CN103785404A - Preparation method of hydrotreatment catalyst - Google Patents
Preparation method of hydrotreatment catalyst Download PDFInfo
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- CN103785404A CN103785404A CN201210427762.0A CN201210427762A CN103785404A CN 103785404 A CN103785404 A CN 103785404A CN 201210427762 A CN201210427762 A CN 201210427762A CN 103785404 A CN103785404 A CN 103785404A
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- alumina support
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Abstract
The invention discloses a preparation method of a hydrotreatment catalyst. The method comprises the following process: first preimpregnating an alumina carrier with an ammonium salt solution; then heating the impregnated alumina carrier in a sealed container; and finally loading an active component and an auxiliary agent onto the treated alumina carrier, and drying and roasting to obtain the hydrotreatment catalyst. The method can effectively pretreat the carrier, improve physicochemical properties of the carrier, especially the chemical properties of the surface of the carrier, and enable the active metal component to uniformly distribute on the carrier, so as to prepare the hydrotreatment catalyst with high activity.
Description
Technical field
The present invention relates to a kind of preparation method of hydrotreating catalyst.
Background technology
The hydrotreating catalyst of oil product, generally with γ-Al
2o
3or contain a small amount of other element as γ-Al of Si, P, B, Ti, F
2o
3for carrier, take W, the Mo of VI family and Co, the Ni of VIII family as hydrogenation activity component.
High-activity hydrogenation catalyst is the target that people pursue always, and high-activity hydrogenation catalyst can make the petroleum of high sulfur-bearing, nitrogen under the operating condition relaxing, and makes sulphur, nitrogen compound wherein change into corresponding oxide and be excluded.Also can under harsh operating condition, improve treating capacity simultaneously, or the service life of extending catalyst, to reach the object of flexible operating.
Although at present the activity of heavy oil hydrogenating treatment catalyst is quite high, more highly active hydrotreating catalyst is still that we pursue.A highly active hydrotreating catalyst, except outside the Pass having with supported metal species, amount of metal, also has direct relation with the character of carrier.The distribution of main is metal component on carrier is wanted evenly.And this distributivity is relevant with carrier surface character.
US4,317,746 have described carrier after preimpregnation and vapor portion preimpregnation, then soak active metal, can suitably improve like this distribution of metal on carrier, thereby can improve catalyst activity.US4,446,248; US4,540,483 have described respectively the carrier of three kinds of different pore size distributions, adopt the ammonium hydroxide aqueous solution preimpregnation, dry of concentration 20～30w%, wetting with citric acid again, then soak metallic solution, thereby make specific activity without the active high hydrotreating catalyst of ammonia preimpregnation.The method providing by above-mentioned patent, catalyst carrier is processed, although there is certain effect, but still large not to the increase rate of catalyst activity, and complex process, cost is high, particularly use the method for the ammonium hydroxide aqueous solution preimpregnation carrier of 20～30w%, because ammonia concentration is high, high volatility, worsens and contaminated environment condition of work.
In order to address the above problem, CN94116958.8 discloses a kind of method of preparing hydrotreating catalyst, is that the macropore aluminium hydroxide that adopts sodium aluminate and aluminum sulfate to make under suitable temperature, pH value is raw material, through overmolding, be dried, γ-Al that roasting obtains
2o
3for carrier, before supporting VI B and VIII family active metal, adopt the preimpregnation of low concentration ammoniacal liquor (0.01～0.1w%) solution, make on final catalyst Metal Distribution even, the activity of catalyst particularly nitric efficiency improves greatly.The commercial Application of this catalyst has greatly met the requirement of country to oil quality at that time, but along with new standard improves gradually to the requirement of oil quality, need to develop active higher catalyst.
Summary of the invention
For existing technical deficiency, the object of the invention is to find a kind of more efficiently method carrier is carried out to pretreatment, improve the physico-chemical property of carrier, especially the chemical property of carrier surface, active metal component is more evenly distributed on carrier, prepares more highly active hydrotreating catalyst.
A preparation method for hydrotreating catalyst, comprises following process: first adopt ammonium salt solution to carry out pre-preg to alumina support; Then the alumina support after dipping is put into airtight container and carry out heat treated; Finally load active component and auxiliary agent on alumina support after treatment, drying, roasting make hydrotreating catalyst.
Ammonium salt solution described in the inventive method is the aqueous solution of ammonium nitrate, ammonium carbonate, ammonium hydrogencarbonate.Ammonium salt solution mass concentration is 10%-20%.When pre-preg, the volume ratio of ammonium salt solution and alumina support is 1-3, and dip time is 1-3 hour.
The treatment temperature of carrying out heat treated in the airtight container described in the inventive method is 150 ℃-250 ℃, and the processing time is 1-4 hour.
Alumina support described in the inventive method is the alumina support after moulding.The shape of alumina support is spherical, bar shaped (comprising cylindrical, trilobal, quatrefoil etc.), sheet shape or granulated, take bar shaped as best.Alumina support can adopt commercially available formed alumina carrier, also can adopt conventional method to make by oneself.Preferably adopt with the following method self-control: the aluminum sulfate of metering or aluminium chloride and ammoniacal liquor or sodium metaaluminate etc. are neutralized under 30-85 ℃ and pH6-10 condition, the boehmite of generation again through aging, washing, be dried, the step such as roasting, moulding makes alumina support.
MoO containing metering for the loading process of the active component described in the inventive method and auxiliary agent
3, NiO and P the alumina support of maceration extract pretreatment, maceration extract is preferably a kind of containing 10-80g/100mlMoO
3, the solution of 2-20g/100mlNiO and 1-10g/100mlP, the concentration of maceration extract can be determined according to the metal composition on final catalyst.Described dipping can adopt volume dipping, incipient impregnation, spray impregnating.The preferred volume dipping of crossing in all dipping methods, dip time is 1-5 hour.After load active component and auxiliary agent, comprise dry and roasting process.Described is dried as dry 6-10 hour at 80-120 ℃, and described roasting is roasting 3-6 hour at 400-600 ℃.
A kind of hydrotreating catalyst, adopts said method to be prepared, catalyst consist of MoO
3%(is heavy) 20-30, NiO%(is heavy) and 1-10, P
2o
5%(is heavy) 1-10, all the other are alumina catalyst support.
In the inventive method, alumina support is through ammonium salt aqueous solution preimpregnation before dipping active metal component, and the alumina support after dipping is placed in closed container heat-treats.Alumina support after ammonium salt preimpregnation has further improved the surface property of alumina support in the airtight container with uniform temperature and pressure after heat treatment, active component is evenly distributed on carrier, thereby improve the catalytic activity of catalyst, particularly significantly improved denitrification percent.The inventive method is without significantly adjusting original preparation technology, and operating process is simple, is suitable for commercial Application.
The specific embodiment
Further illustrate the effect of the inventive method below in conjunction with embodiment, but be not limited to following examples.
The aluminum sulfate of metering or aluminium chloride and ammoniacal liquor or sodium metaaluminate etc. are neutralized under 30-85 ℃ and pH6-10 condition, the boehmite generating forms alumina support through aging, washing, dry, moulding and roasting again, the present invention's alumina support used is bar shaped, length is 3-5 millimeter, diameter is 1.3 millimeters, is shaped as clover.
Take appropriate above-mentioned alumina support, the ammonium nitrate solution that is 10-20% by appropriate mass concentration dipping 1-3 hour, the alumina support after dipping proceeds in autoclave in 150 ℃-250 ℃ sealings, heat treatment 1-4 hour, naturally cools to room temperature.With the appropriate 10-80g/100mlMoO that contains
3, the maceration extract of 2-20g/100mlNiO and 1-10g/100mlP floods above-mentioned carrier 1-5 hour, filters redundant solution, dry 6-10 hour at 80-120 ℃, and at 400-600 ℃, roasting 3-6 hour makes hydrotreating catalyst.
Example 1
Take 100 grams of above-mentioned homemade cloverleaf pattern carrying aluminas, the ammonium nitrate solution that is 10% by 200ml mass concentration dipping 2 hours, elimination redundant solution proceeds in autoclave under 150 ℃ of sealings, self-generated pressure heat treatment 2 hours by the alumina support after dipping, naturally cools to room temperature.With 150ml containing MoO
3105 grams, NiO15 gram and 18ml volumetric concentration are that the maceration extract of 85% phosphoric acid floods above-mentioned carrier 3 hours, filter redundant solution, and at 110 ℃ dry 8 hours, at 500 ℃, roasting made hydrotreating catalyst C1 for 4 hours, and this catalyst consists of MoO
3%(is heavy) 25.3, NiO%(is heavy) 3.8, P
2o
5%(is heavy) 4.2.
Example 2
With example 1, just the mass concentration of ammonium nitrate solution is 15% when carrier pretreatment, and liquor capacity is 150ml, and dip time is 3h, and when heat treatment, temperature is 200 ℃, and the processing time is 1 to make hydrotreating catalyst C2, and this catalyst consists of MoO
3%(is heavy) 26.1, NiO%(is heavy) 3.9, P
2o
5%(is heavy) 4.5.
Example 3
With example 1, while being carrier pretreatment, the mass concentration of ammonium nitrate solution is 20%, and liquor capacity is 150ml, and dip time is 1h, and when heat treatment, temperature is 250 ℃, processing time 4h.In activity component impregnation process, contain MoO with 200ml
3120 grams, NiO30 gram and 20ml concentration are that the maceration extract of 85% phosphoric acid floods above-mentioned carrier 3 hours, make hydrotreating catalyst C3, and this catalyst consists of MoO
3%(is heavy) 27.2, NiO%(is heavy) 4.2, P
2o
5%(is heavy) 5.1.
Example 4
With example 1, while being carrier pretreatment, the mass concentration of ammonium nitrate solution is 18%, and liquor capacity is 160ml, and when heat treatment, temperature is 220 ℃.In activity component impregnation process, contain MoO with 100ml
380 grams, NiO20 gram and 15ml concentration are that the maceration extract of 85% phosphoric acid floods above-mentioned carrier 3 hours, make hydrotreating catalyst C4, and this catalyst consists of MoO
3%(is heavy) 24.7, NiO%(is heavy) 3.6, P
2o
5%(is heavy) 4.0.
Example 5
With example 1, while being carrier pretreatment, the mass concentration of ammonium nitrate solution is 13%, and liquor capacity is 100ml, and when hydrothermal treatment consists, temperature is 175 ℃.In activity component impregnation process, contain MoO with 180ml
390 grams, NiO18 gram and 18ml concentration are that the maceration extract of 85% phosphoric acid floods above-mentioned carrier 3 hours, make hydrotreating catalyst C5, and this catalyst consists of MoO
3%(is heavy) 25.5, NiO%(is heavy) 3.7, P
2o
5%(is heavy) 4.1.
Comparative example 1
With embodiment 5, just adopting mass concentration is 0.05% dilute ammonia solution pre-preg alumina support, makes hydrotreating catalyst C6.
Comparative example 2
With embodiment 5, just after ammonium salt impregnation process, do not seal heat treatment, make hydrotreating catalyst C7.
The denitrification activity of catalyst prepared by above-described embodiment and comparative example is evaluated, and wherein the prepared hydrotreating catalyst C7 of comparative example 2 is as reference catalyst.Each catalyst is evaluated on 200ml small hydrogenation device, and raw materials used oil is same batch of wax tailings, and feedstock oil character, in table 1, is evaluated condition used in table 2, and evaluation result is in table 3.
Table 1
| 20 ℃ of density, g/cm 3 | 0.8845 |
| Flow process ℃ | ? |
| IBP | 225 |
| 10% | 340 |
| 30% | 365 |
| 50% | 372 |
| 70% | 395 |
| 90% | 457 |
| EP | - |
| Sulphur, %(is heavy) | 0.85 |
| Total nitrogen, %(is heavy) | 0.45 |
| Carbon residue, %(is heavy) | 0.1 |
| Colloid, %(is heavy) | 4.2 |
Table 2
| Reaction temperature ℃ | Hydrogen partial pressure MPa | Air speed LHSV, hr -1 | Hydrogen to oil volume ratio |
| 380 | 6.5 | 1.0 | 1000:1 |
Table 3
| Catalyst | C1 | C2 | C3 | C4 | C5 | C6 | C7 |
| Denitrification activity relatively | 124 | 126 | 134 | 132 | 128 | 117 | 100 |
Can find out that by table 3 data the relative comparative catalyst of catalyst who adopts the inventive method to prepare has higher denitrification activity.
Claims (10)
1. a preparation method for hydrotreating catalyst, is characterized in that: comprise following process: first adopt ammonium salt solution to carry out pre-preg to alumina support; Then the alumina support after dipping is put into airtight container and carry out heat treated; Finally load active component and auxiliary agent on alumina support after treatment, drying, roasting make hydrotreating catalyst.
2. method according to claim 1, is characterized in that: described ammonium salt solution is the aqueous solution of ammonium nitrate, ammonium carbonate, ammonium hydrogencarbonate.
3. method according to claim 1 and 2, is characterized in that: described ammonium salt solution mass concentration is 10%-20%.
4. method according to claim 1, is characterized in that: when pre-preg, the volume ratio of ammonium salt solution and alumina support is 1-3, and dip time is 1-3 hour.
5. method according to claim 1, is characterized in that: the treatment temperature of carrying out heat treated in described airtight container is 150 ℃-250 ℃, and the processing time is 1-4 hour.
6. method according to claim 1, is characterized in that: described alumina support is the alumina support after moulding, and being shaped as of alumina support is spherical, bar shaped, sheet shape or granulated.
7. method according to claim 1, is characterized in that: the MoO containing metering for described active component and the loading process of auxiliary agent
3, NiO and P the alumina support of maceration extract pretreatment, in maceration extract containing 10-80g/100mlMoO
3, 2-20g/100mlNiO and 1-10g/100mlP.
8. method according to claim 1, is characterized in that: dipping adopted volume dipping, incipient impregnation, spray dipping.
9. method according to claim 1, is characterized in that: described is dried as dry 6-10 hour at 80-120 ℃, and described roasting is roasting 3-6 hour at 400-600 ℃.
10. a hydrotreating catalyst, adopts either method preparation in claim 1 to 9, catalyst consist of MoO
3%(is heavy) 20-30, NiO%(is heavy) and 1-10, P
2o
5%(is heavy) 1-10, all the other are alumina catalyst support.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106466601A (en) * | 2015-08-14 | 2017-03-01 | 中国石油化工股份有限公司 | A kind of preparation method of hydrocatalyst for saturating arylhydrocarbon and the application of the catalyst prepared by the method and this catalyst |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5215955A (en) * | 1991-10-02 | 1993-06-01 | Chevron Research And Technology Company | Resid catalyst with high metals capacity |
| CN1121048A (en) * | 1994-10-19 | 1996-04-24 | 中国石油化工总公司 | Hydrogenating treatment catalyst |
| CN102451721A (en) * | 2010-10-26 | 2012-05-16 | 中国石油化工股份有限公司 | Hydrogenation catalyst, preparation method and application thereof as well as hydrofining method |
-
2012
- 2012-11-01 CN CN201210427762.0A patent/CN103785404B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5215955A (en) * | 1991-10-02 | 1993-06-01 | Chevron Research And Technology Company | Resid catalyst with high metals capacity |
| CN1121048A (en) * | 1994-10-19 | 1996-04-24 | 中国石油化工总公司 | Hydrogenating treatment catalyst |
| CN102451721A (en) * | 2010-10-26 | 2012-05-16 | 中国石油化工股份有限公司 | Hydrogenation catalyst, preparation method and application thereof as well as hydrofining method |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106466601A (en) * | 2015-08-14 | 2017-03-01 | 中国石油化工股份有限公司 | A kind of preparation method of hydrocatalyst for saturating arylhydrocarbon and the application of the catalyst prepared by the method and this catalyst |
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