CN101468309B - Method for preparing non-supported hydrogenation catalyst - Google Patents
Method for preparing non-supported hydrogenation catalyst Download PDFInfo
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- CN101468309B CN101468309B CN 200710304106 CN200710304106A CN101468309B CN 101468309 B CN101468309 B CN 101468309B CN 200710304106 CN200710304106 CN 200710304106 CN 200710304106 A CN200710304106 A CN 200710304106A CN 101468309 B CN101468309 B CN 101468309B
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Abstract
The invention provides a method for preparing a non-supported hydrogenation catalyst, wherein the method comprises the steps of allowing a solution of at least one VIII-group non-noble metal compound to be in contact with a solution of at least one VIB-group metal compound, obtaining slurry and then subjecting the slurry to hydrothermal treatment. The non-supported hydrogenation catalyst preparedby the method has larger specific surface area and pore volume and smaller in particles, thereby having higher hydrogenation activity. In addition, as no sulfide unbeneficial to environment is introduced during the preparation of the catalyst, the method has the advantages of mild reaction conditions, simple stable operation, low requirements on equipment and low cost.
Description
Technical field
The invention relates to a kind of preparation method of non-supported hydrogenation catalyst.
Background technology
Petroleum distillate especially contains sulphur, nitrogen, oxygen and metal impurities in the heavier petroleum fraction.These impurity often exist with the form of organic compound, and content is often higher.The existence of these impurity not only can influence the character of oil product, and also can discharge the pernicious gas of contaminated environment in the process of using, and under hydro condition, promptly also can reduce activity of such catalysts and life-span under the condition that hydrogen exists simultaneously.
In the hydrotreatment process that with the petroleum hydrocarbon is raw material, raw material reacts with hydrogen under high-temperature and high-pressure conditions, to deviate from the harmful substance in the raw material, and for example organic sulfur compound, organic nitrogen compound and organo-metallic compound etc.Hydrotreatment has comprised technologies such as hydrodesulfurization, hydrodenitrogeneration, hydrogenation deoxidation and aromatic hydrogenation.
Conventional hydrotreating catalyst generally is made up of carrier and reactive metal two parts.As US2873257 and EP0469675 this Preparation of catalysts method has been described.This method mainly is that the aqueous solution of the compound of reactive metal and carrier are flooded, and drying and roasting form then.Wherein used carrier is generally Woelm Alumina, Bio-sil, molecular sieve, amorphous silicic aluminium or their compound or mixture.
Along with the more and more stricter requirement of environmental regulation, hydrotreating catalyst is had higher requirement.Since in the conventional load type catalyst carrier itself not or have seldom catalytic activity, whole activity of such catalysts is relatively low.Utilize conventional load type catalyst to carry out being difficult to satisfy the requirement of environmental regulation to fuel oil after the hydrotreatment, therefore developing a kind of highly active unsupported catalyst has become a current main task.
EP0014218 discloses a kind of preparation method of unsupported catalyst, and this method comprises that the slurries of the spray-dried catalyst aqueous solution form microballoon, bear a certain amount of microballoon sufficient pressure then and form the tablet catalyst.Concrete preparation method comprises potash, two potassium chromates, oxidation alum, iron oxide, silicate, methylcellulose and the graphite that suspends in water carried out spray-drying, obtains unsupported catalyst being higher than to calcine under 500 ℃ of conditions then.Though the catalyst that adopts this method to prepare has comprised a kind of VIII family's base metal and at least a group vib metal, this catalyst activity when carrying out hydrotreatment is not high.
US4596785 discloses a kind of preparation method of hydrotreatment catalyst, and this method comprises mixes at least a metal sulfide of group vib at least and at least a VIII family metal sulfide, it is characterized in that described preparation method comprises the steps:
(a) be under the 4.5-8.0 in the pH value, in the presence of at least a water-soluble vulcanizing agent, the aqueous solution and at least a ammonium salt reaction that contains a kind of VIII family's metal and at least a group vib metal cation with at least a VIII family metal soluble salt form the co-precipitation of sulfide;
(b) from mother liquor, separate the final sediment that forms;
(c) dry described sediment; Then
(d) calcine this sediment.
US4820677 discloses amorphous sulfuration thing that a kind of preparation contains a kind of iron and has been selected from by molybdenum, the carbon monoxide-olefin polymeric of at least a metal in the group that tungsten or its mixture are formed, described Preparation of catalysts method is included under 150 ℃ at least, in the presence of vulcanizing agent and under oxygen free condition, heat the presoma of one or more salt, the time of heating is enough to form described catalyst, wherein, the presoma of described salt comprises molybdenum, the sulfo-metal salt anion of tungsten or its mixture and the cation that contains iron, wherein, the described iron that exists with cation is for by at least a neutrality, the iron ion of the nitrogenous fit chelating of polygamy position basigamy.What this method prepared is a kind of unbodied sulfide.
Above-mentioned two kinds of Preparation of catalysts all need be synthesized under the condition of sulfide and inert gas existence, thereby operating process is comparatively complicated, cost is higher, and is big for environment pollution, and the catalyst for preparing is still not ideal enough in the activity of carrying out the hydrotreatment rear catalyst.
CN1339985A discloses the method that a kind of preparation comprises the carbon monoxide-olefin polymeric of the bulk catalyst particles that contains at least a VIII family's base metal and at least two kinds of group vib metals, this method comprises mixes at least a VIII family's base metal composition and two kinds of group vib metal ingredients and react at least in the presence of protic liquid, the maintenance to small part in whole technical process of wherein at least a metal ingredient is solid-state.Though utilize the unsupported catalyst activity of this kind method preparation to increase, the actual requirement of distance still has certain gap.
Summary of the invention
The objective of the invention is to overcome the lower defective of catalytic activity that adopts the non-supported hydrogenation catalyst that existing method prepares and the preparation method that the higher non-supported hydrogenation catalyst of a kind of catalytic activity is provided.
The invention provides a kind of preparation method of non-supported hydrogenation catalyst, wherein, this method comprises that the solution with at least a VIII family non-noble metal compound contacts with at least a group vib solution of metal compound, obtains slurries, then these slurries is carried out hydrothermal treatment consists.
The whole metal of the non-supported hydrogenation catalyst that adopts method of the present invention to prepare for having the hydrotreatment activity, compare with existing non-supported hydrogenation catalyst, have higher specific area and bigger pore volume, and the catalyst granules that obtains is littler, thereby has higher hydrogenation activity.And adopt the method for hydrothermal treatment consists of the present invention, the physico-chemical parameter such as specific surface, pore volume, particle diameter that can be good at catalyst is regulated and control.In addition, in the process of preparation catalyst of the present invention, do not introduce the disadvantageous sulfide of environment, the reaction condition gentleness, simple to operate and stable, less demanding and cost is low to equipment.
Description of drawings
Fig. 1 is the XRD figure of the non-supported hydrogenation catalyst that adopts method of the present invention and prepare;
Fig. 2 schemes for the TEM of the non-supported hydrogenation catalyst that employing method of the present invention prepares.
The specific embodiment
According to the present invention, described preparation method comprises that the solution with at least a VIII family non-noble metal compound contacts with at least a group vib solution of metal compound, obtains slurries, then these slurries is carried out hydrothermal treatment consists.
According to the present invention, the solution of at least a VIII family non-noble metal compound is not particularly limited with the conditions and environment that at least a group vib solution of metal compound contacts, the condition of contact is generally normal temperature, normal pressure, and the environment of contact is generally in open environment and carries out.
Under the preferable case, in order to obtain comparatively uniform catalyst of particle diameter, the pH value of regulating described slurries is 4-12, be preferably 6-9, the method for regulating described slurry pH value can adopt existing the whole bag of tricks, as adopting acid solution, example hydrochloric acid or alkaline solution are regulated as ammoniacal liquor.For the formation of solid particle in the suspension that obtains after more helping contacting, preferably the pH value of under agitation regulating described suspension.The intensity and the time of stirring are not particularly limited, and those skilled in the art can control according to actual conditions.
To prepare the catalyst with more complete, satisfactory texture and pattern in order making, need to carry out hydrothermal treatment consists to described slurries, the condition of described hydrothermal treatment consists comprises treatment temperature, pressure and time.The temperature of described processing can be 40-220 ℃, is preferably 80-200 ℃; The pressure of handling can be for being not less than 0.007 MPa, and the pressure of described hydrothermal treatment consists is big more favourable more to described hydrothermal treatment consists, but consider energy consumption, and the pressure of described hydrothermal treatment consists is preferably the 0.008-2 MPa; The time of hydrothermal treatment consists can be 0.5-72 hour, is preferably 1-36 hour.
The pressure of described hydrothermal treatment consists can guarantee not seethe with excitement at hydrothermal treatment consists temperature low suspension liquid, under the preferable case, the hydrothermal treatment consists temperature be 40 ℃ to being generally and being not less than 0.007 MPa less than 100 ℃, the pressure handled, be preferably the 0.008-0.1 MPa; Perhaps the hydrothermal treatment consists temperature is during more than or equal to 100 ℃ to 220 ℃, and in order to prevent the boiling of solution, described processing pressure is preferably more than 0.1 MPa to 2 MPa, more preferably 0.12-2 MPa.Therefore, when hydrothermal treatment consists temperature during more than or equal to 100 ℃ to 220 ℃, in order to guarantee hydrothermal treatment consists pressure, this processing is carried out in closed environment usually.
The specific area that the catalyst that the condition of described hydrothermal treatment consists prepares the present invention records with the BET method is a 20-300 rice
2/ gram is preferably 100-300 rice
2/ gram; Pore volume is 0.1-0.7 milliliter/gram, is preferably 0.1-0.7 milliliter/gram; The primary granule diameter is the 2-50 nanometer, is preferably the 2-10 nanometer.
Preparation method according to non-supported hydrogenation catalyst provided by the invention, the solution of described VIII family non-noble metal compound and the consumption of group vib solution of metal compound make that the mol ratio of VIII family base metal and group vib metal is 0.6-1.4 in the described slurries: 1, and 0.8-1.2 more preferably: 1.
According to the present invention, the solution and the described group vib solution of metal compound of described VIII family non-noble metal compound can be the various solution of VIII family non-noble metal compound and group vib metallic compound, are generally the form of the aqueous solution.
The concentration of the solution of described VIII family non-noble metal compound and the concentration of described group vib solution of metal compound are respectively and are less than or equal to solubility VIII family's non-noble metal compound or the saturated concentration of solubility group vib metallic compound in water.
Described VIII family non-noble metal compound can be selected from one or more in any solubility VIII family non-noble metal compound; As, can be selected from nitrate, chloride and the acetate of VIII family base metal iron, cobalt, nickel one or more; Be preferably selected from cobalt nitrate, cobalt chloride, cobalt acetate, ferric nitrate, iron chloride, frerrous chloride, ferric acetate, nickel nitrate, nickel chloride and the nickel acetate one or more.
Described group vib metallic compound can be selected from one or more in any solubility group vib metallic compound; As, can be selected from metatungstic acid, wolframic acid, ethyl metatungstic acid, metatungstate, ethyl metatungstate, molybdic acid, para-molybdic acid and the molybdate one or more; Be preferably selected from metatungstic acid, wolframic acid, ammonium metatungstate, sodium tungstate, metatungstic acid potassium, ethyl metatungstic acid, ethyl ammonium metatungstate, ethyl metatungstic acid sodium, ethyl metatungstic acid potassium, molybdic acid, ammonium molybdate, sodium molybdate and the potassium molybdate one or more.
According to the present invention, this method also comprises filters product, wash and dry step and the step of product being carried out moulding.
Described filtration, washing and dry method can adopt this area the whole bag of tricks commonly used, described washing is generally washing, the condition of washing is not particularly limited, have only product washed to filtrate and get final product for neutral (being that pH value of filtrate is about 7), condition to described drying is not particularly limited, and can be this area various drying conditions commonly used, for example, the temperature of described drying can be 80-200 ℃, and the dry time can be 0.5-12 hour.
Product is carried out the forming method that method that moulding prepares finished catalyst can adopt this area routine, prepare the finished catalyst of different shape as the forming method of compressing tablet or extrusion, as bar shaped of sheet, bulk, sphere, bar shaped and hollow etc.The condition of moulding is conventionally known to one of skill in the art, here repeats no more.
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, carry 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 carried out hydrotreatment, has hydrocarbon fraction than low boiling and lower molecular weight with production.Described hydrocarbon raw material can be various heavy mineral oils or artificial oil or their mixed fraction oil, as straight run gas oil (straight run gas oil), vacuum gas oil (VGO) (vacuum gas oil), metal removal oil (demetallizedoils), reduced crude (atmospheric residue), depitching decompression residuum (deasphalted vacuumresidue), coker distillate (coker distillates), catalytic cracking distillate oil (catalytic crackingdistillates), shale oil (shale oil), asphalt sand oil (tar sand oil), liquefied coal coil (coal liquid) etc.
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 250-510 ℃, reaction pressure 3-24 MPa, preferred 4-15 MPa, volume space velocity 0.1-15 hour
-1, preferred 0.2-12 hour
-1, hydrogen to oil volume ratio 100-5000, preferred 100-1000.
The following examples will the present invention is described further.Agents useful for same among the embodiment except that specifying, is chemically pure reagent.
Embodiment 1
Present embodiment illustrates the preparation of non-supported hydrogenation catalyst provided by the invention.
With 76 gram ammonium metatungstate (NH
4)
6H
2W
12O
40Be dissolved in 1 premium on currency that to form concentration be the ammonium metatungstate aqueous solution of 0.026 mol.With 57 gram nickel chloride NiCl
26H
2O is dissolved in 1 premium on currency that to form concentration be the nickel chloride aqueous solution of 0.24 mol.Then nickel chloride aqueous solution and ammonium metatungstate aqueous solution is mixed and obtain slurries (mol ratio of metallic nickel and tungsten is 0.8: 1), and under agitation, the pH value of regulating described slurries is 8 that mixing time is 0.5 hour.Then these slurries are poured in the crystallizing kettle, under 80 ℃, 0.05 MPa pressure, placed 18 hours.After being cooled to room temperature, product is poured out crystallizing kettle, after filtration, washing product to pH value of filtrate is about 7,150 ℃ of dry back extruded mouldings, obtains catalyst C1.The specific area of this catalyst C1 that employing BET method records is 156 meters
2/ gram, pore volume are 0.17 milliliter/gram, and the primary granule diameter is 5 nanometers.
Fig. 1 is the XRD diffraction pattern of catalyst C1, and as can be seen from Figure 1, catalyst C1 is a wolframic acid nickel crystal;
Fig. 2 is the TEM figure of catalyst C1.
Embodiment 2
Present embodiment illustrates the preparation of non-supported hydrogenation catalyst provided by the invention.
Method according to embodiment 1 prepares catalyst, and different is, the temperature of hydrothermal treatment consists is 140 ℃, and pressure is 0.4 MPa, and the processing time is 26 hours.Prepare catalyst C2.The specific area of this catalyst C2 that employing BET method records is 150 meters
2/ gram, pore volume are 0.4 milliliter/gram, and the primary granule diameter is 15 nanometers.
Embodiment 3
Present embodiment illustrates the preparation of non-supported hydrogenation catalyst provided by the invention.
Method according to embodiment 1 prepares catalyst, and different is, described slurries are for being mixed the aqueous solution that the concentration that forms is 0.31 mol and restraining nitric acid nickel (NO by 72.7 with 1 premium on currency by 78.1 gram wolframic acids
3)
26H
2It is (mol ratio of metallic nickel and tungsten is 0.8: 1) that the aqueous solution of 0.25 mol obtains that O is dissolved in the concentration that forms in 1 premium on currency.Prepare catalyst C3.The specific area of this catalyst C3 that employing BET method records is 200 meters
2/ gram, pore volume are 0.5 milliliter/gram, and the primary granule diameter is 12 nanometers.
Embodiment 4
Present embodiment illustrates the preparation of non-supported hydrogenation catalyst provided by the invention.
Method according to embodiment 1 prepares catalyst, and different is that described slurries are by 26.4 gram sodium tungstate Na
2WO
42H
2O is dissolved in the aqueous solution that the concentration that forms in 1 premium on currency is 0.08 mol and by 23.8 gram cobalt chloride CoCl
26H
2It is (mol ratio of metallic cobalt and tungsten is 1.2: 1) that the aqueous solution of 0.1 mol obtains that O is dissolved in the concentration that forms in 1 premium on currency.And under agitation, the pH value of regulating these slurries is 11.The temperature of hydrothermal treatment consists is that 180 ℃, pressure are 1.1 MPas, and the processing time is 18 hours.Prepare catalyst C4.The specific area of this catalyst C4 that employing BET method records is 200 meters
2/ gram, pore volume are 0.6 milliliter/gram, and the primary granule diameter is 10 nanometers.
Present embodiment illustrates the preparation of non-supported hydrogenation catalyst provided by the invention.
Method according to embodiment 1 prepares catalyst, and different is, described slurries are for being dissolved in the aqueous solution that the concentration that forms in 1 premium on currency is 0.017 mol and by 80.8 gram ferric nitrate Fe (NO by 50.2 gram ammonium metatungstates
3)
39H
2It is (mol ratio of metallic iron and tungsten is 1: 1) that the aqueous solution of 0.2 mol obtains that O is dissolved in the concentration that forms in 1 premium on currency.And under agitation, the pH value of regulating these slurries is 6.The temperature of hydrothermal treatment consists is that 120 ℃, pressure are 0.2 MPa, and the processing time is 8 hours.Obtain catalyst C5.The specific area of this catalyst C5 that employing BET method records is 180 meters
2/ gram, pore volume are 0.5 milliliter/gram, and the primary granule diameter is 8 nanometers.
Embodiment 6
Present embodiment illustrates the preparation of non-supported hydrogenation catalyst provided by the invention.
Method according to embodiment 1 prepares catalyst, and different is that described slurries are by 17.3 gram ammonium heptamolybdate (NH
4)
6Mo
7O
244H
2O is dissolved in the aqueous solution that the concentration that forms in 1 premium on currency is 0.014 mol and by 21.9 gram nickel acetate C
4H
6NiO
44H
2It is (mol ratio of metallic nickel and metal molybdenum is 0.9: 1) that the aqueous solution of 0.088 mol obtains that O is dissolved in the concentration that forms in 1 premium on currency.And under agitation, the pH value of regulating these slurries is 6.The temperature of hydrothermal treatment consists is that 150 ℃, pressure are 0.5 MPa, and the processing time is 9 hours.Prepare catalyst C6.The specific area of this catalyst C5 that employing BET method records is 230 meters
2/ gram, pore volume are 0.5 milliliter/gram, and the primary granule diameter is 10 nanometers.
Comparative Examples 1
The preparation of the non-supported hydrogenation catalyst of this Comparative Examples explanation prior art.
Adopt industrial hydrogenation catalyst RN-10, note is reference catalyst CS1.
Comparative Examples 2
The preparation of the non-supported hydrogenation catalyst of this Comparative Examples explanation prior art.
With 1 7.65 gram ammonium heptamolybdate (NH
4)
6Mo
7O
244H
2O and 24.6 gram ammonium metatungstate (NH
4)
6H
2W
12O
40Be dissolved in 800 ml waters, obtain pH value under the room temperature and be 5.2 solution, subsequently this solution is heated to 90 ℃, obtain solution A.
35.3 gram basic nickel carbonates are suspended in 200 ml waters, suspension are heated to 90 ℃ then, obtain suspension B.
Suspension B was joined in the solution A in 10 minutes, then the gained slurries were kept 18 hours down at 90 ℃ under continuous stirring, subsequent filtration, washing product to pH value of filtrate are about 7,150 ℃ of dry back extruded mouldings, prepare reference catalyst CS2.
Comparative Examples 3
The preparation of the non-supported hydrogenation catalyst of this Comparative Examples explanation prior art.
Adopt the method for the disclosed embodiment 1 of US4596785 to prepare non-supported hydrogenation catalyst, note is reference catalyst CS3.
Comparative Examples 4
The preparation of the non-supported hydrogenation catalyst of this Comparative Examples explanation prior art.
Adopt the method for the disclosed embodiment 1 of US4820677 to prepare non-supported hydrogenation catalyst, note is reference catalyst CS4.
Embodiment 7-12
Following examples are used to estimate the catalytic activity of hydrogenation catalyst.
Adopt microreactor to estimate the catalytic activity of hydrogenation catalyst.The catalyst C1-C6 compressing tablet that embodiment 1-6 is prepared becomes graininess, sieves into the 40-60 order then.By the catalyst that the foregoing description 1-6 prepares, is that model compound carry out hydrodesulfurization reaction with the thiophene with 0.2 gram.Conditions of vulcanization contains 5 weight %CS for adopting
2N-hexane be sulfurized oil in air speed 36 hours
-1Under vulcanized 3 hours, feed rate is 0.3 ml/min, H
2Flow is 180 ml/min, and pressure is 4.2 MPas.Reaction condition is for being reaction oil with the n-hexane that contains 10 weight % thiophene, at H
2Pressure is 4.2 MPas, and volume space velocity is 12 hours
-1, feed rate is 0.2 ml/min, hydrogen to oil volume ratio is 600, begins sampling after 3 hours in reaction under 300 ℃, samples once more after 1 hour in reaction under 280 ℃.Under 300 ℃ and 280 ℃, investigate the hydrogenation activity of catalyst respectively.Hydrogenation activity refers to the conversion ratio of thiophene, i.e. desulfurization degree.The result is as shown in table 1 below.
Comparative Examples 5-8
This Comparative Examples is used to estimate the catalytic activity of hydrogenation catalyst.
According to the catalytic activity of the evaluation of the method shown in the foregoing description 7-12 hydrogenation catalyst, different is to be changed into the reference catalyst CS1-CS4 that is made by Comparative Examples 1-4 by the catalyst that the foregoing description 1-6 makes.The result is as shown in table 1 below.
Table 1
| The catalyst source | Catalyst | 300 ℃ of hydrogenation activity % | 280 ℃ of hydrogenation activity % |
| Embodiment 1 | C1 | 75.05 | 59.25 |
| Embodiment 2 | C2 | 76.68 | 60.23 |
| Embodiment 3 | C3 | 80.90 | 69.79 |
| Embodiment 4 | C4 | 60.21 | 50.01 |
| |
C5 | 63.48 | 53.40 |
| Embodiment 6 | C6 | 77.58 | 61.28 |
| Comparative Examples 1 | CS1 | 36.21 | 14.73 |
| Comparative Examples 2 | CS2 | 50.10 | 32.79 |
| Comparative Examples 3 | CS3 | 40.82 | 20.29 |
| Comparative Examples 4 | CS4 | 35.20 | 13.33 |
Data from last table 1 are compared with reference catalyst as can be seen, adopt catalyst that method provided by the invention prepares under same reaction temperature, have higher hydrogenation activity.
Claims (9)
1. the preparation method of a non-supported hydrogenation catalyst, it is characterized in that, this method comprises the solution of at least a VIII family non-noble metal compound is contacted with at least a VI B family solution of metal compound, obtain slurries, then these slurries are carried out hydrothermal treatment consists, the pH value of described slurries is 4-12.
2. method according to claim 1, wherein, the pH value of described slurries is 6-9.
3. method according to claim 1, wherein, the condition of hydrothermal treatment consists comprises that the temperature of processing is 40-220 ℃, and the pressure of processing is for being not less than 0.007 MPa, and the time of processing is 0.5-72 hour.
4. method according to claim 3, wherein, the temperature of processing is 80-200 ℃, and the pressure of processing is the 0.008-2 MPa, and the time of processing is 1-36 hour.
5. method according to claim 1, wherein, the solution of described VIII family non-noble metal compound and the consumption of VI B family solution of metal compound make that the mol ratio of VIII family base metal and VI B family metal is 0.6-1.4 in the described slurries: 1.
6. method according to claim 5, wherein, the solution of described VIII family non-noble metal compound and the consumption of VI B family solution of metal compound make that the mol ratio of VIII family base metal and VI B family metal is 0.8-1.2 in the described slurries: 1.
7. method according to claim 1, wherein, the solution of described VIII family non-noble metal compound is the aqueous solution of VIII family non-noble metal compound, described VIII family non-noble metal compound is selected from one or more in the solubility VIII family non-noble metal compound; Described VI B family solution of metal compound is the aqueous solution of VI B family metallic compound, and described VI B family metallic compound is selected from one or more in the solubility VI B family metallic compound.
8. according to claim 1 or 7 described methods, wherein, described VIII family non-noble metal compound is selected from one or more in the non-noble metal nitrate of VIII family, chloride and the acetate; Described VI B family metallic compound is selected from one or more in metatungstic acid, wolframic acid, ethyl metatungstic acid, tungstates, metatungstate, ethyl metatungstate, molybdic acid, para-molybdic acid and the molybdate.
9. method according to claim 8, wherein, described VIII family non-noble metal compound is selected from one or more in cobalt nitrate, cobalt chloride, cobalt acetate, ferric nitrate, iron chloride, frerrous chloride, ferric acetate, nickel nitrate, nickel chloride and the nickel acetate; Described VI B family metallic compound is selected from one or more in metatungstic acid, wolframic acid, ammonium metatungstate, sodium tungstate, metatungstic acid potassium, ethyl metatungstic acid, ethyl ammonium metatungstate, ethyl metatungstic acid sodium, ethyl metatungstic acid potassium, molybdic acid, ammonium molybdate, sodium molybdate and the potassium molybdate.
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