-10.According to this embodiment, can further improve the hydrogenation activity of hydrogenation catalyst.
Described organic additive can be oxygen-containing organic compound and/or organic compounds containing nitrogen.Preferably, this oxygen-containing organic compound is selected from one or more in ethylene glycol, glycerine, polyethylene glycol, acetate, maleic acid, oxalic acid, tartaric acid and the citric acid; Described organic compounds containing nitrogen is an aminotriacetic acid, 1,2-CDTA, ethylenediamine and/or ethylenediamine tetra-acetic acid.
Described hydrogenation activity component can be the hydrogenation activity component of routine, for example can comprise the metal component of VIII family and the metal component of group vib.The metal component of described VIII family is preferably nickel, and the metal component of described group vib is preferably molybdenum and tungsten, and by oxide, the weight ratio of nickel, molybdenum and tungsten can be 1: 0.1-10: 1-50.
Described alumina support can be in hibbsite, monohydrate alumina and the amorphous hydroted alumina one or more.
Described alumina support has the specific surface and the pore volume of general carrier routine, and for example, specific surface can be 150-300 rice
2/ restrain, be preferably 180-250 rice
2/ gram, pore volume can be 0.4-1 milliliter/restrain, be preferably 0.5-0.8 milliliter/gram.
Described alumina support can prepare by the method for routine, for example, and with moulding of alumina support predecessor and roasting.According to method provided by the invention, the moulding of described alumina support predecessor adopts conventional method to carry out, and all can as methods such as compressing tablet, spin, extrusions.For example when adopting the extrusion method, one or more alumina support predecessors can be mixed extrusion molding then with suitable quantity of water, extrusion aid and/or adhesive.Extrusion aid wherein, the kind of peptizing agent and consumption all can be the methods of this area routine.
Described hydrogenization catalyst preparation method provided by the invention comprises:
The aqueous solution of the presoma of inorganic assistant is contacted with described carrier, dry also roasting, so that inorganic assistant is loaded on the carrier, wherein, the presoma of described inorganic assistant is one or more in the soluble compound of IIA family metallic element, IIB family metallic element, IVB family metallic element, lanthanide element and gallium; And, the aqueous solution that will contain hydrogenation activity component predecessor and organic additive contacts with carrier, dry, roasting or not roasting, hydrogenation activity component and organic additive are incorporated on the carrier, perhaps, the aqueous solution that will contain hydrogenation activity component predecessor contacts with carrier, drying, roasting or not roasting are incorporated into the hydrogenation activity component on the carrier, the aqueous solution that will contain organic additive then contacts with catalyst carrier, drying, roasting or not roasting are incorporated into organic additive on the catalyst carrier.
In the process of the described hydrogenation catalyst of preparation, it is benchmark that the consumption of each material makes the total amount with catalyst, and the content of described carrier can be 30-85 weight %, is preferably 40-80 weight %; The content of described organic additive can be 0.5-20 weight %, is preferably 1-15 weight %; The content of described inorganic assistant can be 0.5-10 weight %, is preferably 0.5-6 weight %; In oxide, described hydrogenation activity components contents can be 5-60 weight %, is preferably 10-50 weight %.
Inorganic assistant the method on the carrier of loading on is comprised that the aqueous solution with the presoma of inorganic assistant contacts dry and roasting with described carrier.
Wherein, the aqueous solution that is preferably with the presoma of inorganic assistant of the method that the aqueous solution of the presoma of inorganic assistant is contacted with described carrier floods described catalyst carrier.According to hydrogenization catalyst preparation method provided by the invention, the temperature of described dipping is not particularly limited, can be all temps that maceration extract can reach.Time to dipping is not particularly limited, as long as can make the inorganic assistant presoma of aequum in the catalyst carrier load, for example, the temperature of dipping can be 15-60 ℃, and dip time can be 0.5-10 hour.
The temperature of described drying can be 80-350 ℃, is preferably 100-300 ℃; The dry time can be 0.5-24 hour, is preferably 1-12 hour.
The temperature of roasting can be 360-700 ℃, is preferably 400-650 ℃; The time of roasting can be 0.2-12 hour, is preferably 1-10 hour.
The presoma of described inorganic assistant can be in the soluble compound of IIA family metallic element, IIB family metallic element, IVB family metallic element, lanthanide element and gallium one or more, is preferably in nitrate, carbonate, subcarbonate, sulfate and the chloride of Mg, Zn, La, Ce, Ga and Zr one or more.
The presoma of described inorganic assistant is preferably one or more in nitrate, carbonate, subcarbonate, sulfate and the chloride of two or more element among Mg, Zn, La, Ce, Ga and the Zr, and the consumption of the presoma of inorganic assistant makes that the weight ratio of any two kinds of inorganic assistants is 1: 0.1-10.According to this embodiment, can further improve the hydrogenation activity of hydrogenation catalyst.
The presoma of described inorganic assistant is one or more in nitrate, carbonate, subcarbonate, sulfate and the chloride of Zn, La, Ce, Ga and Zr more preferably, and one or more in nitrate, carbonate, subcarbonate, sulfate and the chloride of two or more element among Zn, La, Ce, Ga and the Zr more preferably, the consumption of the presoma of inorganic assistant makes that the weight ratio of any two kinds of inorganic assistants is 1: 0.1-10.According to this embodiment, can further improve the hydrogenation activity of hydrogenation catalyst.
According to method provided by the invention, hydrogenation activity component and organic additive can load on the carrier simultaneously, also can step load on carrier.When step load is on carrier, preferred earlier the hydrogenation activity component being loaded on the carrier, and then organic additive is loaded on the carrier.
In the process of load hydrogenation activity component and/or organic additive, the temperature of described dipping is not particularly limited, can be all temps that maceration extract can reach.Time to dipping is not particularly limited, as long as can make the hydrogenation activity component predecessor and the organic additive of aequum in the catalyst carrier load, for example, the temperature of dipping can be 15-60 ℃, and dip time can be 0.5-10 hour.
There is no particular limitation to the condition of described drying and roasting, can be this area various dryings and roasting condition commonly used, and for example, the temperature of described drying can be 80-350 ℃, is preferably 100-300 ℃; The dry time can be 0.5-24 hour, is preferably 1-12 hour; The temperature of roasting can be 360-700 ℃, is preferably 400-650 ℃; The time of roasting can be 0.2-12 hour, is preferably 1-10 hour.
Described hydrogenation activity component predecessor can for example can comprise the soluble metal compound of at least a group VIII metal and the soluble metal compound of at least a group vib metal for the hydrogenation activity component predecessor of routine.
The kind of the soluble metal compound of described group VIII metal is conventionally known to one of skill in the art.For example, can be selected from nitrate, acetate, carbonate, subcarbonate, chloride and the soluble complexes of VIII family metal one or more.Under the preferable case, the soluble metal compound of described group VIII metal is one or more in nitrate, acetate, carbonate, subcarbonate, chloride and the soluble complexes of nickel.
The kind of the soluble compound of described group vib metal is conventionally known to one of skill in the art, under the preferable case, the soluble compound of described group vib metal comprises one or more in one or more and wolframic acid, metatungstic acid, ethyl metatungstic acid, tungstates, metatungstate and the ethyl metatungstic acid in molybdic acid, para-molybdic acid, molybdate and the paramolybdate.
The consumption of hydrogenation activity component predecessor makes that in oxide, the weight ratio of nickel, molybdenum and tungsten is 1: 0.1-10: 1-50.
According to the conventional method in this area, hydrogenization catalyst preparation method provided by the invention preferably also is included in before the use, in the presence of hydrogen, under 140-370 ℃ temperature, catalyst is carried out presulfurization with sulphur, hydrogen sulfide or sulfur-bearing raw material, this presulfurization can be carried out also can original position vulcanizing in device outside device, is translated into sulfide type.
The hydrogenation catalyst that adopts hydrogenization catalyst preparation method provided by the invention to make is applicable to hydrocarbon raw material is carried out hydrotreatment, with production high-quality hydrocarbon fraction.Described hydrocarbon raw material can be various mineral oil or artificial oil or their mixed fraction oil, as straight run gas oil, vacuum gas oil (VGO), metal removal oil, reduced crude, depitching decompression residuum, coker distillate, catalytic treatment distillate oil, shale oil, asphalt sand oil, ICL for Indirect Coal Liquefaction oil, DCL/Direct coal liquefaction wet goods.
When the hydrogenation catalyst that adopts hydrogenization catalyst preparation method provided by the invention to make is used for the hydrocarbon raw material hydrotreatment, can under the hydroprocessing technique condition of routine, use, as reaction temperature 200-650 ℃, preferred 300-510 ℃, reaction pressure 3-24MPa, preferred 4-15MPa, liquid hourly space velocity (LHSV) 0.1-23 hour
-1, hydrogen to oil volume ratio is 50-2000.
The following examples will the present invention is described further.Agents useful for same among the embodiment except that specifying, is chemically pure reagent.
Carrier used in following examples makes as follows: take by weighing 1000 gram aluminium hydrate powders (dry glue powder that Chang Ling branch company catalyst plant is produced) and 1000 gram boehmites (Shandong Aluminum Plant's production), being extruded into circumscribed circle diameter with banded extruder is 1.4 millimeters cloverleaf pattern bar, 120 ℃ of dryings 8.0 hours.Then, at blowing air, under 600 ℃ of conditions, calcination process 5.0 hours, air mass flow are 1.6 cubic metres/kilogram. hour, make carrier.
Embodiment 1
This embodiment illustrates the preparation of hydrogenation catalyst provided by the invention.
(1) get above-mentioned carrier 100.0 grams, with 88.0 milliliters of dippings of the aqueous solution that contains magnesium nitrate 11.3 grams 1.0 hours, through 120 ℃ of dryings 6.0 hours, 550 ℃ of roastings 4.0 hours.
(2) continue with 86.0 milliliters of dippings of the aqueous solution of containing ammonium molybdate 10.5 grams 1.0 hours, through 120 ℃ of dryings 6.0 hours, 450 ℃ of roastings 4.0 hours.Then, again with 84.0 milliliters of dippings of the aqueous solution of containing nickel nitrate 26.2 gram, ammonium metatungstate 36.4 grams, tartaric acid 7.5 grams 1.0 hours, 210 ℃ of dryings 4.0 hours obtain catalyst C
1Catalyst C
1Middle Mg, Mo, Ni, W and content of organics see Table 1.
Embodiment 2
This embodiment illustrates the preparation of hydrogenation catalyst provided by the invention.
(1) get above-mentioned carrier 100.0 grams, with 88.0 milliliters of dippings of the aqueous solution that contains zinc nitrate 16.4 grams 1.0 hours, through 120 ℃ of dryings 6.0 hours, 550 ℃ of roastings 4.0 hours.
(2) continue with 86.0 milliliters of dippings of the aqueous solution of containing ammonium molybdate 9.7 grams, glycerine 24.5 grams 1.0 hours, through 150 ℃ of dryings 6.0 hours.Then, again with 60.0 milliliters of dippings of the aqueous solution of containing nickel nitrate 24.1 gram, ammonium metatungstate 36.2 grams 1.0 hours, 170 ℃ of dryings 4.0 hours obtain catalyst C
2Catalyst C
2Middle Zn, Mo, Ni, W and content of organics see Table 1.
Embodiment 3
This embodiment illustrates the preparation of hydrogenation catalyst provided by the invention.
(1) get above-mentioned carrier 100.0 grams, with 88.0 milliliters of dippings of the aqueous solution that contains lanthanum nitrate 4.0 grams 1.0 hours, through 130 ℃ of dryings 4.0 hours, 460 ℃ of roastings 4.0 hours.
(2) continue with 87.0 milliliters of dippings of the aqueous solution of containing ammonium molybdate 8.7 grams 1.0 hours, through 130 ℃ of dryings 4.0 hours, 450 ℃ of roastings 4.0 hours.Then, again with 85.0 milliliters of dippings of the aqueous solution of containing nickel nitrate 18.9 gram, ammonium metatungstate 43.8 grams, ethylenediamine tetra-acetic acid 8.7 grams 1.0 hours, 210 ℃ of dryings 4.0 hours obtain catalyst C
3Catalyst C
3Middle La, Mo, Ni, W and content of organics see Table 1.
Embodiment 4
This embodiment illustrates the preparation of hydrogenation catalyst provided by the invention.
(1) get above-mentioned carrier 100.0 grams, with 88.0 milliliters of dippings of the aqueous solution that contains cerous nitrate 9.5 grams 1.0 hours, through 140 ℃ of dryings 4.0 hours, 470 ℃ of roastings 4.0 hours.
(2) continue with 88.0 milliliters of dippings of the aqueous solution of containing ammonium molybdate 6.0 grams, nickel nitrate 20.0 grams and ammonium metatungstate 59.6 grams 1.0 hours 200 ℃ of dryings 4.0 hours.Again with 72.0 milliliters of dippings of the aqueous solution of containing ethylene glycol 19.5 gram 1.0 hours, 180 ℃ of dryings 4.0 hours obtain catalyst C
4Catalyst C
4Middle Ce, Mo, Ni, W and content of organics see Table 1.
Embodiment 5
This embodiment illustrates the preparation of hydrogenation catalyst provided by the invention.
(1) get above-mentioned carrier 100.0 grams, with 88.0 milliliters of dippings of the aqueous solution that contains gallium nitrate 7.2 grams 1.0 hours, through 130 ℃ of dryings 4.0 hours, 460 ℃ of roastings 4.0 hours.
(2) continue with 87.0 milliliters of dippings of the aqueous solution of containing ammonium molybdate 2.2 grams 1.0 hours, through 130 ℃ of dryings 4.0 hours.Then, again with 86.0 milliliters of dippings of the aqueous solution of containing nickel nitrate 36.8 gram, ammonium metatungstate 74.9 grams, citric acid 8.5 grams 1.0 hours, 200 ℃ of dryings 4.0 hours obtain catalyst C
5Catalyst C
5Middle Ga, Mo, Ni, W and content of organics see Table 1.
Embodiment 6
This embodiment illustrates the preparation of hydrogenation catalyst provided by the invention.
(1) get above-mentioned carrier 100.0 grams, with 88.0 milliliters of dippings of the aqueous solution that contains zirconyl nitrate 6.8 grams 1.0 hours, through 140 ℃ of dryings 4.0 hours, 450 ℃ of roastings 4.0 hours.
(2) continue with 86.0 milliliters of dippings of the aqueous solution of containing ammonium molybdate 4.8 grams, nitrilotriacetic acid 13.3 grams 1.0 hours, through 180 ℃ of dryings 6.0 hours.Then, again with 69.0 milliliters of dippings of the aqueous solution of containing nickel nitrate 18.5 gram, ammonium metatungstate 53.1 grams 1.0 hours, 170 ℃ of dryings 4.0 hours obtain catalyst C
6Catalyst C
6Middle Zr, Mo, Ni, W and content of organics see Table 1.
Embodiment 7
This embodiment illustrates the preparation of hydrogenation catalyst provided by the invention.
Prepare catalyst C according to the method identical with embodiment 1
7, different is to contain magnesium nitrate 5.7 grams and zinc nitrate 3.2 grams in the maceration extract of step (1).Catalyst C
7Middle Mg, Zn, Mo, Ni, W and content of organics see Table 1.
Embodiment 8
This embodiment illustrates the preparation of hydrogenation catalyst provided by the invention.
Prepare catalyst C according to the method identical with embodiment 2
8, different is to contain cerous nitrate 3.8 grams and zinc nitrate 10.9 grams in the maceration extract of step (1).Catalyst C
8Middle Ce, Zn, Mo, Ni, W and content of organics see Table 1.
Embodiment 9
This embodiment illustrates the preparation of hydrogenation catalyst provided by the invention.
Prepare catalyst C according to the method identical with embodiment 3
9, different is to contain lanthanum nitrate 2.0 grams and zinc nitrate 2.8 grams in the maceration extract of step (1).Catalyst C
9Middle La, Zn, Mo, Ni, W and content of organics see Table 1.
Embodiment 10
This embodiment illustrates the preparation of hydrogenation catalyst provided by the invention.
Prepare catalyst C according to the method identical with embodiment 6
10, different is to contain zirconyl nitrate 3.4 grams and cerous nitrate 3.9 grams in the maceration extract of step (1).Catalyst C
10Middle Zr, Ce, Mo, Ni, W and content of organics see Table 1.
Embodiment 11
This embodiment illustrates the preparation of hydrogenation catalyst provided by the invention.
Prepare catalyst C according to the method identical with embodiment 3
11, different is to contain zirconyl nitrate 1.1 grams, lanthanum nitrate 1.3 grams and gallium nitrate 1.4 grams in the maceration extract of step (1).Catalyst C
11Middle Zr, La, Ga, Mo, Ni, W and content of organics see Table 1.
Comparative Examples 1
Prepare catalyst according to the method identical with embodiment 1, note is done reference agent 1, and different is aqueous tartaric acid solution dipping of no use.Mg, Mo, Ni and W content see Table 1 in the reference agent 1.
Comparative Examples 2
Prepare catalyst according to the method identical with embodiment 1, note is done reference agent 2, and different is magnesium nitrate solution dipping of no use, aqueous tartaric acid solution dipping also of no use.Mo, Ni and W content see Table 1 in the reference agent 2.
Comparative Examples 3
Prepare catalyst according to the method identical with embodiment 1, note is done reference agent 3, and different is magnesium nitrate solution dipping of no use.Mo, Ni, W and content of organics see Table 1 in the reference agent 3.
Comparative Examples 4
The method that provides according to CN1085934A prepares reference agent 4.Mg, Ni and W content see Table 1 in the reference agent 4.
Table 1
Embodiment 12-22
Embodiment 12-22 explanation embodiment of the invention 1-10 provides the hydrogenation performance of catalyst.
The catalyst activity evaluation is carried out on the continuous-flow high-pressure micro-device.Catalyst carries out presulfurization earlier to be handled.Conditions of vulcanization: sulfurized oil is CS
2Mixture (CS with cyclohexane
2Account for 5.0 weight % of this amount of the mixture), 360 ℃ of curing temperatures, the hydrogen dividing potential drop is 4.2MPa.Vulcanize after 3.0 hours, feed reaction raw materials (mixture of toluene and n-hexane, toluene account for 8.0 weight % of this amount of the mixture).The catalyst loading amount is 0.15g, and with the dilution of 1.0g quartz sand, reaction temperature is 350 ℃, and the hydrogen dividing potential drop is 4.2MPa.Sampling is analyzed after the stable reaction.
The toluene hydrogenation reaction is handled by first order reaction, the relative hydrogenation activity of catalyst with toluene in the recently expression of reaction rate constant on the catalyst with reaction rate constant in the reference agent.Catalyst micro-activity evaluation result sees Table 2.
Comparative Examples 5-8
Comparative Examples 5-8 explanation Comparative Examples 1-4 of the present invention provides the hydrogenation performance of catalyst.
According to the method identical with embodiment 12-22, measure the relative hydrogenation activity of toluene that Comparative Examples 1-4 provides catalyst respectively, the result is as shown in table 2.
Table 2
| The embodiment numbering | Catalyst | The relative hydrogenation activity of toluene |
| Embodiment 12 | ??C 1 | ??124 |
| Embodiment 13 | ??C 2 | ??128 |
| Embodiment 14 | ??C 3 | ??127 |
| Embodiment 15 | ??C 4 | ??126 |
| Embodiment 16 | ??C 5 | ??128 |
| Embodiment 17 | ??C 6 | ??130 |
| Embodiment 18 | ??C 7 | ??137 |
| Embodiment 19 | ??C 8 | ??136 |
| Embodiment 20 | ??C 9 | ??137 |
| Embodiment 21 | ??C 10 | ??140 |
| Embodiment 22 | ??C 11 | ??144 |
| Comparative Examples 5 | Reference agent 1 | ??115 |
| Comparative Examples 6 | Reference agent 2 | ??108 |
| Comparative Examples 7 | Reference agent 3 | ??117 |
| Comparative Examples 8 | Reference agent 4 | ??100 |
Can illustrate to have higher aromatic hydrogenation activity by catalyst provided by the invention by the data in the table 2.
Embodiment 23 and Comparative Examples 9
Embodiment 23 and Comparative Examples 9 further specify the reactivity worth that the invention provides catalyst.
Adopt a kind of refractive power (n
D 20) be 1.5315, sulfur content is 0.68 weight %, nitrogen content is that the catalytic diesel oil of 842 μ g/g is a reaction raw materials, on 20mL fixed bed hydrogenation device to catalyst C
10Estimate with reference agent 4.The reaction procatalyst vulcanized 8.0 hours under 300 ℃ of conditions earlier, switched to feedstock oil afterwards, 360 ℃ of reaction temperatures, and hydrogen dividing potential drop 6.0MPa, hydrogen to oil volume ratio 300, volume space velocity 2.0h
-1React sample analysis after 12.0 hours under the condition.The results are shown in Table 3.
Table 3
| Embodiment 23 | Comparative Examples 9 | |
| Catalyst | ??C 10 | Reference agent 4 |
| Product characteristics | ||
| Refractive power (n D 20) | ??1.5011 | ??1.5034 |
| ??S/(μg.g -1) | ??478.7 | ??633.7 |
| ??N/(μg.g -1) | ??146.1 | ??257.0 |
By table 3 as seen, catalyst provided by the invention has higher hydrodesulfurization, hydrodenitrogeneration and aromatic hydrogenation reactivity than reference agent.
Claims (19)
1. hydrogenation catalyst, this catalyst contains carrier and the hydrogenation activity component and the organic additive that load on this carrier, it is characterized in that, this catalyst also contains the inorganic assistant that loads on the described carrier, and this inorganic assistant is selected from one or more in IIA family metal in the periodic table of elements, IIB family metal, IVB family metal, rare earth metal and the gallium.
2. catalyst according to claim 1, wherein, total amount with described catalyst is a benchmark, the content of described carrier is 30-85 weight %, the content of described organic additive is 0.5-20 weight %, in oxide, the content of described inorganic assistant is 0.5-10 weight %, and described hydrogenation activity components contents is 5-60 weight %.
3. catalyst according to claim 1 and 2, wherein, described inorganic assistant is one or more in the oxide of Mg, Zn, La, Ce, Ga and Zr.
4. catalyst according to claim 3, wherein, described inorganic assistant is two or more in the oxide of Mg, Zn, La, Ce, Ga and Zr, the weight ratio of any two kinds of inorganic assistants is 1: 0.1-10.
5. catalyst according to claim 1 and 2, wherein, described inorganic assistant is one or more in the oxide of Zn, La, Ce, Ga and Zr.
6. catalyst according to claim 5, wherein, described inorganic assistant is two or more in the oxide of Zn, La, Ce, Ga and Zr, the weight ratio of any two kinds of inorganic assistants is 1: 0.1-10.
7. catalyst according to claim 1 and 2, wherein, described organic additive is oxygen-containing organic compound and/or organic compounds containing nitrogen.
8. catalyst according to claim 7, wherein, described oxygen-containing organic compound is selected from one or more in ethylene glycol, glycerine, polyethylene glycol, acetate, maleic acid, oxalic acid, tartaric acid and the citric acid; Described organic compounds containing nitrogen is an aminotriacetic acid, 1,2-CDTA, ethylenediamine and/or ethylenediamine tetra-acetic acid.
9. catalyst according to claim 1 and 2, wherein, described carrier is an aluminium oxide; Described hydrogenation activity component comprises the metal component of VIII family and the metal component of group vib.
10. catalyst according to claim 9, wherein, the metal component of described VIII family is a nickel, and the metal component of described group vib is molybdenum and tungsten, and wherein, by oxide, the weight ratio of nickel, molybdenum and tungsten is 1: 0.1-10: 1-50.
11. the described hydrogenization catalyst preparation method of claim 1 is characterized in that, this method comprises:
The aqueous solution of the presoma of inorganic assistant is contacted with described carrier, dry also roasting, so that inorganic assistant is loaded on the carrier, wherein, the presoma of described inorganic assistant is one or more in the soluble compound of IIA family metallic element, IIB family metallic element, IVB family metallic element, lanthanide element and gallium; And, the aqueous solution that will contain hydrogenation activity component predecessor and organic additive contacts with carrier, dry, roasting or not roasting, hydrogenation activity component and organic additive are incorporated on the carrier, perhaps, the aqueous solution that will contain hydrogenation activity component predecessor contacts with carrier, drying, roasting or not roasting are incorporated into the hydrogenation activity component on the carrier, the aqueous solution that will contain organic additive then contacts with catalyst carrier, drying, roasting or not roasting are incorporated into organic additive on the catalyst carrier.
12. method according to claim 11, wherein, it is benchmark that the consumption of each material makes the total amount with catalyst, the content of described carrier is 30-85 weight %, the content of described organic additive is 0.5-20 weight %, the content of described inorganic assistant is 0.5-10 weight %, and in oxide, described hydrogenation activity components contents is 5-60 weight %.
13. according to claim 11 or 12 described methods, wherein, the presoma of described inorganic assistant is one or more in nitrate, carbonate, subcarbonate, sulfate and the chloride of Mg, Zn, La, Ce, Ga and Zr.
14. method according to claim 13, wherein, the presoma of described inorganic assistant is one or more in nitrate, carbonate, subcarbonate, sulfate and the chloride of Zn, La, Ce, Ga and Zr.
15. method according to claim 14, wherein, the presoma of described inorganic assistant is one or more in nitrate, carbonate, subcarbonate, sulfate and the chloride of two or more element among Zn, La, Ce, Ga and the Zr, and the consumption of the presoma of inorganic assistant makes that the weight ratio of any two kinds of inorganic assistants is 1: 0.1-10.
16. according to claim 11 or 12 described methods, wherein, described organic additive is oxygen-containing organic compound and/or organic compounds containing nitrogen.
17. method according to claim 16, wherein, described oxygen-containing organic compound is selected from one or more in ethylene glycol, glycerine, polyethylene glycol, acetate, maleic acid, oxalic acid, tartaric acid and the citric acid; Described organic compounds containing nitrogen is an aminotriacetic acid, 1,2-CDTA, ethylenediamine and/or ethylenediamine tetra-acetic acid.
18. method according to claim 11, wherein, described hydrogenation activity component predecessor comprises the soluble metal compound of at least a group VIII metal and the soluble metal compound of at least a group vib metal.
19. method according to claim 18, wherein, the soluble metal compound of described group VIII metal is one or more in the nitrate, acetate, carbonate, subcarbonate, chloride of nickel; The soluble compound of described group vib metal comprises one or more in one or more and wolframic acid, metatungstic acid, ethyl metatungstic acid, tungstates, metatungstate and the ethyl metatungstic acid in molybdic acid, para-molybdic acid, molybdate and the paramolybdate; The consumption of hydrogenation activity component predecessor makes that by oxide, the weight ratio of nickel, molybdenum and tungsten is 1: 0.1-10: 1-50.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200810224593 CN101722039B (en) | 2008-10-21 | 2008-10-21 | Hydrogenation catalyst and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200810224593 CN101722039B (en) | 2008-10-21 | 2008-10-21 | Hydrogenation catalyst and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101722039A true CN101722039A (en) | 2010-06-09 |
| CN101722039B CN101722039B (en) | 2011-08-10 |
Family
ID=42443943
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 200810224593 Active CN101722039B (en) | 2008-10-21 | 2008-10-21 | Hydrogenation catalyst and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101722039B (en) |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102284295A (en) * | 2010-06-21 | 2011-12-21 | 中国石油化工股份有限公司 | Dipping solution of hydrogenation catalyst and method for preparing hydrogenation catalyst |
| CN102658208A (en) * | 2012-04-28 | 2012-09-12 | 重庆紫光天化蛋氨酸有限责任公司 | Methyl mercaptan catalyst, and preparation method and application thereof |
| CN103055916A (en) * | 2011-10-21 | 2013-04-24 | 中国石油化工股份有限公司 | Preparation method of catalytic cracking catalyst |
| CN103769222A (en) * | 2012-10-24 | 2014-05-07 | 中国石油化工股份有限公司 | Distillate oil hydro-treatment catalyst |
| CN103769220A (en) * | 2012-10-24 | 2014-05-07 | 中国石油化工股份有限公司 | Preparation method of catalyst for distillate oil hydro-treatment |
| CN105457649A (en) * | 2015-11-17 | 2016-04-06 | 西南化工研究设计院有限公司 | A NiMo catalyst for crude-benzene hydrogenation to prepare refined benzene, a preparing method of the catalyst and applications of the catalyst |
| CN106140323A (en) * | 2015-04-15 | 2016-11-23 | 中国石油化工股份有限公司 | A kind of hydrogenation catalyst activation method and application thereof |
| CN106140308A (en) * | 2015-03-30 | 2016-11-23 | 中国石油化工股份有限公司 | A kind of hydrogenation catalyst and hydrogenation method for hydrocarbon oils |
| CN106140316A (en) * | 2015-04-15 | 2016-11-23 | 中国石油化工股份有限公司 | A kind of hydrogenation catalyst and the application in hydrocarbon oil hydrogenation thereof |
| CN115475652A (en) * | 2021-06-16 | 2022-12-16 | 中国石油化工股份有限公司 | Catalyst for alkane dehydrogenation and preparation method and application thereof |
| CN116832822A (en) * | 2023-05-26 | 2023-10-03 | 山东亿科化学有限责任公司 | Hydrogenation catalyst and preparation method and application thereof |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100415369C (en) * | 2004-08-04 | 2008-09-03 | 中国石油化工股份有限公司 | Coarse octyl alcohol liquid phase hydrogenation refining catalyst and hydrogenation reaction technique thereof |
| CN100425676C (en) * | 2005-04-29 | 2008-10-15 | 中国石油化工股份有限公司 | Hydrogenation cracking catalyst composition |
| CN100439477C (en) * | 2005-10-19 | 2008-12-03 | 中国石油化工股份有限公司 | Hydroprocessing catalyst and its uses |
-
2008
- 2008-10-21 CN CN 200810224593 patent/CN101722039B/en active Active
Cited By (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102284295B (en) * | 2010-06-21 | 2013-09-04 | 中国石油化工股份有限公司 | Dipping solution of hydrogenation catalyst and method for preparing hydrogenation catalyst |
| CN102284295A (en) * | 2010-06-21 | 2011-12-21 | 中国石油化工股份有限公司 | Dipping solution of hydrogenation catalyst and method for preparing hydrogenation catalyst |
| CN103055916B (en) * | 2011-10-21 | 2015-06-17 | 中国石油化工股份有限公司 | Preparation method of catalytic cracking catalyst |
| CN103055916A (en) * | 2011-10-21 | 2013-04-24 | 中国石油化工股份有限公司 | Preparation method of catalytic cracking catalyst |
| CN102658208A (en) * | 2012-04-28 | 2012-09-12 | 重庆紫光天化蛋氨酸有限责任公司 | Methyl mercaptan catalyst, and preparation method and application thereof |
| 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 |
| CN103769222B (en) * | 2012-10-24 | 2018-06-15 | 中国石油化工股份有限公司 | A kind of catalyst for hydrogenation of fraction oil |
| CN103769220A (en) * | 2012-10-24 | 2014-05-07 | 中国石油化工股份有限公司 | Preparation method of catalyst for distillate oil hydro-treatment |
| CN103769222A (en) * | 2012-10-24 | 2014-05-07 | 中国石油化工股份有限公司 | Distillate oil hydro-treatment catalyst |
| CN106140308A (en) * | 2015-03-30 | 2016-11-23 | 中国石油化工股份有限公司 | A kind of hydrogenation catalyst and hydrogenation method for hydrocarbon oils |
| CN106140308B (en) * | 2015-03-30 | 2019-06-14 | 中国石油化工股份有限公司 | A kind of hydrogenation catalyst and hydrogenation method for hydrocarbon oils |
| CN106140323A (en) * | 2015-04-15 | 2016-11-23 | 中国石油化工股份有限公司 | A kind of hydrogenation catalyst activation method and application thereof |
| CN106140316A (en) * | 2015-04-15 | 2016-11-23 | 中国石油化工股份有限公司 | A kind of hydrogenation catalyst and the application in hydrocarbon oil hydrogenation thereof |
| CN106140316B (en) * | 2015-04-15 | 2018-09-28 | 中国石油化工股份有限公司 | A kind of hydrogenation catalyst and its application in hydrocarbon oil hydrogenation |
| CN105457649A (en) * | 2015-11-17 | 2016-04-06 | 西南化工研究设计院有限公司 | A NiMo catalyst for crude-benzene hydrogenation to prepare refined benzene, a preparing method of the catalyst and applications of the catalyst |
| CN115475652A (en) * | 2021-06-16 | 2022-12-16 | 中国石油化工股份有限公司 | Catalyst for alkane dehydrogenation and preparation method and application thereof |
| CN116832822A (en) * | 2023-05-26 | 2023-10-03 | 山东亿科化学有限责任公司 | Hydrogenation catalyst and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101722039B (en) | 2011-08-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101722039B (en) | Hydrogenation catalyst and preparation method thereof | |
| CN100388977C (en) | Fluorinated and phosphor-contained hydrogenation catalyst with silicon oxide-alumina as carrier and its production | |
| CN100469440C (en) | Hydrogenation catalyst and production thereof | |
| CA2755448A1 (en) | An oil and polar additive impregnated composition useful in the catalytic hydroprocessing of hydrocarbons, a method of making such catalyst, and a process of using such catalyst | |
| CN105478129B (en) | A kind of hydrotreating catalyst and its application | |
| CN101152631B (en) | Selective hydrogenation desulfurizing catalyzer and method of producing the same | |
| CN1966615B (en) | Hydrogenation catalyst | |
| CN106867575A (en) | Using the selection method of hydrotreating of the sulphurized catalyst with composition requirement | |
| CN104437518A (en) | Selective hydrodesulfurization catalyst, and preparation and application thereof | |
| CN105745018A (en) | Process for preparing a hydrotreating catalyst | |
| CN100469443C (en) | Phosphor-contained hydrogenation catalyst with silicon oxide-alumin as carrier and its production | |
| CN103157482A (en) | Hydrotreatment catalyst with silicon oxide-alumina as carrier and preparation and application thereof | |
| CN103361110A (en) | Process for the selective hydrogenation of a gasoline | |
| CN103386327B (en) | A kind of catalyst for selectively hydrodesulfurizing and Synthesis and applications thereof | |
| CN100469442C (en) | Fluorinated hydrogenation catalyst with silicon oxide-alumina as carrier and its production | |
| CN1872960B (en) | Hydrogenation catalyst of containing phosphor with alumina being as carrier, and preparation | |
| CN100469444C (en) | Fluorinated and phosphor-contained hydrogenation catalyst with silicon oxide-alumina as carrier and its production | |
| CN1840618B (en) | Hydrogenation catalyst with silicon oxide-alumina as carrier and its preparation | |
| CN101306371B (en) | Selective hydrodesulfurization catalyst and its preparation method | |
| CN103285871B (en) | A kind of hydrotreating catalyst containing promoter metal component and preparation thereof and application | |
| CN103059942B (en) | Method for producing low freezing point diesel oil with excellent quality by coked gasoline and diesel oil | |
| CN106268974B (en) | A kind of activation method of hydrogenation catalyst and its application | |
| CN1276790C (en) | Catalyst in use for refining distillate oil through hydrogenation and preparation method | |
| CN104043473A (en) | Hydrocracking catalyst and use thereof | |
| JP4938178B2 (en) | Hydrocarbon hydrotreating method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |