CN1032408C - Wax hydrofining catalyst - Google Patents
Wax hydrofining catalyst Download PDFInfo
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- CN1032408C CN1032408C CN 92111133 CN92111133A CN1032408C CN 1032408 C CN1032408 C CN 1032408C CN 92111133 CN92111133 CN 92111133 CN 92111133 A CN92111133 A CN 92111133A CN 1032408 C CN1032408 C CN 1032408C
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Abstract
The present invention discloses a wax hydrofining catalyst and a preparation method thereof. The catalyst is characterized in that the porosity of pores with the diameter of 4.0 to 15.0 nm accounts for more than 90% of the porosity of pores with the diameter of 0.0 to 60.0 nm; the porosity of the pores with the diameter of 0.0 to 60.0 nm is from 0.50 to 0.65 ml per gram. The preparation method of the catalyst comprises the steps: Si-Al collosol is pre-aged at low temperature before forming; the mixed acid of H3PO4 and HNO3 is added when wet gel is peptized before forming.
Description
The present invention relates to Wax hydrofining catalyst and preparation method thereof, particularly pore distribution concentration is the carrier and the preparation thereof of matrix with the aluminum oxide.
At present, most of Wax hydrofining catalysts still adopt Mo-Ni/Al
2O
3Material.It is generally acknowledged that the ideal Wax hydrofining catalyst should have following characteristics: more weak acidity, bigger specific surface, pore volume and mean pore size, and the pore distribution of concentrating, higher physical strength.Therefore, people constantly improve Wax hydrofining catalyst towards this direction.
For example, U, S, 4,186,078 has narrated a kind of Wax hydrofining catalyst, is characterized in: (1) adds the alkaline components of (0.2-5.0) w% on carrier, to eliminate SiO
2-Al
2O
3On strong acid center, avoid the wax material overcracking to generate oil.(2) to account for the pore volume per-cent (be defined as pore volume indices P VI) of bore dia in (0-15.0) nm scope be more than 80% to the pore volume of bore dia in (6.0-15.0) nm scope.(3) pore volume of bore dia in (0-60.0) nm scope is between (0.45-0.60) ml/g, and the specific surface of catalyzer is (200-300) m
2/ g.In this patent, though pore volume indices P VI is bigger, the pore volume absolute value of diameter in (6.0-15.0) nm scope is very little, is about (0.040-0.110) g/ml, less than 1/3rd of total pore volume, illustrates that above patent catalyst pores distributes still than disperse.
The objective of the invention is to prepare ideal Wax hydrofining catalyst recited above, particularly prepare the Wax hydrofining catalyst of pore distribution concentration.For the immersion type Hydrobon catalyst, its pore structure is basically by carrier decision, thus emphasis of the present invention be preparation acidity a little less than, specific surface, pore volume and mean pore size are bigger, the sufficiently high carrier of pore distribution concentration and physical strength.
The present invention is a kind of Wax hydrofining catalyst, is active ingredient with VIII family and vib metal element, with SiO
2-P
2O
5-Al
2O
3Be carrier, the pore volume of catalyst pores diameter in (4.0-15.0) nm scope accounts for bore dia more than 90% of pore volume in (0.0-60.0) nm scope, bore dia pore volume in (0.0-60.0) nm scope contains MoO in the catalyzer between (0.50-0.65) ml/g
3(18-24) w%, NiO (4-6) w% contains SiO in the support of the catalyst
2(5-10) w%, P
2O
5(2-5) w%, Al
2O
3(85-93) w%.The specific surface area of catalyzer is (220-280) m
2/ g.
Main points of the present invention are as follows.
(1) when the wet gel peptization, H induces one
3PO
4, with strong acid center and the minimizing total acid content of eliminating carrier.
By table 1 as seen, phosphorate and changed SiO
2～Al
2O
3Acid matter.(table is seen the literary composition back)
(2) take following two kinds of methods to improve the pore structure of carrier.
(A) add Si and P in carrier, test-results sees Table 2.(table is seen the literary composition back)
By table 2 as seen, add Si respectively and P can improve its pore volume and specific surface in alumina supporter, when adding Si and P simultaneously, the increasing degree of carrier pore volume and specific surface is bigger.In addition, when in alumina supporter, introducing an amount of Si and P, do not reduce its physical strength.
(B) silicon-aluminium colloidal sol mixed solution carries out the low temperature preconditioning before becoming glue.Test-results sees Table 3.(table is seen the literary composition back)
By table 3 as seen, when silicon-aluminium colloidal sol carried out preconditioning in (10-17) ℃ temperature range, final carrier had big pore volume and specific surface, and physical strength does not descend.
Carrier of the present invention and Preparation of catalysts process are:
(1) preparation and the preconditioning of silicon one aluminium colloidal sol
Containing Al
2O
3The aluminum chloride colloidal sol of (4-6) g/100ml with contain SiO
2The acidified sodium silicate of (6.0-9.0) g/100ml mixes, and regulates pH＜3 of mixed solution, and temperature remains on (10-17) ℃, aging (1-5) h.
(2) become glue
With temperature (10-17) ℃, the mixed sols of the ammoniacal liquor of concentration (8-11) % neutralization (1), control pH (7.0-9.0), (8-12) m/n total reaction time duration of contact (0.5-2.0) h
(3) filter, with chemical water purification washing leaching cake.
The washing operation condition is: wash temperature (23-27) ℃, and washing time (20-50) min, washing times (2-4) is inferior.
(4) wet gel peptization
Mix peptization acid concentration: H
3PO
4(50-55) w%, HNO
3(31-34) w%.Above-mentioned H
3PO
4The solution add-on is (70-140) g/kg butt, (31-34) w%HNO
3Add-on is (80-220) ml/kg butt.Peptization time is (1.5-4.0) h.Stir during peptization.
(5) balling-up
(4) the false sol solutions of step gained is dripped by water dropper, by being in the oil ammonia column under the room temperature,
Wet bulb soaks full (1-4) h in the ammoniacal liquor of (3-6) w% then.
(6) drying and roasting
Wet bulb takes out from ammoniacal liquor, at (70-100) ℃ down dry (2-6) h, at (550-700) ℃ following roasting (2-5) h.
(7) impregnating metal component, drying and roasting
(6) the bead carrier of step gained can also can carry out saturated spraying with ammonium molybdate ammonia soln and nickel nitrate aqueous solution respectively with ammonium molybdate and a supersaturation of nickelous nitrate ammonia soln dipping.For the supersaturation dipping, carrier need be under certain vacuum condition, and used impregnation concentration is MoO
3(20-26) g/100ml, NiO (6.0-8.0) g/100ml.Spray for saturated, used immersion liquid concentration is respectively and contains MoO
3(20-34) g/100ml and contain NiO (6.0-10.0) g/100ml.Carrier carries out drying and roasting after soaking metallic solution.Drying temperature is (100-140) ℃, and time (2-5) h, maturing temperature are (450-540) ℃, time (2-5) h.
Catalyzer main character in order to the preparation of top method is as shown in table 4.
The main character of table 4 catalyzer of the present invention
The project indicator
Chemical constitution w%
MoO
3??????????????????????????????18.0—24.0
NiO????????????????????????????????4.0—6.0
SiO
2/(SiO
2＋P
2O
5＋Al
2O
3)???5.0—10.0
P
2O
5/(SiO
2＋P
2O
5＋Al
2O
3)??2.0—5.0
Total pore volume ml/g 0.50-0.65
Specific surface m
2/ g 220-280
Average pore diameter nm 8.0-12.0
Tap density g/ml 0.65-0.76
Physical strength N/ grain 50-110
Pore distribution %
＜4.0nm????????????????????????????3.0—7.0
4.0—15.0nm????????????????????????90.0—95.0
＞15.0nm???????????????????????????1.0—4.0
PVI％??????????????????????????????90—94
*PVI＝(6—15nm/0—15nm)×100
By table 4 as seen, catalyzer of the present invention has bigger pore volume, specific surface and mean pore size, and higher physical strength particularly has concentrated pore distribution.Hole more than 90% concentrates in (4.0-15.0) nm scope, and the absolute pore volume in this scope is up to (0.45-0.60) ml/g.
Catalyzer of the present invention can be used for the hydrofining of wax class, to remove the impurity in the paraffin class, produces high-quality food packing wax, food wax and medical ventolin.
When catalyzer of the present invention was used for the hydrofining of wax class, suitable reaction conditions was: temperature of reaction (240-300) ℃, pressure (5.0-10.0) MPa, hydrogen wax be than (100-300), volume space velocity (0.5-2.0) h.
In order to improve the quality of wax, two or more reactors in series can be got up carry out multistage hydrofining.
Below with embodiment the present invention is described in more detail.
Embodiment 1
(1) preparation and the preconditioning of silicon-aluminium colloidal sol
Containing Al
2O
3The aluminum chloride colloidal sol 101 of 5g/100ml with contain SiO
27.The acidified sodium silicate 0.51 of 5g/100ml mixes, and regulates pH to 2.8, and temperature remains on 15 ℃, leaves standstill 3h.(2) become glue
With 15 ℃ of temperature, with above-mentioned colloidal sol mixed solution, the flow of control ammoniacal liquor makes reaction contact time 10min in the ammonia soln of concentration 9%, total reaction time 90min, and material pH is 7.8 in the neutralization tank.
(3) filter and wash
Use filtration under diminished pressure.With chemical water purification washing leaching cake.Operational condition is; 25 ℃ of wash temperatures, washing time 40min, washing times 3 times.
(4) wet colloidal sol peptization
Corresponding to the wet gel amount of 1kg butt, add 81g53w%H
3PO
4Solution and 190ml33w%HNO
3Stir 2.0h under the solution, room temperature.
(5) balling-up
Colloidal sol by (4) gained is dripped by water dropper, and by being in the oil ammonia column under the room temperature, wet rubber ball soaks 3.0h in 5% ammoniacal liquor then.
(6) drying and roasting
Dry 3h by (5) gained wet bulb down at 90 ℃, then at 620 ℃ of following roasting 4h.
(7) make catalyzer by carrier
Take by weighing by (6) gained bead carrier 200g, place filter flask, vacuumize 1h after, add and to contain MoO
325g/100ml, the ammonium molybdate of NiO6.0g/100ml and nickelous nitrate ammonia soln 400ml leave standstill the 1h after-filtration.The bead of inhaling full solution is dried 3h down at 120 ℃, at 530 ℃ of following roasting 3h.
Embodiment 2
In embodiment 1, the colloidal sol preconditioning temperature in (1) step and be used for the neutral ammonia temperature and change 13 ℃ into, i.e. cost example.
Embodiment 3
In (4) step in embodiment 2,53%H
3PO
4Consumption changes 120g into, i.e. the cost example.
Embodiment 4
In embodiment 2, use saturated pickling process carrying metal component instead, i.e. the cost example.
The concrete method of spraying is: take by weighing the bead carrier 200g after the roasting, place rotary drum, rotate rotary drum, spray into and contain MoO
3The Mo-NH of 30g/100ml
3Solution 200ml.Take out bead, dry 3h down, place rotary drum again, spray into the nickel nitrate solution 192ml that contains NiO8g/100ml, take out bead, at 110 ℃ of oven dry 3h, at 480 ℃ of following roasting 3h at 140 ℃.
Reference example 1
In (1) step of embodiment 1.Colloidal sol does not carry out the low temperature preconditioning, but directly becomes glue down at 26 ℃, does not add phosphoric acid in (4) step, i.e. the cost reference example.
Reference example 2
In (4) step in embodiment 1, add 210g53w%H
3PO
4And 160ml33w%HNO
3Solution, i.e. cost example.
Embodiment 5
This example has been enumerated the main character of above each routine catalyzer.(table is seen the literary composition back)
By table 5 as seen, (1) compares with reference example, catalyzer of the present invention has the pore distribution of concentrating, bigger pore volume and specific surface, this is owing to adopted following two kinds of technology in the process of preparation catalyzer of the present invention: the one, and silicon-aluminium colloidal sol becomes glue glue to carry out the low temperature preconditioning, the 2nd, when wet gel carries out peptization before the ball, add an amount of phosphoric acid.(2) as seen, the phosphoric acid of adding can not be excessive, the disperse otherwise the pore distribution of catalyzer will become from reference example 2.
In addition, by table 1 as seen, carrier of the present invention has more weak strength of acid and less total acid content.
Embodiment 6
This example is above each routine activity rating of catalyst result.During evaluate catalysts, raw materials used is No. 58 smart sweat waxes.Reaction process condition is: hydrogen pressure 4.9MPa, 270 ℃ of temperature, volume space velocity 1.5h
-1, hydrogen wax is than 100.(table is seen the literary composition back)
As seen from Table 6, catalyzer of the present invention has good effect to hydrorefining paraffin wax, with reference example relatively, the stability of purified product number low No., the aromaticity content that the ultraviolet extinction value is characterized is also lower.Prove that thus catalyst for hydrogen refining of paraffin wax should have bigger specific surface and pore volume and concentrated pore distribution.
Table 1 phosphorus is to SiO
2-Al
2O
3The carrier that influences of support acidity matter is formed w% indicator method acid distribution mmol/g
| ?P 2O 5 | ?SiO 2 | ?Al 2O 3 | ＜-8.2 | -8.2～-5.6 | -5.6～-3.0 | -3.0～+3.3 | Total acid | |
| ?1 | ?3.0 | ?7.3 | ?89.7 | ?0.00 | ????0.05 | ????0.00 | ????0.25 | ?0.30 |
| ?2 | ?0.0 | ?7.5 | ?92.5 | ?0.45 | ????0.05 | ????0.05 | ????0.10 | ?0.65 |
Table 2 Si and P are to the influence of carrier hole structure
| Numbering | Carrier is formed w% | Pore volume | Specific surface | Tap density | Physical strength | ||
| SiO 2 | ?P 2O 5 | Al 2O 3 | ????ml/g | ????m/g | ????g/ml | The N/ grain | |
| ????1 | ?0.0 | ????0.0 | Surplus | ????0.451 | ????204 | ????0.86 | ????115 |
| ????2 | ?0.0 | ????3.7 | Surplus | ????0.520 | ????268 | ????0.76 | ????124 |
| ????3 | ?5.0 | ????0.0 | Surplus | ????0.550 | ????271 | ????0.77 | ????105 |
| ????4 | ?7.5 | ????3.7 | Surplus | ????0.753 | ????343 | ????0.71 | ????112 |
The effect of table 3 silicon-aluminium colloidal sol low temperature preconditioning
| Numbering | Aging temperature ℃ | Digestion time h | Pore volume ml/g | Specific surface m 2/g | Tap density g/ml | Physical strength N/ grain |
| ?1 | ????10 | ????4 | ????0.805 | ????334 | ????0.58 | ????118 |
| ?2 | ????15 | ????4 | ????0.921 | ????347 | ????0.49 | ????108 |
| ?3 | ????17 | ????4 | ????0.856 | ????329 | ????0.55 | ????111 |
| ?4 | ????24 | ????4 | ????0.742 | ????324 | ????0.60 | ????75 |
| ?5 | ????34 | ????4 | ????0.530 | ????285 | ????0.76 | ????108 |
The main character of each routine catalyzer of table 5
| Catalyzer | Example 1 | Example 2 | Example 3 | Example 4 | With reference to 1 | With reference to 2 |
| Chemical constitution w%:MoO 3 | ????18.9 | ?19.3 | ???20.0 | ?21.8 | ?18.0 | ?19.0 |
| ????NiO | ????4.6 | ?4.8 | ???5.1 | ?5.6 | ?4.8 | ?4.9 |
| P 2O 5(SiO 2＋P 2O 5＋Al 2O 3) | ????3.0 | ?3.0 | ???4.4 | ?3.0 | ?0.0 | ?7.5 |
| SiO 2/(SiO 2＋P 2O 5＋Al 2O 3) | ????7.3 | ?7.3 | ???7.2 | ?7.3 | ?7.5 | ?6.9 |
| Total pore volume ml/g | ????0.57 | ?0.54 | ???0.61 | ?0.53 | ?0.41 | ?0.60 |
| Specific surface m 2/g | ????252 | ?230 | ???262 | ?225 | ?196 | ?240 |
| Physical strength N/ grain | ????64 | ?70 | ???55 | ?80 | ?76 | ?60 |
| Tap density g/ml | ????0.70 | ?0.73 | ???0.67 | ?0.74 | ?0.80 | ?0.67 |
| Pore distribution %:＜4.0nm | ????3.2 | ?5.0 | ???6.2 | ?3.5 | ?14.0 | ?9.5 |
| ????4.0—1?5.0nm | ????93.3 | ?94.2 | ???91.3 | ?92.6 | ??82.2 | ?71.2 |
| ????＞15.0nm | ????3.5 | ?0.8 | ???2.5 | ?3.9 | ??3.8 | ?19.3 |
| ????PVI％ | ????92.2 | ?93.1 | ???90.4 | ?91.5 | ??86.1 | ?87.7 |
Each routine activity rating of catalyst result of table 6
The hydrofining wax product
| Project | Raw material | Example 1 | Example 2 | Example 3 | Example 4 | With reference to 1 | With reference to 2 |
| Oleaginousness W% | ??0.48 | ??0.46 | ??0.45 | ?0.44 | ????0.46 | ??0.48 | ????0.45 |
| Look number | ????4 | ????＜1 | ???＜1 | ???＜1 | ????＜1 | ????＜1 | ????＜1 |
| Stability number | ???5-6 | ????2-3 | ???2-3 | ???2-3 | ????2-3 | ????3-4 | ????3-4 |
| Readily carbonizable substance | Defective | Qualified | Qualified | Qualified | Qualified | Qualified | Qualified |
| Ultraviolet extinction value (simplified method) 280um | ???- | ??0.24 | ??0.20 | ??0.34 | ????0.20 | ???0.46 | ????0.40 |
| ????290um | ???- | ??0.14 | ??0.18 | ??0.20 | ????0.16 | ???0.28 | ????0.25 |
Claims (2)
1. a Wax hydrofining catalyst is an active ingredient with VIII family and group vib metallic element, with SiO
2-P
2O
5-Al
2O
3Be carrier, it is characterized in that carrier contains SiO
25-10w%, P
2O
52-5w%, Al
2O
385-93W%, catalyzer contains MoO
318-24w%, NiO4-6w%, the pore volume of catalyst pores diameter in the 4.0-15.0nm scope accounts for more than 90% of the pore volume of bore dia in the 0.0-60.0nm scope, and between 0.50-0.65ml/g/, the specific surface area of catalyzer is 220-280m to bore dia at the pore volume of 0.0-60.0nm scope
2/ g.
2. according to the described Wax hydrofining catalyst of claim 1, it is characterized in that catalyzer follows these steps to preparation:
(1) containing Al
2O
3The aluminum chloride colloidal sol of 4-6g/100ml with contain SiO
26.0-9.0g/ml acidified sodium silicate mix, regulate pH＜3 of mixed solution, temperature remains on 10-17 ℃, aging 1-5 hour;
(2) at 10-17 ℃, with the mixed sols that the neutralization of the ammoniacal liquor of 8-11% is obtained by (1), control pH is 7.0-9.0, and be 8-12min duration of contact, and total reaction time is 0.5-2.0 hour;
(3) filtration and washing are by the throw out of (2) gained, wash temperature 23-27 ℃, washing time 20-50min, washing times 2-4 time;
(4) be the phosphoric acid of 50-55w% and nitric acid peptization that concentration is 31-34w% wet gel with concentration by (3) gained, the add-on of phosphoric acid is the 70-140g/kg butt, the add-on of nitric acid is the 80-220ml/kg butt, and peptization time is 1.5-4.0 hour, stirs during peptization;
(5) the false sol solutions by (4) gained is dripped by water dropper, and by being in the oil ammonia column under the room temperature, wet bulb soaked 1-4 hour in the ammoniacal liquor of 3-6w%;
(6) wet bulb takes out from ammoniacal liquor, descends dry 2-6 hour at 70-100 ℃, then at 550-700 ℃ of following roasting 2-5 hour;
(7) with the bead of the aqueous solution dipping that contains molybdenum and/or nickel by (6) gained, at 100-140 ℃, dry 2-5 hour, then at 450-540 ℃, roasting 2-5 hour.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 92111133 CN1032408C (en) | 1992-10-14 | 1992-10-14 | Wax hydrofining catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 92111133 CN1032408C (en) | 1992-10-14 | 1992-10-14 | Wax hydrofining catalyst |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1085594A CN1085594A (en) | 1994-04-20 |
| CN1032408C true CN1032408C (en) | 1996-07-31 |
Family
ID=4945166
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 92111133 Expired - Fee Related CN1032408C (en) | 1992-10-14 | 1992-10-14 | Wax hydrofining catalyst |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1032408C (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1045099C (en) * | 1996-09-11 | 1999-09-15 | 中国石油化工总公司 | Hydrogenation post-refining process for lubricant oil |
| CN1054151C (en) * | 1996-12-10 | 2000-07-05 | 中国石油化工总公司 | Catalyst for hydrodesulfurization fraction oil |
| CN1089032C (en) * | 1996-12-10 | 2002-08-14 | 中国石油化工集团公司 | Porous and silicon contg. alumina carrier beads, and method for making same |
| CN1102643C (en) * | 1998-09-28 | 2003-03-05 | 中国石油化工集团公司 | Catalyst for hydrorefining pertroleum wax and its preparing process |
| WO2004037408A1 (en) * | 2002-10-10 | 2004-05-06 | China Petroleum & Chemical Corporation | A silicon-containing alumina support, preparation thereof and a catalyst comprising the alumina support |
-
1992
- 1992-10-14 CN CN 92111133 patent/CN1032408C/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN1085594A (en) | 1994-04-20 |
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