CN1144861C - Saturated loaded noble metal catalyst for distilling oil arenes and its prep. - Google Patents
Saturated loaded noble metal catalyst for distilling oil arenes and its prep. Download PDFInfo
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- CN1144861C CN1144861C CNB001231367A CN00123136A CN1144861C CN 1144861 C CN1144861 C CN 1144861C CN B001231367 A CNB001231367 A CN B001231367A CN 00123136 A CN00123136 A CN 00123136A CN 1144861 C CN1144861 C CN 1144861C
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Abstract
The present invention discloses a loading type noble metal catalyst for aromatic saturation of distillate oil and a preparation method thereof. Modified Y-type zeolite having the advantages of high crystallinity, low unit cell parameters, large specific surface area, ideal acidity and ideal acid distribution is adopted as a carrier so that loaded noble metal has very high sulphur resistance. The prepared catalyst is especially suitable for the process of the aromatic saturation of the distillate oil.
Description
The present invention relates to a kind of saturated loaded noble metal catalyst of distillate aromatic hydrocarbons and preparation method thereof that is used for.
Owing to contain impurity such as aromatic hydrocarbons and sulphur nitrogen, in use can form NO in the vehicle fuel
x, SO
xReach the solid particulate discharge and cause environmental pollution.Therefore, in petroleum refining process, the aromatic hydrocarbons in the diesel oil is carried out hydrotreatment, can improve oil quality, reduce the waste discharge amount of engine, have very high economic benefit and social benefit.
At present, be used to produce the precious metal dearomatization catalyst of clean fuel, how do carrier, and support VIII family precious metal with aluminum oxide, silicon oxide, amorphous aluminum silicide, y-type zeolite, β zeolite etc., as active ingredient, has higher distillate hydrogenation activity as Pt, Pd, Rh, Ir etc.Yet, contain a certain amount of sulphur compound in the raw material usually, can cause precious metal to be poisoned.Therefore, industrial employing two-stage method technology is used the base metal desulfurization catalyst at first section, the sulphur in the raw material is taken off to the utmost point low; Second section is adopted above-mentioned noble metal catalyst to carry out hydrotreatment.Adopt this two-stage method technology, can handle the higher distillate of sulphur content, but complex process, investment is big, energy consumption is high.
For improving the sulfur resistance of noble metal catalyst, research is in recent years thought, adopts the carrier of peracid amount, and precious metal is produced the electrophilic effect, weakens the bond energy between sulphur and precious metal, can obtain anti-preferably sulphur effect.
Introduce a kind of boiling range scope that is applicable in the United States Patent (USP) 5308814 and taken off the noble metal catalyst of aromatic hydrocarbons, desulfurization, denitrogenation at 66～371 ℃ hydro carbons, carrier is made up of y-type zeolite and aluminum oxide in the catalyzer, the content of y-type zeolite be total weight of carrier 50～80%, Na content is 1.5～5.0w% in the y-type zeolite, Si/Al=1.5～7.0.Hydrogenation metal is Pt and Pd, and content is 0.1～2.0w% of catalyzer total amount, wherein Pd: Pt (molecular ratio)=3: 1～1: 1.The aromaticity content of outlet oil is 9.9v%, aromatics conversion rate 84%, and sulphur content is 17 μ g/g.
United States Patent (USP) 5391291 has been introduced a kind of boiling range scope that is applicable at 125～625 ℃ raw material aromatic hydrogenation.This support of the catalyst adopts a kind of y-type zeolite, the preparation method of carrier carries out ion-exchange with y-type zeolite and one or more alkaline including earth metal ionic aqueous solution, making alkaline earth metal content on it is on the original y-type zeolite 1.5 times of alkaline earth metal content or more, mixes with aluminum oxide again.Lattice constant＜the 2.440nm of the y-type zeolite that adopts, SiO
2/ Al
2O
3＞25, alkaline-earth metal＜0.15%.Pt, Pd content are 0.03～3.0% on the carrier, Pt: Pd (molecular ratio)=0.1～0.5.Can reduce to below the 20w% with the distillate aromaticity content after this catalyst treatment.
The common drawback that above-mentioned patent exists is that the used Y molecular sieve non-modified of carrier is handled, and therefore, does not possess ideal acidity and higher thermostability, makes the anti-sulphur poor effect of the precious metal that supports, and the transformation efficiency of aromatic hydrocarbons is not high.
The purpose of this invention is to provide a kind of boiling range scope that is applicable at saturated noble metal catalyst of distillate aromatic hydrogenation of 85～625 ℃ and preparation method thereof, prepared catalyzer has than high antisulphuric ability, high reactivity and high thermal stability.
The characteristics that noble metal catalyst of the present invention has are, carrier is made up of modified zeolite of Y-type and aluminum oxide, active metal component is selected from group VIII noble metals in the periodic table of elements, weight percent with catalyzer is a benchmark, each components contents is: described modified zeolite of Y-type accounts for 40～90%, is preferably 77.9～79.9%, and described aluminum oxide accounts for 10～60%, be preferably 19.1～21.1%, precious metal 0.2～2.0%.
The specific surface area of catalyzer is 500～800m
2/ g, pore volume are 0.40～0.55ml/g.
Described precious metal better is to be selected from one or more of Pt, Pd, Rh, Ir, preferably is selected among Pt, the Pd one or both.
The characteristics that noble metal catalyst of the present invention has also are, the character of the modified zeolite of Y-type that carrier is used: unit cell parameters 2.435～2.455nm, SiO
2/ Al
2O
3Value is 5～70, and degree of crystallinity is greater than 95%, specific surface area 700～900m
2/ g, pore volume 0.35～0.55ml/g.Infrared acidity 0.2～2.0mmol/g, Na
2O content is less than 0.20w%.The character of the used modified zeolite of Y-type of above-mentioned carrier is preferably: unit cell parameters 2.435～2.450nm, SiO
2/ Al
2O
3Value is 15～60, and degree of crystallinity is greater than 97%, specific surface area 750～850m
2/ g, pore volume 0.40～0.50ml/g.Infrared acidity 0.5～1.5mmol/g, Na
2O content is less than 0.15w%.
Preparation of catalysts method of the present invention is, above-mentioned modified Y zeolite is mixed with aluminum oxide powder, after moulding, drying, roasting, make carrier, contact with one or more VIII family precious metal aqueous solution again, noble metal component is loaded on the described carrier, more after filtration, dry, roasting, make catalyzer of the present invention.
The preparation process of modified Y zeolite of the present invention can be: earlier NaY zeolite raw material is carried out the ammonium exchange, remove the Na ion, carry out hydrothermal treatment consists then, carry out acid treatment afterwards, the product that obtains after filtration, after the washing, drying, make modified Y zeolite of the present invention.
Described modified zeolite of Y-type can be directly mixed with aluminum oxide powder, and use sour peptization; Also can mix with modified Y zeolite again behind aluminum oxide powder and the sour peptization.Used acid can be mineral acid, also can be organic acid.Comprise hydrochloric acid, sulfuric acid, nitric acid, acetic acid, oxalic acid etc.The consumption of acid is with H in the acid
+Al in ion and the aluminum oxide powder
2O
3Mol ratio be 0.1～0.4 to add, used acid concentration is 0.3～3mol/l.
In described carrier moulding process,, generally need to add an amount of water and extrusion aid, and mix for the ease of moulding.Extrusion aid comprises one or more of sesbania powder, citric acid, oxalic acid, Mierocrystalline cellulose, starch, polymeric surface active agent etc.
Material after the banded extruder moulding needs 100～130 ℃ of dryings 2～5 hours, and carrier is made in 350～750 ℃ of roastings 2～4 hours.The profile of carrier can be cylindrical, cloverleaf pattern, Herba Galii Bungei shape or other shape.Be of a size of 0.5～3mm, preferably 1～2mm.
The carrier that aforesaid method is made contacts with the aqueous solution of VIII family precious metal, adopts ion exchange method or pickling process to introduce metal ion, preferably adopts ion exchange method.The introducing process is carried out under usual conditions, promptly under normal temperature, the normal pressure.VIII family precious metal comprises Pt, Pd, Rh, Ir etc., preferably Pt, Pd.Can be a kind of, also can be multiple.Strength of solution (by the metal quality) is 0.2～2.0w%, preferably 0.4～1.5w%.Adopt in the ion exchange method solutions employed precious metal and OH-, NH
3-form complex cation to exist, allow other positively charged ion and exist, as H
+Ion, H
+With the mol ratio of precious metal ion 1: 1～50: 1.Negatively charged ion can be Cl
-, NO
3 -, SO
4 2-Deng; Adopt the pickling process solutions employed, precious metal can with Cl
-, NO
3 -, SO
4 2-Ion forms complexing ion, and positively charged ion is H
+, also can have other positively charged ion to exist.
The aqueous solution of above-mentioned VIII family precious metal and the duration of contact of carrier are 3～10 hours, preferably 4～8 hours.Solidliquid mixture dried in the shade under room temperature 5～12 hours after filtering.And it is following dry 1～4 hour at 110～130 ℃.Then under 350～700 ℃, preferably under 400～600 ℃, loaded noble metal catalyst is made in roasting 2～5 hours.
The concrete preparation method of modified Y zeolite of the present invention can carry out according to following steps:
1. in the NaY zeolite, add ammonium salt solution, under 30～100 ℃, exchange 0.5～5 hour, and constantly stir.In the described ammonium salt solution H can be arranged
+Ion also can have other metallic cation to exist.H
+Ion is provided by acid.Used ammonium salt can be the inorganic salt or the organic salt of ammonium, as ammonium chloride, ammonium sulfate, ammonium nitrate, volatile salt, ammonium oxalate etc.NH
4 +Ionic concn is 0.5～5mol/l.Solution usage and zeolite weight ratio are 1～10.The character of described NaY zeolite is unit cell parameters 2.462～2.475nm, degree of crystallinity 90%～105%, SiO
2/ Al
2O
3Be about 4～6, Na
2O content is about 9%～11%.
2. the product that step 1 is obtained after filtration, after the washing, drying, put into the hydrothermal treatment consists stove and carry out steam-treated.Treatment temp is 250～850 ℃, and water partial pressure is 0.05～1.00MPa, and the treatment time is 0.5～10 hour, preferably 0.5～5 hour.
3. the product that step 2 is obtained places the aqueous solution with multiple positively charged ion existence to handle, and in this solution H must be arranged
+And NH
4 +Two kinds of positively charged ions also can have other metallic cation to exist.H wherein
+Ion is provided by acid, example hydrochloric acid, nitric acid, sulfuric acid etc.Used ammonium salt can be the inorganic salt or the organic salt of ammonium, as ammonium chloride, ammonium sulfate, ammonium nitrate, volatile salt, ammonium oxalate etc.NH in the solution
4 +Ionic concn is 0.5～5mol/l.The pH value of solution value is 1～6, preferably 2～5.Treatment temp is 30～100 ℃, and the treatment time is 0.2～5 hour, preferably 0.5～3 hour.Filter then.This step repeats 2～5 times.
The product that obtains of step 3 in 100～130 ℃ dry 1～3 hour down.Make modified zeolite of Y-type.
Compared with prior art, the present invention has following beneficial effect:
Catalyzer of the present invention is owing to adopt modified zeolite of Y-type to do carrier, and this zeolite has characteristics such as high-crystallinity, low unit cell parameters, bigger serface, ideal acidity and acid distribution, thereby make the precious metal that is supported have very high anti-sulphur, can be used for hydrocracking, hydrotreatment and the hydro-upgrading of distillate.Be specially adapted to the aromatic hydrogenation saturated reaction of distillate, and can bear sulphur content to 50 in the stock oil～500 μ g/g.
Example 1
A. use NaY zeolite 100g (unit cell parameters 2.472nm, degree of crystallinity 100%, the Na of Wenzhou catalyst plant production
2O content 10w%, SiO
2/ Al
2O
3=5: 1, butt 100%) is put in and is dissolved with 160gNH
4NO
3In 1 liter of the aqueous solution of 3ml concentrated nitric acid (1.4g/ml, 65%), be warming up to 80 ℃, stir 1 hour after-filtration, washing, drying.Place afterwards in the sealed furnace, handled 2 hours down for 620 ℃, put into 1 liter of the foregoing aqueous solution then in water partial pressure 0.2MPa, temperature, stir 1 hour after-filtration down at 80 ℃, after repeating 3 times, product in 120 ℃ times dry 2 hours, is made modified zeolite of Y-type.
B. Germany is produced SB aluminum oxide powder (Al
2O
3Contents on dry basis 75%) 20g mixes with the aqueous solution 50ml that is dissolved with 4.5ml concentrated nitric acid (1.4g/ml, 65%), and stirs, and makes tackiness agent.
C. a, b step products therefrom are mixed, and add 1g citric acid, 1g sesbania powder and an amount of water, on banded extruder, be extruded into Φ 1.5mm cloverleaf pattern bar, in 120 ℃ dry 3 hours down, carrier is made in 550 ℃ of following roastings 4 hours.
D. with the Pd (NH of above-mentioned carrier and 100ml
3)
4Cl
2Solution carries out ion-exchange, contains Pd0.8g in the solution.Exchange is carried out at normal temperatures and pressures, and the time is 5 hours.Afterwards in 120 ℃ dry 2 hours down, catalyst A is made in 500 ℃ of following roastings 3 hours.
Example 2
With example 1, be the NH in a step
4NO
3Change NH into
4Cl, the hydrothermal treatment consists temperature is 700 ℃.Solution in the d step changes H into
2PdCl
4, the Pd content in the solution is 1.4g, adopts pickling process to introduce metal.Make catalyst B.
Example 3
With example 1, just in a step before the used solution of exchanged water solution be 1 liter and be dissolved with 160gNH
4NO
3The aqueous solution.Back clearing house is 1 liter with solution and is dissolved with 160g NH
4NO
3The aqueous solution with 3ml concentrated nitric acid (1.4g/ml, 65%).Solution is Pd (NH in the d step
3)
4Cl
2, Pt (NH
3)
4Cl
2Mixed solution, the Pt in the solution, Pd total amount are 0.8g, Pt: Pd=1: 4 (mol ratios).Make catalyzer C.
Example 4
With example 3, just the water partial pressure of the hydrothermal treatment consists in a step is 0.3MPa, and temperature is 550 ℃, and the time is 3 hours, and back exchange temperature is 85 ℃.It is cylindrical to be extruded into Φ 1.5mm in the C step.Make catalyzer D
Example 5
With example 1, just the water partial pressure of the hydrothermal treatment consists in a step is 0.3MPa, and temperature is 650 ℃, and the treatment time is 5 hours.Make catalyzer E.
The character of table 1 catalyst A～E of the present invention and used molecular sieve thereof
A B C D E
Molecular sieve character
Degree of crystallinity, % 95 97 85 82 98
a
0，nm 2.442 2.439 2.447 2.453 2.436
Specific surface area, m
2/ g 840 774 814 768 819
Pore volume, ml/g 0.49 0.46 0.36 0.42 0.50
SiO
2/Al
2O
3 15.2 21.3 7.30 5.39 51.3
Na
2O，m％ 0.05 0.03 0.08 0.07 0.02
The meleic acid amount, mmol/g 0.712 0.328 0.958 1.325 0.425
Catalyzer is formed
Aluminum oxide, w% 19.1 20.2 19.8 18.9 21.1
Molecular sieve, w% 79.9 78.8 79.0 81.1 77.9
Pt，w％ - - 0.31 0.28 -
Pd，w％ 1.02 0.98 0.78 0.76 0.97
Specific surface area, m
2/ g 626 598 617 559 620
Pore volume, ml/g 0.46 0.45 0.47 0.46 0.47
Example 6
Adopting A of the present invention, D, E catalyzer, is example with the hydrogenation dearomatization hydrocarbon reaction of distillate, has carried out activity rating.Processing condition see Table 2, and stock oil character sees Table 3.
Table 2 processing condition
| Pressure, MPa | 4.2 |
| Temperature, ℃ | 280 |
| Volume space velocity, h -1 | 1.0 |
| Hydrogen-oil ratio | 800 |
Table 3 stock oil character
Index I II
Density, d
4 200.8077 0.7925
S，μg/g 347 108
N，μg/g 98 248
Aromatic hydrocarbons, v% 63 15
Alkene, v% 1.8 0.3
IBP，℃ 163 98
EP，℃ 369 381
Cetane value 39 21
Condensation point, ℃-2-18
The results are shown in Table 4, as can be seen, adopt catalyzer of the present invention to be used for the hydrogenation dearomatization hydrocarbon reaction of distillate, can handle the higher raw material of aromaticity content, and have higher aromatics conversion rate.Can in the presence of higher sulphur compound, react.
Table 4 evaluation result
Catalyzer numbering A D E
Stock oil numbering II I I
Runtime, h 200 320 400
Generate oil
S，μg/g 12.4 17.1 12.8
Aromatic hydrocarbons, v% 3.4 8.5 6.2
Aromatics conversion rate, % 77.3 86.5 90.2
Claims (21)
1, a kind of saturated loaded noble metal catalyst of distillate aromatic hydrocarbons that is used for, with y-type zeolite and aluminum oxide is carrier, with the group VIII noble metals is active ingredient, weight percent with catalyzer is a benchmark, the content that it is characterized in that described y-type zeolite is 77.9～79.9%, and alumina content is 19.1～21.1%, and group VIII noble metals content is 0.2～2.0%, described y-type zeolite unit cell parameters is 2.435～2.455nm, SiO
2/ Al
2O
3Value is 5～70, Na
2O content is less than 0.20w%.
2,, it is characterized in that described precious metal is to be selected from one or more of Pt, Pd, Rh, Ir according to the described loaded noble metal catalyst of claim 1.
3,, it is characterized in that described precious metal is to be selected among Pt, the Pd one or both according to the described loaded noble metal catalyst of claim 1.
4,, it is characterized in that described y-type zeolite degree of crystallinity is greater than 95% according to the described loaded noble metal catalyst of claim 1.
5,, it is characterized in that described y-type zeolite specific surface area is 700～900m according to the described loaded noble metal catalyst of claim 1
2/ g, pore volume 0.35～0.55ml/g.
6,, it is characterized in that the infrared acidity of described y-type zeolite is 0.2～2.0mmol/g according to the described loaded noble metal catalyst of claim 1.
7, according to the described loaded noble metal catalyst of claim 1, the specific surface area that it is characterized in that described catalyzer is 500～800m
2/ g, pore volume are 0.40～0.55ml/g.
8, the preparation method of the described loaded noble metal catalyst of claim 1 comprises:
Modified Y zeolite is mixed with aluminum oxide powder, after moulding, drying, roasting, make carrier, contact with one or more VIII family precious metal aqueous solution again, noble metal component is loaded on the described carrier, more after filtration, dry, roasting, make described catalyzer.
9, according to the preparation method of the described loaded noble metal catalyst of claim 8, the preparation process that it is characterized in that described modified Y zeolite is: earlier NaY zeolite raw material is carried out the ammonium exchange, remove the Na ion, carry out hydrothermal treatment consists then, carry out acid treatment afterwards, the product that obtains after filtration, make described modified Y zeolite after the washing, drying.
10, according to the preparation method of the described loaded noble metal catalyst of claim 8, it is characterized in that the described modified zeolite of Y-type that makes be with aluminum oxide powder directly mixed after, sour peptization again.
11,, it is characterized in that the described modified zeolite of Y-type that makes is mixed with the aluminum oxide powder behind the peracid peptization according to the preparation method of the described loaded noble metal catalyst of claim 8.
12,, it is characterized in that also having added in the described moulding process water and extrusion aid according to the preparation method of the described loaded noble metal catalyst of claim 8.
13, according to the preparation method of the described loaded noble metal catalyst of claim 8, it is characterized in that material after the described moulding 100～130 ℃ of dryings 2～5 hours, carrier is made in 350～750 ℃ of roastings 2～4 hours.
14, according to the preparation method of the described loaded noble metal catalyst of claim 8, it is characterized in that precious metal concentration is 0.2～2.0w% in the aqueous solution of described VIII family precious metal, the aqueous solution of VIII family precious metal and the duration of contact of carrier are 3～10 hours.
15,, it is characterized in that described VIII family precious metal is incorporated on the described carrier by ion exchange method according to the preparation method of the described loaded noble metal catalyst of claim 8.
16, according to the preparation method of the described loaded noble metal catalyst of claim 8, the aqueous solution that it is characterized in that described VIII family precious metal is with after described carrier contacts, after filtration, under room temperature, dried in the shade 5～12 hours then, and it is following dry 1～4 hour at 110～130 ℃, under 350～700 ℃, described loaded noble metal catalyst is made in roasting 2～5 hours.
17, according to the preparation method of the described loaded noble metal catalyst of claim 9, it is characterized in that described NaY zeolite is that unit cell parameters is 2.462～2.475nm, degree of crystallinity is 90～105%, SiO
2/ Al
2O
3Be 4～6, Na
2O content is 9～11 zeolite.
18, according to the preparation method of the described loaded noble metal catalyst of claim 9, the detailed process that it is characterized in that described ammonium exchange is: add ammonium salt solution in the NaY zeolite, under 30～100 ℃, exchange 0.5～5 hour, and constantly stir NH in the described ammonium salt solution
4 +Ionic concn is 0.5～5mol/l, and solution usage and zeolite weight ratio are 1～10.
19, according to the preparation method of the described loaded noble metal catalyst of claim 9, the detailed process that it is characterized in that described hydrothermal treatment consists is: after the described product filtration that exchange obtains through ammonium, washing, drying, put into the hydrothermal treatment consists stove and carry out steam-treated, treatment temp is 250～850 ℃, water partial pressure 0.05～1MPa, the treatment time is 0.5～10 hour.
20, according to the preparation method of the described loaded noble metal catalyst of claim 9, it is characterized in that described acid-treated detailed process is: the product that described hydrothermal treatment consists is obtained places and comprises H
+And NH
4 +In the aqueous solution that interior multiple positively charged ion exists, handle, filter then; NH in the described solution
4 +Ionic concn is 0.5～5mol/l, and the pH value of solution value is 1～6, and described treatment temp is 30～100 ℃, and the treatment time is 0.2～5 hour, and acid-treated number of times is 2～5 times.
21,, it is characterized in that the described product that obtains through peracid treatment is to descend dry 1～3 hour at 100～130 ℃, makes modified zeolite of Y-type according to the preparation method of the described loaded noble metal catalyst of claim 9.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB001231367A CN1144861C (en) | 2000-10-26 | 2000-10-26 | Saturated loaded noble metal catalyst for distilling oil arenes and its prep. |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB001231367A CN1144861C (en) | 2000-10-26 | 2000-10-26 | Saturated loaded noble metal catalyst for distilling oil arenes and its prep. |
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| Publication Number | Publication Date |
|---|---|
| CN1370814A CN1370814A (en) | 2002-09-25 |
| CN1144861C true CN1144861C (en) | 2004-04-07 |
Family
ID=4589611
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB001231367A Expired - Lifetime CN1144861C (en) | 2000-10-26 | 2000-10-26 | Saturated loaded noble metal catalyst for distilling oil arenes and its prep. |
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Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1323139C (en) * | 2004-08-31 | 2007-06-27 | 中国石油化工股份有限公司 | One-step super-depth method for removing arenes from natural gas synthetic oil |
| CN103102989B (en) * | 2011-11-10 | 2015-11-18 | 中国石油化工股份有限公司 | A kind of method that Vaseline is deeply hydrodearomatized |
| CN105727941B (en) | 2014-12-10 | 2018-09-04 | 中国石油天然气股份有限公司 | A kind of sulfur-tolerant type aromatic saturated hydrogenation catalyst and preparation method thereof |
| CN105728024B (en) * | 2014-12-10 | 2018-09-04 | 中国石油天然气股份有限公司 | Preparation method, noble metal hydrogenation catalyst and the application of noble metal hydrogenation catalyst |
| CN108114737B (en) * | 2016-11-28 | 2020-03-17 | 中国石油化工股份有限公司 | Hydrogenation saturation catalyst, preparation method and application thereof |
| CN109954512B (en) * | 2017-12-22 | 2022-07-12 | 中国石油化工股份有限公司 | Reduced bimetallic hydrogenation saturation catalyst |
| CN109957424B (en) * | 2017-12-22 | 2020-10-27 | 中国石油化工股份有限公司 | Process method for converting catalytic cracking light cycle oil into jet fuel |
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2000
- 2000-10-26 CN CNB001231367A patent/CN1144861C/en not_active Expired - Lifetime
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