CN1626625A - Demetallization catalyst of addig hydrogen to residual oil and preparation method - Google Patents

Demetallization catalyst of addig hydrogen to residual oil and preparation method Download PDF

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CN1626625A
CN1626625A CN 200310117322 CN200310117322A CN1626625A CN 1626625 A CN1626625 A CN 1626625A CN 200310117322 CN200310117322 CN 200310117322 CN 200310117322 A CN200310117322 A CN 200310117322A CN 1626625 A CN1626625 A CN 1626625A
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carrier
catalyzer
weight
gram
halogen
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CN1267537C (en
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胡大为
杨清河
朱立
刘滨
聂红
牛传峰
戴立顺
石亚华
李大东
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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Abstract

A hdyrocatalyst for removing metals from residual oil is composed of a macroreticular aluminium carrier and the Mo and/or W and Co and/or Ni, which are carried by said carrier. It features that said carrier contains aluminium oxide (95-99 wt%) and halogen (1-5) and has lower acidity, resulting in high demetallizing activity and low carbon deposit.

Description

A kind of residuum hydrogenating and metal-eliminating catalyst and preparation method thereof
Technical field
The invention relates to a kind of Hydrobon Catalyst And Its Preparation Method, more specifically say so about a kind of residuum hydrogenating and metal-eliminating catalyst and preparation method thereof.
Background technology
Be used for the particularly Hydrodemetalation catalyst of the higher vacuum residuum of metal content of mink cell focus, because the deposition of metallic impurity such as nickel, vanadium, cause the quick decline and the inactivation of catalyst activity easily.Have catalyzer than large pore volume and big bore dia hold metal and hold the carbon ability strong, can slow down catalyzer deactivation rate, prolonged the running period of catalyzer.
The pore structure of catalyzer is by the carrier decision that constitutes catalyzer.Therefore, preparing the carrier that has than large pore volume and big bore dia is that preparation residual oil, especially preparation are used for the key of the higher vacuum residuum Hydrodemetalation catalyst of metal content.
So-called macropore alumina supporter, be meant here can several apertures greater than a class alumina supporter of 14 nanometers.The aluminum oxide that is directly obtained by market generally can several apertures less (less than 10 nanometers), need usually could use after reaming.
CN1054393C discloses a kind of residuum hydrogenating and metal-eliminating catalyst and preparation method thereof, and this catalyzer is an active ingredient with VIII family and/or group vib metallic element, loads on a kind of large-pore alumina carrier.This carrier pore volume is 0.80-1.20ml/g (mercury penetration method), and specific surface area is 110-200m 2/ g, can reach the aperture is the 15-20 nanometer, tap density is 0.50-0.60g/ml.Its preparation method is in the pseudo-boehmite kneading process, adds physics expanding agent and chemical enlargement agent simultaneously, mixes and pinches into plastic, extruded moulding, dry, roasting makes carrier, in the spray mode active ingredient is added on the carrier again, and drying, roasting make catalyzer.
Except that pore volume and aperture, the acid content of carrier also is the important factor that influences catalyst carbon deposition.Generally speaking, the acid content of support of the catalyst is big more, intensity is high more, and the carbon deposition quantity of catalyzer is high more, stable unfavorable to catalyst activity.
Now finding, the acid content height of the macropore alumina supporter in the existing Hydrodemetalation catalyst is the carbon deposition quantity height by the shortcoming of the Hydrodemetalation catalyst of this class preparing carriers.
Summary of the invention
The objective of the invention is to overcome the existing high shortcoming of Hydrodemetalation catalyst carbon deposition quantity, a kind of new Hydrodemetalation catalyst with lower carbon deposition quantity and greater activity and preparation method thereof is provided.
Catalyzer provided by the invention contains a kind of macropore alumina supporter and the molybdenum and/or tungsten and cobalt and/or the nickel metal component that load on this carrier, it is characterized in that, described carrier contains a kind of halogen, with the carrier total amount is benchmark, this carrier contains the aluminum oxide of 95-99 weight %, in element, the halogen of 0.1-5 weight %, its acid amount is less than 0.2 mmole/gram.
Preparation of catalysts method provided by the invention is included in and introduces molybdenum and/or tungsten and nickel and/or cobalt metal component in the macropore alumina supporter, it is characterized in that, described carrier contains a kind of halogen, with the carrier total amount is benchmark, this carrier contains the aluminum oxide of 95-99 weight %, in element, the halogen of 0.1-5 weight %, its acid amount is less than 0.2 mmole/gram.
Catalyzer provided by the invention is made by the lower macropore alumina supporter load molybdenum of acid content and/or tungsten and cobalt and/or nickel metal component, and its carbon deposition quantity reduces, and has higher hydrodemetallation (HDM) activity simultaneously.
For example, be that 30.4ppm, content of vanadium are that the long residuum of 100ppm is the raw material evaluate catalysts with nickel content, carrier pore volume provided by the invention is that 0.77 milliliter/gram, specific surface are 176 meters 2/ gram, can several apertures be 15 nanometers, acid content be 0.11mmol/g contain molybdenum oxide 5.5 weight %, the catalyzer of nickel oxide 1.1 weight % reacts sampling analysis after 200 hours, coke on regenerated catalyst is 9.1%, demetallization per is 63%; Contain molybdenum oxide 5.5 weight % and existing method provides, the catalyzer of nickel oxide 1.1 weight %, its carrier pore volume are 178 meters of 0.69 milliliter/gram, specific surfaces 2/ gram, can several apertures 14 nanometers, acid content 0.22mmol/g, react sampling analysis after 200 hours, coke on regenerated catalyst is up to 11.5%, demetallization per only is 59%.
Embodiment
According to catalyzer provided by the invention, wherein said halogen is preferably fluorine, and the content of halogen is preferably 0.2-3 weight %.The acid amount of described carrier is preferably 0.05-0.2 mmole/gram.
The acid amount of carrier is used on the absorption instrument by NH at TP-5000 more 3-TPD method is measured.Concrete operations are: sample is placed the sample chamber, be cooled to 60 ℃ at 450 ℃ after 1 hour with helium purge, introduce the ammonia saturated vapo(u)r to adsorption equilibrium; Be warming up to 150 ℃ and purged 2 hours, ℃ carry out the ammonia desorption with 10 ℃/minute heat-up rate temperature programming to 750 afterwards; Ammonia behind the desorption absorbs with aqueous hydrochloric acid, uses the hydrochloric acid of aqueous sodium hydroxide solution overtitration afterwards, defines the acid amount of carrier with the amount that absorbs hydrochloric acid that ammonia is consumed.
Described carrier is by comprising a kind of hydrated aluminum oxide and expanding agent through mixing, the method of moulding and roasting makes, described expanding agent comprises a kind of organic expanding agent and a kind of halogenide, maturing temperature is 600-850 ℃, be preferably 650-800 ℃, roasting time 1-10 hour, be preferably 2-8 hour, with the carrier is benchmark, the consumption of each component makes final carrier contain the aluminum oxide of 95-99 weight %, is preferably 97-99 weight %, in element, 0.1-5 the halogen of weight %, be preferably 0.2-3 weight %, the acid amount is preferably 0.05-0.2 mmole/gram less than 0.2 mmole/gram.
Wherein said hydrated aluminum oxide is selected from one or more the mixture among hibbsite, boehmite, pseudo-boehmite and the amorphous hydroted alumina.They can be that commercially available commodity also can be by any one method preparation in the prior art.
Described organic expanding agent can be one or more in starch, synthetic cellulose, polymeric alcohol and the tensio-active agent, synthetic cellulose wherein is preferably one or more in carboxymethyl cellulose, methylcellulose gum, ethyl cellulose, the hydroxyl fiber fat alcohol polyethylene ether, polymeric alcohol is preferably one or more in polyoxyethylene glycol, poly-propyl alcohol, the polyvinyl alcohol, and it is the acrylic copolymer of 200-10000 and in the maleic acid copolymer one or more that tensio-active agent is preferably fat alcohol polyethylene ether, fatty alkanol amide and derivative thereof, molecular weight.
Described halogenide is preferably fluorochemical, for example Neutral ammonium fluoride and/or hydrofluoric acid.
Described moulding can be carried out according to a conventional method, all can as methods such as compressing tablet, spin, extrusions.For example when extrusion, described mixture can be mixed and add an amount of peptizing agent, extrusion moulding then with an amount of water.The kind of described peptizing agent and consumption all can be this area routines.
Described carrier except that having above-mentioned composition and acid amount, also have general macropore alumina supporter routine can several apertures, specific surface and pore volume.It can be preferably the 14-20 nanometer in several apertures, and pore volume is preferably 0.6-1.2 milliliter/gram, is more preferably 0.6-1 milliliter/gram, and specific surface area is preferably 150-250 rice 2/ gram is more preferably 150-200 rice 2/ gram.
The content of cobalt in the described catalyzer and/or nickel, molybdenum and/or tungsten is the content of Hydrodemetalation catalyst routine, in general, with the catalyzer is benchmark, in oxide compound, the content of cobalt and/or nickel is 0.3-8 weight %, is preferably 0.5-5 weight %, and the content of molybdenum and/or tungsten is 0.5-15 weight %, be preferably 3-15 weight %, the carrier of equal amount.
Method for preparing catalyst provided by the invention is included in to be enough to molybdenum and/or tungsten and nickel and/or cobalt metal component are deposited under the condition on the described macropore alumina supporter, with macropore alumina supporter with contain molybdenum and/or tungsten and nickel and/or the cobalt solution of metal compound contacts, for example pass through methods such as dipping, co-precipitation, preferred pickling process.Wherein, in oxide compound, the consumption of each component makes cobalt and/or the nickel of the molybdenum that contains 0.5-15 weight % in the final catalyzer and/or tungsten, 0.3-8 weight %.
Described molybdate compound is selected from one or more in the soluble compound that contains molybdenum, as in molybdenum oxide, molybdate, the paramolybdate one or more, and preferred molybdenum oxide, ammonium molybdate, ammonium paramolybdate wherein.
Described Tungstenic compound is selected from one or more in the soluble compound of tungstenic, as in tungstate, metatungstate, the ethyl metatungstate one or more, and the preferred inclined to one side tungsten ammonium of ammonium metawolframate, ethyl wherein.
Said cobalt compound is selected from one or more in the soluble compound that contains cobalt, as in the soluble complexes of Xiao Suangu, Cobaltous diacetate, cobaltous dihydroxycarbonate, cobalt chloride and cobalt one or more, is preferably Xiao Suangu, cobaltous dihydroxycarbonate.
Described nickel compound containing is selected from one or more in the nickeliferous soluble compound, as in the soluble complexes of nickelous nitrate, nickel acetate, basic nickel carbonate, nickelous chloride and nickel one or more, is preferably nickelous nitrate, basic nickel carbonate.
Catalyzer provided by the invention is made by the low macropore alumina supporter load cobalt of acid amount and/or nickel and molybdenum and/or tungsten metal component, and its carbon deposition quantity reduces, and has higher hydrodemetallation (HDM) activity simultaneously.Therefore, be particularly suitable for, comprise that raw materials such as crude oil, long residuum, vacuum residuum carry out the catalyzer use of hydrodemetallation (HDM) heavy hydrocarbon feedstocks.
Following example will the present invention will be further described.
Agents useful for same in the example except that specifying, is chemically pure reagent.
Example 1-5 explanation preparation the invention provides used macropore alumina supporter of catalyzer and preparation method thereof.
Example 1
(butt is 73% to take by weighing the dry glue powder that Chang Ling refinery catalyst plant produces, wherein pseudo-boehmite content is 68 weight %, gibbsite content is 5 weight %, surplus is an amorphous alumina) 300 grams, 9 gram sesbania powder (Lankao, Henan sesbania gum factory product) mix, 360 milliliters of the aqueous solution that add fluorinated ammonium (Tianjin chemical reagent three factory's products) 12 gram afterwards, on the twin screw banded extruder, be extruded into the trilobal bar of 1.1 millimeters of φ, wet bar through 120 ℃ of dryings after 4 hours in 700 ℃ of roastings 2 hours, obtain carrier Z1.Measure Z1 acid amount, fluorine content, specific surface, can reach aperture, pore distribution and pore volume, the results are shown in Table 1.
Fluorine content adopts x-ray fluorescence spectrometry, specific surface, can several apertures, pore distribution and pore volume adopt B E T Brunauer Emett Teller method of nitrogen adsorption at low temperature to measure.
The alumina supporter that the existing method of Comparative Examples 1-3 explanation provides.
Comparative Examples 1
Take by weighing dry glue powder (with example 1) 300 gram, 9 gram sesbania powder mix, and are extruded into the trilobal bar of 1.1 millimeters of φ on the twin screw banded extruder, wet bar through 120 ℃ of dryings after 4 hours in 700 ℃ of roastings 2 hours, obtain carrier D1.Measure D1 acid amount, fluorine content, specific surface, can several apertures, pore distribution and pore volume, the results are shown in Table 1.
Comparative Examples 2
Take by weighing dry glue powder (with example 1) 300 grams, add carbon black powder (place of production) 24 grams, the 12 gram mixing of sesbania powder, add afterwards and contain 360 milliliters of the aqueous solution that concentration is phosphoric acid 2.4 grams of 85 weight %, mix and pinched 15 minutes, on the twin screw banded extruder, be extruded into the butterfly bar of φ 1.5mm, wet bar through 120 ℃ of dryings after 4 hours in 700 ℃ of constant temperature 2 hours, carrier D2.Measure the phosphorus content of D2, sour amount, specific surface, can several apertures, pore distribution and pore volume, the results are shown in Table 1.
Phosphorus content adopts x-ray fluorescence spectrometry.
Comparative Examples 3
Take by weighing dry glue powder (with example 1) 300 gram, 9 gram sesbania powder mix, and are extruded into the trilobal bar of 1.1 millimeters of φ on the twin screw banded extruder, wet bar through 120 ℃ of dryings after 2 hours in 950 ℃ of roastings 2 hours, carrier D3.Measure D3 acid amount, specific surface, can several apertures, pore distribution and pore volume, the results are shown in Table 1.
Example 2
Take by weighing dry glue powder (with example 1) 300 grams, 12 gram polyvinyl alcohol (Chang Ling catalyst plant) mix, 360 milliliters of solution that add hydrofluoric acid containing (Beijing Chemical Plant's product) 18 gram afterwards, being extruded into external diameter on the twin screw banded extruder is 3.5 millimeters, internal diameter is 1.0 millimeters a Raschig ring shape bar, wet bar through 150 ℃ of dryings after 2 hours in 780 ℃ of roastings 2 hours, obtain carrier Z2.Measure Z2 acid amount, fluorine content, specific surface, can several apertures, pore distribution and pore volume, the results are shown in Table 1.
Example 3
(butt is 74% to take by weighing the aluminium hydrate powder that Shanxi Aluminium Plant produces, wherein pseudo-boehmite content is 82 weight %, gibbsite content is 5 weight %, surplus is an amorphous alumina) 300 grams, 9 gram sesbania powder, 9 gram methylcellulose gum mix, and add 360 milliliters of the aqueous solution of fluorinated ammonium 5 grams afterwards, are extruded into the butterfly bar of 1.5 millimeters of φ on the twin screw banded extruder, wet bar through 120 ℃ of dryings after 4 hours in 750 ℃ of constant temperature 2 hours, carrier Z3.Measure Z3 acid amount, fluorine content, specific surface, can several apertures, pore distribution and pore volume, the results are shown in Table 1.
Example 4
Adopt with example 3 same procedure to prepare carrier, the consumption of different is Neutral ammonium fluoride is 24 grams, carrier Z4.Measure Z4 acid amount, fluorine content, specific surface, can several apertures, pore distribution and pore volume, the results are shown in Table 1.
Example 5
Adopt with example 1 same procedure to prepare carrier, different is that maturing temperature is 800 ℃, gets carrier Z5.Measure Z5 acid amount, fluorine content, specific surface, can several apertures, pore distribution and pore volume, the results are shown in Table 1.
Table 1
Example ??1 Comparative Examples 1 Comparative Examples 2 Comparative Examples 3 ??2 ??3 ???4 ???5
Carrier ??Z1 ???D1 ????D2 ???D3 ??Z2 ??Z3 ???Z4 ???Z5
Specific surface, rice 2/ gram ??176 ???266 ????210 ???178 ??186 ??179 ???177 ???170
Pore volume, milliliter/gram ??0.77 ???0.7 ????0.72 ???0.69 ??0.87 ??0.71 ???0.92 ???0.8
Can several apertures, nanometer ??15 ???9 ????10 ???14 ??16 ??14 ???18 ???17
Pore size distribution % <10 nanometers ??9 ???63 ????51 ???9 ??9 ??10 ???5 ???6
The 10-20 nanometer ??75 ???30 ????39 ???79 ??77 ??78 ???80 ???77
>20 nanometers ??16 ???7 ????10 ???12 ??14 ??12 ???15 ???17
F, weight % ??2 ???/ ????P 2O 5,0.6 ???/ ??2.6 ??0.6 ???2.9 ???1.9
Acid amount/mmol/g ??0.11 ???0.26 ????0.28 ???0.22 ??0.13 ??0.15 ???0.1 ???0.08
Example 6-10 illustrates Catalysts and its preparation method provided by the invention.
Example 6
Get carrier Z1 200 grams of example 1 preparation, contain MoO with 500 milliliters 360 grams per liters, the ammonium molybdate of NiO12 grams per liter and nickelous nitrate mixing solutions dipping 1 hour filters the back in 120 ℃ of oven dry 2 hours, and 500 ℃ of roastings 4 hours obtain catalyzer C1.Molybdenum oxide among the catalyzer C1, the content of nickel oxide are listed in the table 2.
Comparative Examples 4
This Comparative Examples explanation Comparative Examples Catalysts and its preparation method.
Get carrier D3 200 grams of Comparative Examples 3 preparations, contain MoO with 500 milliliters 360 grams per liters, the ammonium molybdate of NiO 12 grams per liters and nickelous nitrate mixing solutions dipping 1 hour filters the back in 120 ℃ of oven dry 2 hours, and 500 ℃ of roastings 2 hours obtain catalyzer CD1.The molybdenum oxide among the catalyzer CD1 and the content of nickel oxide are listed in the table 2.
Example 7
Get carrier Z2 200 grams of example 2 preparations, contain MoO with 220 milliliters 360 grams per liters, the ammonium molybdate of NiO12 grams per liter and nickelous nitrate mixing solutions dipping 2 hours, in 120 ℃ of oven dry 2 hours, 550 ℃ of roastings 2 hours obtained catalyzer C2.Molybdenum oxide among the catalyzer C2, the content of nickel oxide are listed in the table 2.
Example 8
Get carrier Z3 200 grams of example 3 preparations, contain MoO with 500 milliliters 3120 grams per liters, the ammonium molybdate of NiO25 grams per liter and nickelous nitrate mixing solutions dipping 1 hour filters the back in 120 ℃ of oven dry 2 hours, and 480 ℃ of roastings 4 hours obtain catalyzer C3.Molybdenum oxide among the catalyzer C3, the content of nickel oxide are listed in the table 2.
Example 9
Get carrier Z4 200 grams of example 4 preparations, contain WO with 500 milliliters 370 grams per liters, the ammonium metawolframate of NiO28 grams per liter and nickelous nitrate mixing solutions dipping 1 hour filters the back in 120 ℃ of oven dry 2 hours, and 450 ℃ of roastings 4 hours obtain catalyzer C4.Tungsten oxide 99.999 among the catalyzer C4, the content of nickel oxide are listed in the table 2.
Example 10
Get carrier Z5 200 grams of example 5 preparations, contain MoO with 500 milliliters 350 grams per liters, the molybdic acid of CoO15 grams per liter acid ammonium and Xiao Suangu mixing solutions dipping 1 hour filter the back in 120 ℃ of oven dry 2 hours, and 480 ℃ of roastings 4 hours obtain catalyzer C5.Molybdenum oxide among the catalyzer C5, the content of cobalt oxide are listed in the table 2.
Table 2
Example number Used carrier The catalyzer numbering Metal oxide content, heavy %
????MoO 3 ???WO 3 ????NiO ??CoO
????6 ??Z1 ??C1 ????5.5 ???/ ????1.1 ??/
Comparative Examples 4 ??D3 ??CD1 ????5.5 ???/ ????1.1 ??/
????7 ??Z2 ??C2 ????7.9 ???/ ????1.8 ??/
????8 ??Z3 ??C3 ????11.2 ???/ ????2.2 ??/
????9 ??Z4 ??C4 ????/ ???6.2 ????3.0 ??/
????10 ??Z5 ??C5 ????4.8 ???/ ????/ ??1.6
Example 11-15
Example 11-15 explanation the invention provides the performance of catalyzer.
With nickel content is that 30.4ppm, content of vanadium are that the long residuum of 100ppm is a raw material, evaluate catalysts on 100 milliliters of small stationary bed bioreactors.
Catalyzer C1, C2, C3, C4, C5 are broken into the particle of diameter 2-3 millimeter, and the catalyzer loading amount is 100 milliliters.Reaction conditions is: 390 ℃ of temperature of reaction, hydrogen dividing potential drop 14 MPas, liquid hourly space velocity are 0.7 hour -1, hydrogen to oil volume ratio is 1000, reacts sampling after 200 hours.
Adopt plasma emission spectrum (AES/ICP) method to measure the content that generates nickel, vanadium in the oil, calculate demetallization per, the results are shown in table 3.
Catalyzer after estimating is cleaned twice with toluene, use toluene extracting 12 hours in the Soxhlet extraction plant again, adopt the RIPP106-90 method to measure carbon content in the catalyzer afterwards, the results are shown in table 3.
Comparative Examples 5
The performance of this Comparative Examples explanation Comparative Examples catalyzer.
According to the hydrodemetallation (HDM) performance of the method evaluate catalysts CD1 of example 11 with estimate the carbon content of rear catalyst, the results are shown in Table 3.
Table 3
Example number The catalyzer numbering Demetallization per/% Carbon content/%
????11 ????C1 ????63 ????9.1
Comparative Examples 5 ????CD1 ????59 ????11.5
????12 ????C2 ????68 ????8.9
????13 ????C3 ????72 ????9.8
????14 ????C4 ????61 ????9.4
????15 ????C5 ????60 ????10.1
Hydrogenation active metals component, the content of catalyzer C1 provided by the invention and Comparative Examples catalyzer CD1 identical (seeing Table 2), different is that the carrier that C1 adopts is carrier Z1 provided by the invention, its acid content is 0.11 mmole/gram, the carrier that CD1 adopts is existing macropore alumina supporter D3, and its acid content is 0.22 mmole/gram (seeing Table 1).Can see that by table 3 result the demetallization per of C1 exceeds 4 percentage points than CD1, and the post catalyst reaction carbon content is hanged down 2.4 percentage points.The hydrodemetallation (HDM) activity of catalyzer C3 provided by the invention is more up to 72%, and the post catalyst reaction carbon content is 9.8 only, shows that the hydrodemetallation (HDM) activity of catalyzer provided by the invention is better than existing catalyzer, has anti-carbon performance preferably simultaneously.

Claims (10)

1, a kind of residuum hydrogenating and metal-eliminating catalyst, this catalyzer contains a kind of macropore alumina supporter and the molybdenum and/or tungsten and cobalt and/or the nickel metal component that load on this carrier, it is characterized in that, described carrier contains a kind of halogen, with the carrier total amount is benchmark, and this carrier contains the aluminum oxide of 95-99 weight %, in element, 0.1-5 the halogen of weight %, its acid amount is less than 0.2 mmole/gram.
2, catalyzer according to claim 4 is characterized in that, described halogen is a fluorine, and content is 0.2-3 weight %.
3, catalyzer according to claim 1 is characterized in that, described acid amount is 0.05-0.2 mmole/gram.
4, catalyzer according to claim 1 is characterized in that, described carrier can several apertures be that 14-20 nanometer, pore volume are that 0.6-1.2 milliliter/gram, specific surface area are 150-250 rice 2/ gram.
5, catalyzer according to claim 1 is characterized in that, is benchmark in oxide compound and with the catalyzer, and described catalyzer contains the carrier of the cobalt of the molybdenum of 0.5-15 weight % and/or tungsten, 0.3-8 weight % and/or nickel, equal amount.
6, the described Preparation of catalysts method of claim 1, this method is included in and introduces molybdenum and/or tungsten and nickel and/or cobalt metal component in the macropore alumina supporter, it is characterized in that, described carrier contains a kind of halogen, with the carrier total amount is benchmark, and this carrier contains the aluminum oxide of 95-99 weight %, in element, 0.1-5 the halogen of weight %, its acid amount is less than 0.2 mmole/gram.
7, according to the described method of claim 6, it is characterized in that, in oxide compound and with the catalyzer is benchmark, and the introducing amount of described molybdenum and/or tungsten and cobalt and/or nickel metal component makes cobalt and/or the nickel of the molybdenum that contains 0.5-15 weight % in the final catalyzer and/or tungsten, 0.3-8 weight %.
8, method according to claim 6, it is characterized in that, described carrier by comprise with a kind of hydrated aluminum oxide and expanding agent through mix, the method for moulding and roasting makes, described expanding agent comprises a kind of organic expanding agent and a kind of halogenide, maturing temperature is 600-850 ℃, roasting time 1-10 hour, with the carrier is benchmark, and the consumption of each component makes final carrier contain the aluminum oxide of 95-99 weight %, in element, 0.1-5 the halogen of weight %, the acid amount is less than 0.2 mmole/gram.
9, described according to Claim 8 method is characterized in that, described maturing temperature is 650-800 ℃, and roasting time is 2-8 hour.
10, method according to claim 8 is characterized in that, described halogenide is fluorochemical.
CN 200310117322 2003-12-10 2003-12-10 Demetallization catalyst of addig hydrogen to residual oil and preparation method Expired - Lifetime CN1267537C (en)

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