CN1205315C - Catalyst for hydrogenation treatment of diesel oil and its preparation method - Google Patents
Catalyst for hydrogenation treatment of diesel oil and its preparation method Download PDFInfo
- Publication number
- CN1205315C CN1205315C CN 01123765 CN01123765A CN1205315C CN 1205315 C CN1205315 C CN 1205315C CN 01123765 CN01123765 CN 01123765 CN 01123765 A CN01123765 A CN 01123765A CN 1205315 C CN1205315 C CN 1205315C
- Authority
- CN
- China
- Prior art keywords
- aluminum oxide
- zeolite
- catalyzer
- oxide
- pore volume
- 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.)
- Expired - Lifetime
Links
Landscapes
- Catalysts (AREA)
Abstract
The present invention relates to a hydrotreating catalyst of diesel oil, which comprises a carrier, molybdenum and/or tungsten and nickel and/or cobalt, wherein the molybdenum and/or the tungsten and the nickel and/or the cobalt are loaded on the carrier composed of aluminum oxide and zeolite, and the weight ratio of the aluminum oxide to the zeolite is from 90:10 to 50:50. The aluminum oxide is formed by compounding microporous aluminum oxide and macroporous aluminum oxide according to the weight ratio of 75:25 to 50:50; in the microporous aluminum oxide, the volume of pores with the diameter smaller than 80 angstroms accounts for more than 95% of the total pore volume; in the macroporous aluminum oxide, the volume of pores with the diameter of 60 to 600 angstroms accounts for more than 70% of the total pore volume.
Description
Technical field
The invention relates to a kind of hydrotreating catalyst and preparation method thereof, more specifically say so about a kind of catalyst for hydrogenation treatment of diesel oil that contains molybdenum and/or tungsten and nickel and/or cobalt and preparation method thereof.
Background technology
In recent years, market increases year by year to the demand of diesel oil, and high-yield diesel oil becomes a direction of catalytic cracking process, the characteristics of catalytic cracking diesel oil are sulphur, nitrogen and aromaticity content height, and therefore, its cetane value is low, storage stability is poor, the toxic gas that discharges during burning is many, is not suitable for environmental requirement.Diesel oil is carried out hydrotreatment can remove wherein sulphur, nitrogen, reduce aromaticity content wherein, therefore, hydrotreatment is the effective ways that improve diesel oil character, and its gordian technique is a catalyzer.
Hydrotreating catalyst generally contains a kind of support of the catalyst and the molybdenum and/or tungsten component and nickel and/or the cobalt component that load on this carrier, also contain adjuvant components such as fluorine, phosphorus in some catalyzer, support of the catalyst is aluminum oxide, silicon oxide, and some catalyzer also contains zeolite.
CN1169336A discloses a kind of catalyst for hydrorefining distillate oil, it consists of the heavy % of heavy %, fluorine 1-9 of nickel oxide 1-5 heavy %, Tungsten oxide 99.999 12-35, all the other are alumina supporter, described aluminum oxide be by little porous aluminum oxide and macroporous aluminium oxide according to 75: 25-50: 50 weight ratio is composited, wherein macroporous aluminium oxide is that the pore volume in bore dia 60-600 dust hole accounts for the aluminum oxide of total pore volume more than 70%, and to be bore dia account for the aluminum oxide of total pore volume more than 95% less than the pore volume in 80 dust holes to little porous aluminum oxide.This catalyzer has higher desulfurization, nitrogen activity, but because the aromatic hydrocarbons saturability is relatively poor, is not suitable for use in catalyst for hydrogenation treatment of diesel oil.
CN1178238A discloses a kind of catalyst for hydrocracking diesel oil, and carrier that this catalyzer is made up of aluminum oxide, amorphous aluminum silicide and molecular sieve and the hydrogenation active metals that loads on this carrier are formed WO in the catalyzer
3Content be that the content of 10-30 heavy %, NiO is that the content of the heavy % of 2-15, molecular sieve is that the content of the heavy % of 5-45, aluminum oxide is that the content of the heavy % of 30-70, amorphous aluminum silicide is the heavy % of 5-25, described molecular sieve is a Y zeolite, its infrared total acid content is 0.5-1 mmole/gram, and lattice constant is the 2.436-2.444 nanometer.Described aluminum oxide is pore volume 0.8-1.1 milliliter/gram, surface-area 230-400 rice
2The little porous aluminum oxide of/gram.
CN1184843A discloses a kind of catalyst for hydrocracking diesel oil, and consist of aluminum oxide 40-80 heavy %, amorphous aluminum silicide 0-20 heavy %, the molecular sieve 5-30 of this catalyzer weigh %, and described molecular sieve is pore volume 0.40-0.52 milliliter/gram, specific surface 750-900 rice
2/ gram, lattice constant 2.420-2.500, the Y zeolite of silica alumina ratio 7-15, the heavy % of group vib metal content 10-30, the content of VIII family metal oxide are the heavy % of 2-15.
US5,030,780 disclose a kind of saturation process of aromatic hydroxy compound, this method has been used a kind of catalyzer, described catalyzer contains the hydrogenation metal that loads on a kind of carrier, described support of the catalyst contains a kind of zeolite and a kind of porous heat-resistant inorganic oxide, particularly contain the heat-resistant inorganic oxide that is dispersed in the silicon-aluminium in the alumina host, described zeolite comprises the various crystalline silico-alumino zeolites of known nature or synthetic, as faujusite, mordenite, the erionite zeolite, y-type zeolite, X type zeolite, the L zeolite, omega zeolite, the ZSM-4 zeolite, Beta zeolite etc.
Summary of the invention
The purpose of this invention is to provide a kind of new catalyst for hydrogenation treatment of diesel oil of better catalytic performance and preparation method thereof that has.
Catalyzer provided by the invention contains a kind of carrier and the molybdenum and/or tungsten and nickel and/or the cobalt that load on this carrier, wherein, described carrier is made up of aluminum oxide and zeolite, the weight ratio of aluminum oxide and zeolite is 90: 10-50: 50, described aluminum oxide be by little porous aluminum oxide and macroporous aluminium oxide according to 75: 25-50: the aluminum oxide that 50 weight ratio is composited, wherein, to be diameter account for the aluminum oxide of total pore volume more than 95% less than the pore volume in 80 dust holes to little porous aluminum oxide, and macroporous aluminium oxide is that the pore volume in diameter 60-600 dust hole accounts for the aluminum oxide of total pore volume more than 70%.
Preparation of catalysts method provided by the invention comprises the precursor of aluminum oxide and zeolite mixing moulding, roasting, aqueous solution dipping with nickeliferous and/or cobalt and molybdenum and/or tungsten, drying and roasting then, it is characterized in that, the precursor of the described aluminum oxide pore volume that to be bore dia account for the precursor of the little porous aluminum oxide of total pore volume more than 95% and bore dia 60-600 dust hole less than the pore volume in 80 dust holes accounts for the mixture of the precursor of the macroporous aluminium oxide of total pore volume more than 70%, aperture aluminum oxide precursor, it is 75 that the consumption of macroporous aluminium oxide precursor and zeolite makes the weight ratio that obtains medium and small porous aluminum oxide of catalyzer and macroporous aluminium oxide: 25-50: 50, and the aluminum oxide gross weight is 90 with the ratio of zeolite weight: 10-50: 50.
Compare with existing catalyst for hydrogenation treatment of diesel oil, catalyzer provided by the invention has better catalytic performance, shows that catalyzer provided by the invention not only has better hydrodesulfurization activity and denitrification activity, and has the higher aromatic hydrocarbons activity of taking off.For example, adopt the WO that contains provided by the invention
325.0 heavy %, NiO 5.0 heavy % catalyzer are 0.8963 gram per centimeter to density
3, sulphur content is that 4900ppm, nitrogen content are that the catalytic cracking diesel oil of 707ppm carries out hydrotreatment, is 360 ℃ in temperature of reaction, hydrogen dividing potential drop 3.2 MPas, liquid hourly space velocity 2.0 hours
-1, under the condition of hydrogen to oil volume ratio 350, desulfurization degree is 93.0 heavy %, and denitrification percent reaches 99.9 heavy %, and diesel oil density reduction value reaches 0.0475 gram per centimeter
3And when under similarity condition, adopting the identical existing catalyzer (support of the catalyst is the mixture of aluminum oxide, amorphous aluminum silicide and y-type zeolite) of the best metal content of performance, desulfurization degree has only 92.0 heavy %, denitrification percent has only 94.3 heavy %, and diesel oil density reduction value has only 0.0410 gram per centimeter
3, use catalyzer provided by the invention to compare with adopting existing catalyzer, diesel oil density reduction value has improved 15.9% at least.
Embodiment
According to catalyzer provided by the invention, the content of described molybdenum and/or tungsten and nickel and/or cobalt is the content of catalyst for hydrogenation treatment of diesel oil routine, in general, in oxide compound and with the catalyzer total amount is benchmark, the content of molybdenum and/or tungsten is the heavy % of 10-35, be preferably the heavy % of 18-32, the content of nickel and/or cobalt is the heavy % of 1-15, is preferably the heavy % of 3-12.Described molybdenum and/or tungsten and nickel and/or cobalt can exist with oxidation state, also can exist with sulphided state.
In the described carrier, the weight ratio of aluminum oxide and zeolite is 90: 10-50: 50, be preferably 90: 10-60: 40.
Described zeolite is selected from one or more in the catalyst for hydrogenation treatment of diesel oil zeolite commonly used, as in faujusite, mordenite, erionite zeolite, zeolite L, omega zeolite, ZSM-4 zeolite, the Beta zeolite one or more, preferred y-type zeolite, particularly preferred zeolite is that total acid content is 0.02 to less than 0.5 mmole/gram, the y-type zeolite of preferred 0.05-0.2 mmole/gram.Total acid content described here adopts pyridine adsorption infrared absorption spectrometry as described below: get the about 10 milligrams y-type zeolite self-supporting sheet of weight and pack in the vacuum heating chamber, under the vacuum of 10-3 handkerchief, in 350 ℃ of heating 3 hours, y-type zeolite self-supporting sheet is carried out surface cleaning, be cooled to 20 ℃, under 20 ℃ of temperature, feed excess pyridine, after absorption reaches balance, continue absorption 30 minutes, 10
-3Be warming up to 350 ℃ under the vacuum of handkerchief, desorption 30 minutes is cooled to 20 ℃, with its infrared absorption spectra of FTS-3000 type determination of infrared spectroscopy of BIO-RAD company production.The acid amount LB=1540cm of B acid
-1The absorbancy of absorption peak is divided by weight/1000 ε of the described zeolite self-supporting of unit surface sheet
B, the acid amount LL=1450cm of L acid
-1The absorbancy of absorption peak is divided by the weight/gram per centimeter of the described zeolite self-supporting of unit surface sheet
2)/1000 ε
L, the total acid content=LB+LL of described y-type zeolite, in the formula, 1540cm
-1The absorbancy of absorption peak is divided by the weight and the 1450cm of the described zeolite self-supporting of unit surface sheet
-1The absorbancy of absorption peak is the A/ gram per centimeter divided by the unit of the weight of the described zeolite self-supporting of unit surface sheet
2, ε
BBe B acid pyridine adsorption mole coefficient, its numerical value be 0.059 (centimetre
2/ micromole) * and A, ε
LBe L acid pyridine adsorption mole coefficient, its numerical value be 0.084 (centimetre
2/ micromole) * and A, wherein, A is the unit of absorbancy.
Can also contain the material that any material that does not influence the catalytic performance of catalyzer provided by the invention maybe can improve the catalytic performance of catalyzer provided by the invention in the catalyzer provided by the invention.Can also contain in the components such as fluorine, phosphorus, magnesium one or more as catalyzer provided by the invention.
According to Preparation of catalysts method provided by the invention, its concrete steps are as follows:
1. the preparation of carrier: precursor and zeolite that the pore volume that bore dia is accounted for precursor, the bore dia 60-600 dust hole of the little porous aluminum oxide of total pore volume more than 95% less than the pore volume in 80 dust holes accounts for the macroporous aluminium oxide of total pore volume more than 70% mix, hydrotreating catalyst forming method moulding routinely, dry then and roasting.
Wherein, it is 75 that the ratio of aperture aluminum oxide precursor and macroporous aluminium oxide precursor makes the weight ratio of medium and small porous aluminum oxide of the support of the catalyst that obtains and macroporous aluminium oxide: 25-50: 50, the consumption of aperture aluminum oxide precursor, macroporous aluminium oxide precursor and zeolite makes that the weight ratio of aluminum oxide and zeolite is 90 in the support of the catalyst: 10-50: 50, be preferably 90: 10-60: 40.
The precursor of described little porous aluminum oxide refers to generate after the roasting one or more in the various hydrated aluminum oxides of described little porous aluminum oxide, and a preferred diaspore content is greater than the hydrated aluminum oxide of 60 heavy %, and it can make with sodium metaaluminate-carbon dioxide process.The precursor of described macroporous aluminium oxide refers to generate after the roasting one or more in the various hydrated aluminum oxides of described macroporous aluminium oxide, and a preferred diaspore content is greater than the hydrated aluminum oxide of 50 heavy %, and it can make with sodium metaaluminate-Tai-Ace S 150 method.Described various hydrated aluminum oxide all can be purchased and get.
Described forming method can adopt existing various forming method, as the method for extruded moulding, the method for compression molding etc., preferably adopts the method for extruded moulding.In the extruded moulding process, can also add an amount of tackiness agent and/or extrusion aid.Described tackiness agent is that those skilled in the art are known, as various mineral acids and organic acid, particularly nitric acid, oxalic acid, citric acid etc.Described extrusion aid also is conventionally known to one of skill in the art, as various starchy materials.
The condition of described drying and roasting is conventional drying and roasting condition, can be preferably 100-150 ℃ from room temperature-200 ℃ as drying temperature.Maturing temperature can be 350-650 ℃, is preferably 400-600 ℃, and roasting time is 2-6 hour, is preferably 3-5 hour.
2. the dipping of molybdenum and/or tungsten and nickel and/or cobalt: the aqueous solution with nickel compound containing and/or cobalt compound and molybdenum compound and/or tungsten compound once or several times floods support of the catalyst, the dry and roasting that the 1st step obtained.
Wherein, described nickel, cobalt, molybdenum, tungsten compound refer to the water-soluble compound of energy separately, as nickelous nitrate, nickel acetate, Xiao Suangu, Cobaltous diacetate, ammonium molybdate, ammonium metawolframate, ammonium tungstate, ethyl ammonium metawolframate, metatungstic acid nickel etc.
Described dipping can once be finished, be about to contain the carrier that the aqueous solution dipping of nickel and/or cobalt and molybdenum and/or tungsten compound obtains, also can finish step by step, promptly use nickeliferous/and or the carrier of the solution impregnating catalyst of cobalt (or molybdenum and/or tungsten) compound, dry or moist, roasting or not roasting, again with contain molybdenum and/aqueous solution of tungsten (or nickel and/or cobalt) compound dipping.
The condition of described drying and roasting is conventional drying and roasting condition.Drying temperature is a room temperature-200 ℃, and maturing temperature can be 400-550 ℃, is preferably 450-500 ℃, and roasting time is 2-6 hour, is preferably 3-4 hour.
Catalyzer provided by the invention is especially suitable for use as the diesel oil hydroprocessing catalyzer.
The following examples will the present invention will be further described.
Example 1-6
Preparation of catalysts provided by the invention.
1. the preparation of support of the catalyst
Take by weighing precursor (first kind of hydrated aluminum oxide of little porous aluminum oxide respectively, name of product is dried pseudo-boehmite, Shandong Aluminum Plant produces, wherein a diaspore content 80 weighs %, the heavy % of gibbsite content 5, the specific surface and the pore distribution of the little porous aluminum oxide (A) that forms after 4 hours through 550 ℃ of roastings are listed in the table 1.), the precursor of macroporous aluminium oxide (second kind of hydrated aluminum oxide, name of product Chang Ling dry glue powder, Chang Ling refinery catalyst plant is produced, one diaspore content, 68 heavy %, gibbsite content 5 heavy %, the specific surface and the pore distribution of the macroporous aluminium oxide (B) that forms after 4 hours through 550 ℃ of roastings are listed in the table 1) and y-type zeolite (Chang Ling refinery catalyst plant is produced, lattice constant is 24.55 nanometers, the total acid content of measuring with preceding method is 0.1 mmole/gram), it is even to press mixed shown in the table 2, adds entry and mixes and to pinch, and is extruded into circumscribed circle diameter and is 1.4 millimeters trilobal bar, 120 ℃ of oven dry, 600 ℃ of roastings obtained support of the catalyst Z in 4 hours
1-Z
4
Table 1
| The aluminum oxide numbering | A | B |
| Specific surface, rice 2/ gram | 236 | 262 |
| Pore volume, milliliter/gram | 0.40 | 0.63 |
| Pore distribution, dust, % 20-40 40-60 60-80 80-100 100-600 | 13.0 54.1 30.6 0.8 1.5 | 0.9 19.9 49.9 15.5 13.8 |
Table 2
| Bearer number | Z 1 | Z 2 | Z 3 | Z 4 |
| The weight ratio of first and second kinds of hydrated aluminum oxides (butt) | 75∶25 | 75∶25 | 70∶30 | 50∶50 |
| The weight ratio (butt) of first and second kinds of hydrated aluminum oxide sums and zeolite | 70∶30 | 80∶20 | 70∶30 | 70∶30 |
2. the dipping of metal component
Take by weighing support of the catalyst Z respectively by the consumption shown in the table 3
1-Z
4With purity is that 98% Nickelous nitrate hexahydrate and the ammonium metatungstate solution that contains Tungsten oxide 99.999 1024.5 grams per liters mix, thin up, obtain the mixed aqueous solution of nickelous nitrate and ammonium metawolframate, wherein, purity is that 98% Nickelous nitrate hexahydrate (being called for short nickelous nitrate in the table), the ammonium metatungstate solution (being called for short ammonium metatungstate solution in the table) and the consumption of water that contains Tungsten oxide 99.999 1024.5 grams per liters are shown in Table 3.Mixed aqueous solution impregnation catalyst agent carrier Z with nickelous nitrate that obtains and ammonium metawolframate
1-Z
4, the roasting of roasting condition shown in the table 3 is pressed in 120 ℃ of oven dry, obtains catalyzer C provided by the invention
1-C
6Catalyzer C
1-C
6Middle nickel oxide and tungsten oxide content are listed in the table 4.Nickel oxide content is got by calculating in the catalyzer.
Comparative Examples 1
The preparation of reference catalyst.
Method by example 1 prepares support of the catalyst, different is not add y-type zeolite, obtains alumina supporter, takes by weighing alumina supporter 200 grams that obtain, ammonium fluoride solution dipping with 150 milliliter of 15 heavy %, 120 ℃ of oven dry, 420 ℃ of roastings 2 hours obtain the alumina supporter of fluorine-containing 5 heavy %, press the consumption of example 1 carrier and nickelous nitrate and ammonium metawolframate mixed aqueous solution, with described mixing solutions dipping fluoro-containing alumina carrier, and drying and roasting under same condition, reference catalyst B obtained
1Reference catalyst B
1Middle nickel oxide and tungsten oxide content are listed in the table 4.
Comparative Examples 2-3
The preparation of reference catalyst.
Method by example 1 prepares catalyzer, different is the mixture of using first kind of hydrated aluminum oxide and first kind of hydrated aluminum oxide of second kind of aqua oxidation aluminium substitution and second kind of hydrated aluminum oxide respectively, and described zeolite is the y-type zeolite that total acid content is 0.011 mmole/gram (Chang Ling catalyst plant product) and obtains reference catalyst B
2And B
3
Reference catalyst B
2And B
3Middle nickel oxide and tungsten oxide content are listed in the table 4.
Comparative Examples 4
The preparation of reference catalyst
Take by weighing hydrated aluminum oxide (the trade(brand)name SB of aluminum alkoxide hydrolysis method preparation, Germany Conden company produces) 95 grams and 12 gram amorphous aluminum silicides and 75 gram total acid contents are y-type zeolite (the Chang Ling catalyst plant product) mixing of 0.55 mmole/gram, adding water mixes, be extruded into circumscribed circle diameter and be 1.4 millimeters trilobal bar, 120 ℃ of oven dry, 600 ℃ of roastings 4 hours obtain support of the catalyst.
Press example 1 each material consumption, the support of the catalyst that obtains with nickelous nitrate and ammonium metawolframate mixing solutions dipping, and dry under the same conditions and roasting obtains reference catalyst B
4B
4The content of middle nickel oxide and Tungsten oxide 99.999 is listed in the table 4.
Comparative Examples 5-6
The preparation of reference catalyst
Method by example 1 prepares catalyzer, different is to use Comparative Examples 4 described hydrated aluminum oxide (trade(brand)name SB respectively, the production of Germany Conden company) mixture of first and second kinds of hydrated aluminum oxides of replacement, and be that the y-type zeolite of 0.011 mmole/gram and y-type zeolite that Comparative Examples 4 described total acid contents are 0.55 mmole/gram replace example 1 described y-type zeolite with the described total acid content of Comparative Examples 2-3 respectively, obtain reference catalyst B
5And B
6B
5And B
6The content of middle nickel oxide and Tungsten oxide 99.999 is listed in the table 4.
Table 3
| Example number | Support of the catalyst | Nickelous nitrate and ammonium metawolframate mixing solutions | Roasting condition | ||||
| Numbering | Consumption, gram | The nickelous nitrate consumption, gram | The ammonium metatungstate solution consumption, ml | Water consumption, gram | Temperature, ℃ | Time, hour | |
| 1 | Z 1 | 100 | 28.0 | 35.0 | 70.0 | 450 | 3 |
| 2 | Z 1 | 100 | 64.0 | 44.0 | 70.0 | 450 | 3 |
| 3 | Z 2 | 100 | 28.0 | 35.0 | 70.0 | 450 | 3 |
| 4 | Z 3 | 100 | 28.0 | 35.0 | 75.0 | 450 | 3 |
| 5 | Z 4 | 100 | 28.0 | 35.0 | 72.0 | 450 | 3 |
| 6 | Z 4 | 100 | 64.0 | 44.0 | 72.0 | 450 | 3 |
Table 4
| Example number | The catalyzer numbering | Nickel oxide content, heavy % | Tungsten oxide content, heavy % |
| 1 | C 1 | 5.0 | 25.0 |
| 2 | C 2 | 10.0 | 28.0 |
| 3 | C 3 | 5.0 | 25.0 |
| 4 | C 4 | 5.0 | 25.0 |
| 5 | C 5 | 5.0 | 25.0 |
| 6 | C 6 | 10.0 | 28.0 |
| Comparative Examples 1 | B 1 | 5.0 | 25.0 |
| Comparative Examples 2 | B 2 | 5.0 | 25.0 |
| Comparative Examples 3 | B 3 | 5.0 | 25.0 |
| Comparative Examples 4 | B 4 | 5.0 | 25.0 |
| Comparative Examples 5 | B 5 | 5.0 | 25.0 |
| Comparative Examples 6 | B 6 | 5.0 | 25.0 |
Example 7-12
Following example illustrates the performance of catalyzer provided by the invention.
With density is 0.8963 gram per centimeter
3, sulphur content is that 4900ppm, nitrogen content are that the catalytic cracking diesel oil of 707ppm is a raw material, estimates catalyzer C provided by the invention on the small stationary bed apparatus
1-C
6Catalytic performance, the catalyzer loading amount is 10 milliliters, reaction conditions is 360 ℃ of temperature of reaction, hydrogen dividing potential drop 3.2 MPas, liquid hourly space velocity 2.0 hours
-1, hydrogen to oil volume ratio is 350.Be worth the variation that characterizes cetane value with the reduction of diesel oil density, the results are shown in Table 5.
Comparative Examples 7-12
The catalytic performance of following Comparative Examples explanation reference catalyst.
Press the activity of the method evaluate catalysts of example 7, different is to use reference catalyst B respectively
1-B
6Replace catalyzer C
1, the results are shown in Table 5.
Table 5
| Example number | The catalyzer numbering | Desulfurization degree, heavy % | Denitrification percent, heavy % | Diesel oil density reduction value, gram per centimeter 3 |
| 7 | C 1 | 93.3 | 99.9 | 0.0475 |
| 8 | C 2 | 93.4 | 99.9 | 0.0475 |
| 9 | C 3 | 92.5 | 97.7 | 0.0461 |
| 10 | C 4 | 92.1 | 97.8 | 0.0460 |
| 11 | C 5 | 92.4 | 96.7 | 0.0466 |
| 12 | C 6 | 91.5 | 98.2 | 0.0465 |
| Comparative Examples 7 | B 1 | 93.0 | 99.5 | 0.0312 |
| Comparative Examples 8 | B 2 | 90.1 | 95.7 | 0.0357 |
| Comparative Examples 9 | B 3 | 91.1 | 92.3 | 0.0305 |
| Comparative Examples 10 | B 4 | 92.0 | 94.3 | 0.0410 |
| Comparative Examples 11 | B 5 | 90.1 | 93.5 | 0.0380 |
| Comparative Examples 12 | B 6 | 91.2 | 93.7 | 0.0401 |
The result of table 5 shows: with used aluminum oxide and zeolite is not that the catalyzer of aluminum oxide of the present invention and zeolite is compared, catalyzer provided by the invention not only has higher desulfurization, denitrification activity, and the density fall of diesel oil increases greatly, and promptly the cetane value increase rate increases greatly.Though not containing desulfurization, the denitrification activity of the disclosed catalyzer of CN1169336A of zeolite can be suitable with catalyzer of the present invention,, the reduction amplitude of diesel oil density is much smaller.This illustrates that catalyzer provided by the invention not only has higher desulfurization, denitrification activity, and has the higher aromatic hydrocarbons activity of taking off.
Example 13
This example illustrates the performance of catalyzer provided by the invention.
With density is 0.9258 gram per centimeter
3, sulphur content is that 2700ppm, nitrogen content are that 1373ppm, cetane value are that 27.3 catalytic cracking diesel oil is a raw material, evaluate catalysts C on 250 milliliters of medium-sized fixed bed devices
1Catalytic performance, reaction conditions and the results are shown in Table 6.
Comparative Examples 9
The catalytic performance of this Comparative Examples explanation reference catalyst.
Press the method evaluation of catalyst activity of example 13, the different reference catalyst B that just use
4Replace catalyzer C
1, reaction conditions and evaluation result are listed in the table 6.
Table 6
| Example number | ||||
| The catalyzer numbering | C 1 | C 1 | B 4 | B 4 |
| Temperature of reaction, ℃ | 360 | 370 | 360 | 370 |
| Reaction pressure, MPa | 6.4 | 6.4 | 6.4 | 6.4 |
| Liquid hourly space velocity, hour -1 | 1.0 | 1.0 | 1.0 | 1.0 |
| Hydrogen to oil volume ratio | 500 | 500 | 500 | 500 |
| Product density, gram per centimeter 3 | 0.8846 | 0.8783 | 0.08873 | 0.8848 |
| Desulfurization degree, heavy % | 92.5 | 93.3 | 89.1 | 92.0 |
| Denitrification percent, heavy % | 98.5 | 99.9 | 90.2 | 94.3 |
| The product cetane value | 36.7 | 37.9 | 35.4 | 36.5 |
| The cetane value increased value | 9.4 | 10.6 | 8.1 | 9.2 |
| Density reduction value, gram per centimeter 3 | 0.0412 | 0.0475 | 0.0385 | 0.0410 |
The result of table 6 shows equally: adopt catalyzer provided by the invention that described diesel oil is carried out hydrotreatment, the cetane value of desulfurization degree, denitrification percent, product, diesel oil density reduction value are all apparently higher than the situation that adopts reference catalyst.Use other reference catalyst also to obtain similar result.This proves that again catalyzer provided by the invention not only has higher desulfurization and denitrification activity, and has the higher aromatic hydrocarbons activity of taking off.
Claims (10)
1. catalyst for hydrogenation treatment of diesel oil, this catalyzer contains a kind of carrier and the molybdenum and/or tungsten and nickel and/or the cobalt that load on this carrier, it is characterized in that, described carrier is made up of aluminum oxide and zeolite, the weight ratio of aluminum oxide and zeolite is 90: 10-50: 50, described aluminum oxide be by little porous aluminum oxide and macroporous aluminium oxide according to 75: 25-50: the aluminum oxide that 50 weight ratio is composited, wherein, to be diameter account for the aluminum oxide of total pore volume more than 95% less than the pore volume in 80 dust holes to little porous aluminum oxide, and macroporous aluminium oxide is that the pore volume in diameter 60-600 dust hole accounts for the aluminum oxide of total pore volume more than 70%.
2. catalyzer according to claim 1 is characterized in that, is benchmark in oxide compound and with the catalyzer total amount, and the content of molybdenum and/or tungsten is the heavy % of 10-35, and the content of nickel and/or cobalt is the heavy % of 1-15.
3. catalyzer according to claim 2 is characterized in that, the content of molybdenum and/or tungsten is the heavy % of 18-32, and the content of nickel and/or cobalt is the heavy % of 3-12.
4. catalyzer according to claim 1 is characterized in that, the weight ratio of described aluminum oxide and zeolite is 90: 10-60: 40.
5. catalyzer according to claim 1 is characterized in that, described zeolite is a y-type zeolite.
6. catalyzer according to claim 5 is characterized in that, the total acid content of described y-type zeolite is 0.02 to less than 0.5 mmole/gram.
7. catalyzer according to claim 6 is characterized in that, the total acid content of described y-type zeolite is 0.05-0.2 mmole/gram.
8. claim 1 Preparation of catalysts method, this method comprises the precursor of aluminum oxide and zeolite mixing moulding, roasting, aqueous solution dipping with nickeliferous and/or cobalt and molybdenum and/or tungsten, drying and roasting then, it is characterized in that, the precursor of the described aluminum oxide pore volume that to be bore dia account for the precursor of the little porous aluminum oxide of total pore volume more than 95% and bore dia 60-600 dust hole less than the pore volume in 80 dust holes accounts for the mixture of the precursor of the macroporous aluminium oxide of total pore volume more than 70%, aperture aluminum oxide precursor, it is 75 that the consumption of macroporous aluminium oxide precursor and zeolite makes the weight ratio that obtains medium and small porous aluminum oxide of catalyzer and macroporous aluminium oxide: 25-50: 50, and the aluminum oxide gross weight is 90 with the ratio of zeolite weight: 10-50: 50.
9. method according to claim 8 is characterized in that, described aluminum oxide gross weight is 90 with the ratio of zeolite weight: 10-60: 40.
10. method according to claim 8 is characterized in that, the precursor of described little porous aluminum oxide is the hydrated aluminum oxide of a diaspore content greater than 60 heavy %, and the precursor of macroporous aluminium oxide is the hydrated aluminum oxide of a diaspore content greater than 50 heavy %.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 01123765 CN1205315C (en) | 2001-07-31 | 2001-07-31 | Catalyst for hydrogenation treatment of diesel oil and its preparation method |
| NO20023626A NO327439B1 (en) | 2001-07-31 | 2002-07-30 | Catalyst for hydrogen treatment of diesel oil and process for producing the catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 01123765 CN1205315C (en) | 2001-07-31 | 2001-07-31 | Catalyst for hydrogenation treatment of diesel oil and its preparation method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1400284A CN1400284A (en) | 2003-03-05 |
| CN1205315C true CN1205315C (en) | 2005-06-08 |
Family
ID=4665276
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 01123765 Expired - Lifetime CN1205315C (en) | 2001-07-31 | 2001-07-31 | Catalyst for hydrogenation treatment of diesel oil and its preparation method |
Country Status (2)
| Country | Link |
|---|---|
| CN (1) | CN1205315C (en) |
| NO (1) | NO327439B1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9469817B2 (en) | 2014-02-20 | 2016-10-18 | China Petroleum & Chemical Corporation | Hydrocracking catalyst and use of the same |
Families Citing this family (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8697598B2 (en) | 2005-04-21 | 2014-04-15 | China Petroleum & Chemical Corporation | Hydrogenation catalyst and use 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 |
| US8883669B2 (en) | 2005-04-29 | 2014-11-11 | China Petroleum & Chemical Corporation | Hydrocracking catalyst, a process for producing the same, and the use of the same |
| CN100448952C (en) * | 2005-04-29 | 2009-01-07 | 中国石油化工股份有限公司 | Hydrogenation cracking catalyst composition containing zeolite |
| CN1986747B (en) * | 2005-12-23 | 2011-06-15 | 中国石油化工股份有限公司 | Diesel oil fraction hydrogenating modification process |
| CN101144033B (en) * | 2006-09-14 | 2011-04-20 | 中国石油化工股份有限公司 | Hydrocracking catalyst and preparation thereof |
| CN101439288B (en) * | 2007-11-19 | 2010-11-10 | 中国石油天然气集团公司 | Combined aluminum oxide-based selective hydrodesulfurization catalyst and preparation method thereof |
| CN101463272B (en) * | 2007-12-20 | 2012-09-05 | 中国石油化工股份有限公司 | Method for generating diesel by hydrotreating biological oil |
| CN101757931B (en) * | 2008-12-25 | 2012-05-30 | 中国石油化工股份有限公司 | Hydrogenation catalyst, preparation method thereof and hydrocracking method |
| CN101864326B (en) * | 2009-04-15 | 2013-11-06 | 中国石油化工股份有限公司 | Hydrogenation deacidfieation method of acid-containing crude oil |
| KR101816668B1 (en) | 2009-10-22 | 2018-01-09 | 차이나 페트로리움 앤드 케미컬 코포레이션 | Catalytic conversion method for increasing cetane number barrel of diesel |
| CN102851067B (en) * | 2011-06-30 | 2015-04-29 | 中国石油化工股份有限公司 | Hydrogenation method for production of ultralow-sulfur clean diesel oil |
| CN103157487A (en) * | 2011-12-15 | 2013-06-19 | 中国石油化工股份有限公司 | Hydrogenation catalyst with silicon oxide as carrier and preparation and application thereof |
| CN103372465B (en) * | 2012-04-13 | 2015-12-02 | 中国石油天然气股份有限公司 | A kind of method of diesel oil hydrofining catalyst carrier calcination activation |
| CN103122260B (en) * | 2013-01-29 | 2015-06-03 | 沈阳三聚凯特催化剂有限公司 | Hydrofining technique of mixture of heavy benzene and absorber oil |
| WO2015167911A1 (en) * | 2014-05-01 | 2015-11-05 | Shell Oil Company | A catalyst and its use for the selective hydrodesulfurization of an olefin containing hydrocarbon feedstock |
-
2001
- 2001-07-31 CN CN 01123765 patent/CN1205315C/en not_active Expired - Lifetime
-
2002
- 2002-07-30 NO NO20023626A patent/NO327439B1/en not_active IP Right Cessation
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9469817B2 (en) | 2014-02-20 | 2016-10-18 | China Petroleum & Chemical Corporation | Hydrocracking catalyst and use of the same |
Also Published As
| Publication number | Publication date |
|---|---|
| NO20023626L (en) | 2003-02-03 |
| NO20023626D0 (en) | 2002-07-30 |
| CN1400284A (en) | 2003-03-05 |
| NO327439B1 (en) | 2009-06-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1205315C (en) | Catalyst for hydrogenation treatment of diesel oil and its preparation method | |
| CN1317368C (en) | Method for preparing lubricating oil base oil | |
| CN1872962B (en) | Hydrotreating catalyst of containing molecular sieve, and preparation method | |
| CN1796500A (en) | Alumina supporter possessing duplicate orifice, catalyst and preparation method | |
| CN1267537C (en) | Demetallization catalyst of addig hydrogen to residual oil and preparation method | |
| CN1243081C (en) | Hydrotreating catalyst and preparing method thereof | |
| CN1966615A (en) | Hydrogenation catalyst | |
| CN1769383A (en) | Distillate hydrogenation catalyst and its preparation method | |
| CN1768946A (en) | Method for preparing alumina supporter | |
| CN1191332C (en) | Reformed oil olefine saturation hydrogenation method | |
| CN1272409C (en) | Refined catalyst for fraction oil hydrogenation and its preparing method | |
| CN1169336A (en) | Refined catalyst made by distillate added with hydrogen and preparation thereof | |
| CN1690172A (en) | Hydrodemetalization catalyst for residual oil and process for preparing same | |
| CN1872960A (en) | Hydrogenation catalyst of containing phosphor with alumina being as carrier, and preparation | |
| CN107961771B (en) | Alumina carrier and preparation method thereof, and hydrofining catalyst and preparation method thereof | |
| CN1180060C (en) | Hydrogenating and demetalization catalyst and its prepn | |
| CN1184288C (en) | Method of hydrogenation demetalization for hydrocarbon oil | |
| CN1234814C (en) | Hydrogenation of distilled oil | |
| CN1689703A (en) | Alumina support with dual apertures and preparation method thereof | |
| CN1508224A (en) | Hydrocracking after-treatment catalyst and preparing method thereof | |
| CN1470608A (en) | Molecular sieve containing catalyst for deep hdyrogenation of middle distillate and its preparing method | |
| CN1163573C (en) | Selectively mercaptan-eliminating catalyst for aviation fuel and its prepn | |
| CN1257962C (en) | Process for hydrofining of fraction oil | |
| CN112717965A (en) | Hydrogenation pretreatment catalyst, and preparation method and application thereof | |
| CN1416955A (en) | Aluminia carrier and its prepn process |
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 | ||
| CX01 | Expiry of patent term | ||
| CX01 | Expiry of patent term |
Granted publication date: 20050608 |