CN103285934A - Distillate oil hydrogenation deacidifcation catalyst carrier containing molecular sieve and preparation method of distillate oil hydrogenation deacidifcation catalyst carrier - Google Patents
Distillate oil hydrogenation deacidifcation catalyst carrier containing molecular sieve and preparation method of distillate oil hydrogenation deacidifcation catalyst carrier Download PDFInfo
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Abstract
The invention relates to a distillate oil hydrogenation deacidification catalyst carrier containing a molecular sieve and a preparation method of the distillate oil hydrogenation deacidification catalyst carrier. The distillate oil hydrogenation deacidification catalyst carrier containing the molecular sieve comprises the following components in percentage by weight (100%): 4-10% of magnesium metered by oxide, 5-35% of phosphorus aluminium molecular sieve and/or silicon aluminium microporous molecular sieve, 3-6 % of peptizing agent, 2-5% of poly vinyl alcohol and balance of alumina; and the molecular sieve is formed by one or more than one of molecular sieves such as APO-5, SAPO-5, SAPO-11, SAPO-31, ZSM-22, ZSM-22 and ZSM-23 or a product obtained by carrying out acid modification and/or hydrothermal modification by virtue of the molecular sieves. The preparation method of the distillate oil hydrogenation deacidification catalyst carrier comprises the following steps of: mixing and pinching pseudo-boehmite with molecular sieve dry powder, moulding, calcining, then dipping with a solution of a magnesium-containing compound, and drying and roasting after dipping; or mixing and pinching pseudo-boehmite, the molecular sieves and magnesium oxide and/or magnesium-containing compound, moulding and roasting. The hydrogenation deacidifcation catalyst carrier prepared by virtue of the catalyst carrier provided by the invention has higher activity and good hydrogen desulfurization and hydrogen denitrogenation performances.
Description
Technical field
The present invention relates to a kind of distillate hydrogenation deacidifying catalyst carrier that contains molecular sieve and preparation method thereof, be specially adapted to that heavy inferior contains acid fraction hydrogenation deacidification catalyst carrier and preparation method thereof in the petroleum refining field.
Background technology
Acidic components in the oil generally refer to aphthenic acids, other carboxylic acid, and inorganic acid, phenols, mercaptan etc., wherein aphthenic acids and other organic acid can be generically and collectively referred to as petroleum acids, and aphthenic acids content in petroleum acids is the highest.The concentration of acid or content use total acid number to represent in the oil.During total acid number (TAN) refers to and the milligram number of 1 gram crude oil or the needed potassium hydroxide of all acidic components of petroleum distillate (KOH), unit is mgKOH/g.What of acidic components in the crude oil are the size of acid value for crude oil reflected.Studies show that when the acid number in the oil surpassed 1mgKOH/g, the acid corrosion meeting was very serious; Can cause equipment corrosion when acid value for crude oil reaches 0.5mgKOH/g, in petroleum refining process, aphthenic acids directly reacts with iron, causes furnace tubing, heat exchanger and other refining equipment to corrode; Aphthenic acids can also react with the diaphragm FeS of oil equipment; make hardware expose new surface; be subjected to new corrosion, if can not in refining process, remove the acidic materials in the oil, will influence end product quality, cause equipment fault, problem such as environmental pollution.Along with the increase of the yield of acid-containing raw oil, the equipment corrosion problem that is caused by acid-containing hydrocarbon oil also more and more is subjected to people's attention.
Contain more aphthenic acids in the crude oil, corresponding each line distillate acid number mostly more than 2.0mgKOH/g, reaches as high as 10.0mgKOH/g, in order to produce the high quality of products of all size, must be removed.
The method that removes the oil middle acid substance at present mainly contains hydrogenation, alkali lye or the washing of amine alcoholic solution, solvent extraction, adsorbing separation etc.Hydrogenation deacidification is that removing in this class feedstock oil of adopting both at home and abroad contains one of main method of acid constituents.Hydrogenation deacidification is that petroleum acids and the hydrogen reaction decarboxylize in the acid-containing hydrocarbon oil generates hydrocarbon and water.
Carrier is the important component part of catalyst, not only disperses the place for metal active constituent provides usually, and carrier itself also participates in reaction simultaneously, works in coordination with other active component and finishes whole catalytic reaction.In the petroleum distillate hydrogenation catalyst, the carrier that contains aluminium oxide and molecular sieve namely has above-mentioned double action.Therefore, the performance of catalyst carrier has important function to final catalyst.Existing catalyst carrier for hydrgenating is salic, molecular sieve and other refractory oxide generally.
USP5897769 discloses a kind of method of acid-containing raw oil selective hydrogenation depickling, adopt the small catalyst of a kind of aperture 5.0nm～8.5nm, be used for selectively removing acid-containing raw oil low-molecular-weight aphthenic acids, but because carrier aperture is little, exist and to stop up the duct easily, service cycle is short and only can make little molecular naphthenic acid hydrogenation and cause the low problem of acid removal rate.
CN1590511A and CN1611576A disclose a kind of distillate hydrogenation deacidifying catalyst, this catalyst carrier is made up of magnesia, macroporous aluminium oxide and aperture aluminium oxide, the weight ratio of wherein little porous aluminum oxide and macroporous aluminium oxide is 75: 25～50: 50, but lower by the catalyst acid removal rate of this preparing carriers.
CN101864326A discloses a kind of hydrogenation deacidfieation method of acid-containing crude oil, and the carrier that this method relates to catalyst is mixed by macroporous aluminium oxide and little porous aluminum oxide, and wherein, the weight ratio of little porous aluminum oxide and macroporous aluminium oxide is 30: 70～70: 30.
CN101537363A discloses a kind of deacidifying catalyst and its preparation method and application, and used carrier is a kind of in aluminium oxide, molecular sieve, diatomite and the silica gel, and the catalyst acid removal rate is lower, and the distillate acid number can only be reduced to 0.50KOH/g.
CN101314733A discloses a kind of hydrogenation depickling method of high-metal acid containing primary oil, and the carrier that this method relates to catalyst is a kind of alumina support of bimodal hole, and its pore volume is 0.8～1.6ml/g, and specific area is 150～350m
2/ g, the aperture accounts for total pore volume 40～90% at the pore volume of 10～30nm, and the aperture accounts for total pore volume 10～50% at the pore volume of 100～2000nm.Acid removal rate is lower, is 83.3%～91.5%.
Summary of the invention
The purpose of this invention is to provide a kind of distillate hydrogenation deacidifying catalyst carrier with higher depickling activity and preparation method thereof.Carrier of the present invention is applicable to handles higher atmospheric distillate and the vacuum distillate of acid content.
Distillate hydrogenation deacidifying catalyst carrier of the present invention is made up of molecular sieve, magnesia, aluminium oxide, peptizing agent and polyvinyl alcohol.By vehicle weight 100%, magnesium with oxide count 4～10%, phosphate aluminium molecular sieve and/or sial micro porous molecular sieve 5～35%, peptizing agent 3～6%, polyvinyl alcohol 2～5%, surplus be aluminium oxide.
Molecular sieve of the present invention is made up of in APO-5, SAPO-5, SAPO-11, SAPO-31, ZSM-22, the ZSM-23 molecular sieve one or more, or by the product of above molecular sieve behind sour modification and/or hydrothermal modification.
The preparation of peptizing agent of the present invention is to add a certain amount of alumina powder gained in organic acid and/or inorganic acid.
Aluminium oxide of the present invention is boehmite.
Aluminium oxide of the present invention preferably aperture is the aluminium oxide more than 70% that the above pore volume of 10nm accounts for total pore volume.
Magnesium-containing compound of the present invention is selected from the inorganic salts of magnesium or in the acylate one or more.
The solution of magnesium-containing compound of the present invention, it has added EDTA in process for preparation, be used for the concentration of control magnesium.
Technical essential of the present invention is: add appropriate amount of alumina, peptizing agent and polyvinyl alcohol among the present invention, aluminium oxide structure is relatively stable, plays skeleton function, can increase the intensity of carrier; The adding of peptizing agent makes cohesiveness enhancing between the alumina powder surface particles; The adding of polyvinyl alcohol is conducive to the carrier extrusion molding.
The preparation method of carrier of the present invention is as follows:
(1) alumina powder and molecular sieve are mixed, add peptizing agent, polyvinyl alcohol and the water mixed plastic of pinching into according to a certain percentage;
(2) with the extrusion molding on banded extruder of (1) gained material;
(3) with (2) gained dry materials, roasting;
(4) with the solution impregnation of (3) gained material with magnesium-containing compound;
(5) (4) gained dry materials, roasting are obtained carrier of the present invention;
Or
(1) alumina powder, molecular sieve are mixed with magnesia and/or magnesium-containing compound, add peptizing agent, polyvinyl alcohol and the water mixed plastic of pinching into according to a certain percentage;
(2) with the extrusion molding on banded extruder of (1) gained material;
(3) (2) gained dry materials, roasting are obtained carrier of the present invention;
Wherein sintering temperature is 400 ℃～600 ℃, and roasting time is 3h～6h.
Catalyst carrier of the present invention is during for the preparation of the hydrogenation deacidification catalyst, can adopt carrying method conventional in the prior art, preferred infusion process, it can be incipient impregnation or supersaturation dipping, can adopt co-impregnation or distribution infusion process, soaked carrier makes final hydrogenation deacidification catalyst after super-dry, roasting.
Catalyst carrier of the present invention adopts phosphate aluminium molecular sieve and/or sial micro porous molecular sieve, selective by molecular sieve, improve the hydrogenation deacidification performance of catalyst, make it under the process conditions that relax, can effectively remove acidic materials in the heavy inferior distillate.Hydrogenation deacidification catalyst with catalyst carrier preparation of the present invention has greater activity, and has certain hydrodesulfurization and hydrodenitrogeneration performance.
The specific embodiment
Aluminium oxide used in the present invention is commercially available boehmite, or has the commercial alumina carrier of suitable pore size distribution.
The preferred bore dia of aluminium oxide is the aluminium oxide more than 70% that the above pore volume of 10nm accounts for total pore volume.
The mixture of magnesia of the present invention, aluminium oxide and molecular sieve can be (1) with boehmite and molecular sieve dry powder mix pinch, after the moulding, roasting with the solution impregnation of magnesium-containing compound, the dry and roasting in dipping back makes; Or (2) boehmite, molecular sieve and magnesia and/or magnesium-containing compound are mixed pinch, moulding and roasting make.
According to method provided by the invention, the preparation of described dipping solution and dipping method are conventional method.Wherein, by adjusting and control to concentration, consumption or the carrier consumption of dipping solution, the method for preparing specified metal content catalyst is conventionally known to one of skill in the art.
The preferred magnesia of described magnesium-containing compound or contain the inorganic acid salt of magnesium, in the acylate one or more is as in magnesium nitrate, magnesium sulfate, the magnesium stearate one or more.
Agents useful for same in the example except specifying, is technical grade reagent.
Pore size distribution adopts B E T Brunauer Emett Teller method of nitrogen adsorption at low temperature to measure, and the content of molybdenum, nickel, magnesium and phosphorus adopts x-ray fluorescence method to measure.
Embodiment 1
Get the 80g boehmite, add 20g phosphate aluminium molecular sieve AlPO
4-5,6.4g acetic acid, 3.1g polyvinyl alcohol, 93g deionized water mix and pinch, mix, extrusion becomes the cloverleaf pattern of 1.5mm, 120 ℃ of oven dry, then at 550 ℃ of roasting 4h, the cooling back is flooded with the aqueous solution 100ml that contains magnesium nitrate 47.5g, wet bar is 120 ℃ of oven dry, roasting 4h under 580 ℃ of air atmospheres makes carrier A then, and its character is listed in table 1.
Embodiment 2
Get the 100g boehmite, interpolation 20g phosphate aluminium molecular sieve SAPO-11,6g nitric acid, 3.1g starch, 112g deionized water mix and pinch, mix, extrusion becomes the cloverleaf pattern of 1.5mm, 120 ℃ of oven dry, then at 550 ℃ of roasting 4h, cooling back is with the aqueous solution 100ml dipping that contains magnesium nitrate 57g, and wet bar is 120 ℃ of oven dry, then roasting 4h under 580 ℃ of air atmospheres, make carrier B, its character is listed in table 1.
Embodiment 3
Get the 96g boehmite, interpolation 24g sial micro porous molecular sieve ZSM-22,6.4g nitric acid, 3.6g polyvinyl alcohol, 112g deionized water mix and pinch, mix, extrusion becomes the cloverleaf pattern of 1.5mm, 120 ℃ of oven dry, then at 550 ℃ of roasting 4h, cooling back is with the aqueous solution 100ml dipping that contains magnesium nitrate 57g, and wet bar is 120 ℃ of oven dry, then roasting 4h under 580 ℃ of air atmospheres, make support C, its character is listed in table 1.
Embodiment 4
Get the 66g boehmite, add 94g dolomol, 24g phosphate aluminium molecular sieve AlPO
4-5,5g acetic acid, 3.6g polyvinyl alcohol, 90.2g deionized water mix and pinch, and mix, and extrusion becomes the cloverleaf pattern of 1.5mm, 120 ℃ of oven dry, and roasting 4h under 580 ℃ of air atmospheres makes carrier D then, and its character is listed in table 1.
Embodiment 5
Get the 90g boehmite, interpolation 115g dolomol, 20g phosphate aluminium molecular sieve SAPO-11,4g nitric acid, 3g starch, 109g deionized water mix and pinch, mix, extrusion becomes the cloverleaf pattern of 1.5mm, 120 ℃ of oven dry, roasting 4h under 580 ℃ of air atmospheres makes carrier E then, and its character is listed in table 1.
Embodiment 6
Get the 70g boehmite, interpolation 90g dolomol, 16.2g sial micro porous molecular sieve ZSM-22,5g nitric acid, 2.7g polyvinyl alcohol, 85.7g deionized water mix and pinch, mix, extrusion becomes the cloverleaf pattern of 1.5mm, 120 ℃ of oven dry, roasting 4h under 580 ℃ of air atmospheres makes carrier F then, and its character is listed in table 1.
Embodiment 7
Get the 80g boehmite, add 10g phosphate aluminium molecular sieve AlPO
4-5,10g SAPO-11,6.4g nitric acid, 2.5g polyvinyl alcohol, 92.4g deionized water mix and pinch, mix, extrusion becomes the cloverleaf pattern of 1.5mm, 120 ℃ of oven dry, then at 550 ℃ of roasting 4h, the cooling back is flooded with the aqueous solution 100ml that contains magnesium nitrate 47g, wet bar is 120 ℃ of oven dry, roasting 4h under 580 ℃ of air atmospheres makes carrier G then, and its character is listed in table 1.
Embodiment 8
Get the 60g boehmite, add 86g dolomol, 10g phosphate aluminium molecular sieve AlPO
4-5,10g sial micro porous molecular sieve ZSM-22,5g acetic acid, 3.6g starch, 80.7g deionized water mix and pinch, and mix, and extrusion becomes the cloverleaf pattern of 1.5mm, 120 ℃ of oven dry, roasting 4h under 580 ℃ of air atmospheres makes carrier H then, and its character is listed in table 1.
Embodiment 9
Get the 100g boehmite, interpolation 10g phosphate aluminium molecular sieve SAPO-11,10g sial micro porous molecular sieve ZSM-22,6.3g acetic acid, 3.6g polyvinyl alcohol, 113g deionized water mix and pinch, mix, extrusion becomes the cloverleaf pattern of 1.5mm, 120 ℃ of oven dry, then at 550 ℃ of roasting 4h, cooling back is with the aqueous solution 100ml dipping that contains magnesium nitrate 57g, and wet bar is 120 ℃ of oven dry, then roasting 4h under 580 ℃ of air atmospheres, make carrier I, its character is listed in table 1.
Comparative Examples 1
Get the 100g boehmite, interpolation 6.3g nitric acid, 3.6g polyvinyl alcohol, 93.5g deionized water mix and pinch, mix, extrusion becomes the cloverleaf pattern of 1.5mm, 120 ℃ of oven dry, then at 550 ℃ of roasting 4h, cooling back is with the aqueous solution 100ml dipping that contains magnesium nitrate 47g, and wet bar is 120 ℃ of oven dry, then roasting 4h under 580 ℃ of air atmospheres, make carrier a, its character is listed in table 1.
Comparative Examples 2
Get the 90g boehmite, interpolation 95g dolomol, 5g nitric acid, 3.6g polyvinyl alcohol, 90.2g deionized water mix and pinch, and mix, extrusion becomes the cloverleaf pattern of 1.5mm, 120 ℃ of oven dry, roasting 4h under 580 ℃ of air atmospheres then, make carrier b, its character is listed in table 1.
Comparative Examples 3
Get the 120g boehmite, add 20g phosphate aluminium molecular sieve AlPO
4-5,5g acetic acid, 3.6g polyvinyl alcohol, 124g deionized water mix and pinch, and mix, and extrusion becomes the cloverleaf pattern of 1.5mm, 120 ℃ of oven dry, and roasting 4h under 580 ℃ of air atmospheres makes carrier c then, and its character is listed in table 1.
Embodiment 10
This example provides the main character of carrier in above-mentioned each example, sees Table 1.
The main character of table 1 carrier
| Example | MgO，％ | Molecular sieve content, % | Specific area, m 2/g | Pore volume, ml/g |
| 1 | 6.71 | 18.1 | 360 | 0.75 |
| 2 | 6.74 | 15.2 | 343 | 0.65 |
| 3 | 6.71 | 18.1 | 357 | 0.70 |
| 4 | 6.62 | 23.9 | 371 | 0.50 |
| 5 | 6.70 | 16.5 | 334 | 0.60 |
| 6 | 6.67 | 17.0 | 346 | 0.67 |
| 7 | 6.68 | 18.2 | 361 | 0.80 |
| 8 | 6.77 | 22.3 | 365 | 0.78 |
| 9 | 6.71 | 15.1 | 340 | 0.66 |
| Comparative Examples 1 | 6.61 | 0 | 275 | 0.45 |
| Comparative Examples 2 | 6.68 | 0 | 243 | 0.42 |
| Comparative Examples 3 | 0 | 13.9 | 334 | 0.67 |
As can be seen from Table 1, catalyst carrier of the present invention contains a certain amount of MgO and molecular sieve, has bigger specific area and pore volume simultaneously.
Embodiment 11
Carrier A, G are with containing molybdenum nickel phosphorus maceration extract (MoO altogether
3Concentration 52g/100ml, NiO concentration 8.5g/100ml, P
2O
53.1g/100ml) behind the room temperature dipping 2h, 120 ℃ of dry 2h, 540 ℃ of roasting 4h of temperature programming make catalyst I, II respectively, and the composition of catalyst sees Table 2.
Comparative Examples 4
Prepare catalyst according to example 11 identical conditions, take by weighing carrier a, c successively, make catalyst I II, IV respectively, the composition of catalyst sees Table 2.
The composition of table 2 catalyst
Comparative Examples 5
Catalyst V is a kind of industrialized hydrogenation deacidification catalyst.This catalyst carrier is made up of magnesia and aluminium oxide, does not contain molecular sieve, MoO in the catalyst
3Content 25.1%, NiO content 5.0wt.%, P
2O
5Content 2.3wt.%, MgO content are 2.5wt.%, Al
2O
3Surplus.
Embodiment 12
This case introduction the hydrogenation deacidification performance of catalyst.
Be reflected on the little inverse spectral apparatus of continuous-flow and carry out, feedstock oil is the hexane solution that contains 10% hexahydrobenzoid acid, and the catalyst loading amount is 0.3g.
Before formal charging, be that sulfurized oil carries out presulfurization to catalyst I, II respectively with the mixed solution that contains 3wt.% carbon disulfide and cyclohexane earlier, conditions of vulcanization is: pressure 4.1MPa, 300 ℃ of temperature, time 2.5h, sulfurized oil feed rate 0.2ml/min, hydrogen flow rate 400ml/min; Cutting feedstock oil afterwards reacts, reaction condition is: pressure 4.1MPa, feedstock oil input 0.1ml/min, the volume of hydrogen oil ratio is 4000: 1, and temperature is 300 ℃, sampling on-line chromatograph analysis behind the reaction 3h, chromatographic column is 3m packed column (101 carriers, OV-17 is phase fixedly), thermal conductivity cell detector, and be calculated as follows the conversion ratio of hexahydrobenzoid acid:
Hexahydrobenzoid acid conversion ratio=[content of hexahydrobenzoid acid in (in the feedstock oil in the content-product of hexahydrobenzoid acid the content of hexahydrobenzoid acid)/feedstock oil] * 100%
The results are shown in Table 3.
Comparative Examples 6
This Comparative Examples explanation comparative catalyst's hydrogenation deacidification performance.
Adopt method evaluation comparative catalyst III, the IV identical with example 12, the results are shown in Table 3.
The conversion ratio of table 3 hexahydrobenzoid acid
As can be seen from Table 3, under same reaction conditions, contain the hexahydrobenzoid acid hydro-conversion activity of catalyst of molecular sieve carrier apparently higher than the Comparative Examples catalyst.Wherein, the hydrogenation activity of the catalyst I I of two kinds of molecular sieves of adding is than the height of catalyst I.The hydrogenation activity of the catalyst of introducing auxiliary agent magnesium has significant improvement than the hydrogenation activity of the catalyst that does not contain magnesium.
Embodiment 13
Present embodiment has been introduced catalyst hydrogenation depickling activity rating result.
Raw materials used oil is Liaohe River atmosphere 3rd side cut oil, and acid number is 5.12mgKOH/g, and its character sees Table 4.
Catalyst I, II are broken into the particle of diameter 2mm～3mm, this catalyst 120ml packs in the 200ml fixed bed reactors, before formal charging, with the kerosene that contains 2wt.% carbon disulfide catalyst is vulcanized earlier, cutting raw material afterwards reacts, conditions of vulcanization and reaction condition see Table 5, the results are shown in Table 6.
Table 4 raw material oil properties
Table 5200ml conditions of vulcanization and reaction condition
Comparative Examples 7
The hydrogenation deacidification performance of this Comparative Examples explanation comparative catalyst's distillate.
Adopt with example 13 same procedure and estimate comparative catalyst III, IV, V, reaction result sees Table 6.
Table 6 catalyst contrast hydrogenation evaluation result
The acid number analysis of distillate and products thereof is measured according to GB/T 264-91; Nitrogen content is measured according to ASTM D4629; Sulfur content is measured according to ASTM D5453.
Claims (9)
1. preparation method who contains the distillate hydrogenation deacidifying catalyst carrier of molecular sieve, it is characterized in that: by weight 100%, magnesium with oxide count 4～10%, phosphate aluminium molecular sieve and/or sial micro porous molecular sieve 5～35%, peptizing agent 3～6%, polyvinyl alcohol 2～5%, surplus be aluminium oxide;
The preparation method of carrier is as follows:
Method one:
(1) alumina powder and molecular sieve are mixed, add peptizing agent, polyvinyl alcohol and the water mixed plastic of pinching in proportion;
(2) with the extrusion molding on banded extruder of (1) gained material;
(3) with (2) gained dry materials, roasting;
(4) with the solution impregnation of (3) gained material with magnesium-containing compound;
(5) (4) gained dry materials, roasting are obtained carrier of the present invention;
Method two:
(1) alumina powder, molecular sieve are mixed with magnesia and/or magnesium-containing compound, add peptizing agent, polyvinyl alcohol and the water mixed plastic of pinching in proportion;
(2) with the extrusion molding on banded extruder of (1) gained material;
(3) (2) gained dry materials, roasting are obtained carrier of the present invention;
Wherein sintering temperature is 400 ℃～600 ℃, and roasting time is 3h～6h.
2. the preparation method who contains the distillate hydrogenation deacidifying catalyst carrier of molecular sieve according to claim 1, it is characterized in that: described molecular sieve is made up of one or more of APO-5, SAPO-5, SAPO-11, SAPO-31, ZSM-22, ZSM-23 molecular sieve, or by the product of above molecular sieve behind sour modification and/or hydrothermal modification.
3. the preparation method who contains the distillate hydrogenation deacidifying catalyst carrier of molecular sieve according to claim 1 is characterized in that: the preparation of peptizing agent is to add the alumina powder gained in organic acid and/or inorganic acid.
4. the preparation method who contains the distillate hydrogenation deacidifying catalyst carrier of molecular sieve according to claim 1, it is characterized in that: aluminium oxide is boehmite.
5. the distillate hydrogenation deacidifying catalyst carrier that contains molecular sieve according to claim 1 is characterized in that: described aluminium oxide aperture is the aluminium oxide more than 70% that the above pore volume of 10nm accounts for total pore volume.
6. the preparation method who contains the distillate hydrogenation deacidifying catalyst carrier of molecular sieve according to claim 1 is characterized in that: described magnesium-containing compound is selected from the inorganic salts of magnesium or in the acylate one or more.
7. according to the described preparation method who contains the distillate hydrogenation deacidifying catalyst carrier of molecular sieve of claim 1, it is characterized in that: the solution of described magnesium-containing compound, it has added EDTA in process for preparation, be used for the concentration of control magnesium.
8. distillate hydrogenation deacidifying catalyst carrier that contains molecular sieve is characterized in that: it is according to preparation method's preparation of the described distillate hydrogenation deacidifying catalyst carrier that contains molecular sieve of claim 1.
9. application that contains the distillate hydrogenation deacidifying catalyst carrier of molecular sieve according to claim 8 is characterized in that: contain acid fraction hydrogenation deacidification catalyst carrier as heavy inferior.
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|---|---|---|---|---|
| CN104693357A (en) * | 2013-12-04 | 2015-06-10 | 中国科学院大连化学物理研究所 | An oxidation desulphurization method for C9 petroleum resin |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1289824A (en) * | 1999-09-29 | 2001-04-04 | 中国石油化工集团公司 | Hydrogenating catalyst for heavy oil and its preparing process |
| CN1295111A (en) * | 1999-11-04 | 2001-05-16 | 中国石油化工集团公司 | Gasoline fraction hydrogenating and modifying catalyst containing zeolite |
| EP1516667A1 (en) * | 2003-09-19 | 2005-03-23 | Institut Français du Pétrole | Hydrorefining and/or hydroconversion catalyst comprising an active phase in the form of a solid solution sulfide of molybdenum and tungsten |
| CN1778874A (en) * | 2004-11-26 | 2006-05-31 | 中国石油天然气股份有限公司 | Hydrogenation dearomatization catalyst containing molecular screen |
-
2012
- 2012-03-01 CN CN2012100517517A patent/CN103285934A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1289824A (en) * | 1999-09-29 | 2001-04-04 | 中国石油化工集团公司 | Hydrogenating catalyst for heavy oil and its preparing process |
| CN1295111A (en) * | 1999-11-04 | 2001-05-16 | 中国石油化工集团公司 | Gasoline fraction hydrogenating and modifying catalyst containing zeolite |
| EP1516667A1 (en) * | 2003-09-19 | 2005-03-23 | Institut Français du Pétrole | Hydrorefining and/or hydroconversion catalyst comprising an active phase in the form of a solid solution sulfide of molybdenum and tungsten |
| CN1778874A (en) * | 2004-11-26 | 2006-05-31 | 中国石油天然气股份有限公司 | Hydrogenation dearomatization catalyst containing molecular screen |
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