CN105709765B - A kind of preparation method of residuum hydrogenating and metal-eliminating catalyst - Google Patents
A kind of preparation method of residuum hydrogenating and metal-eliminating catalyst Download PDFInfo
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Abstract
The present invention discloses a kind of preparation method of residuum hydrogenating and metal-eliminating catalyst, comprises the following steps：（1）By expanding agent, boehmite dry glue powder, extrusion aid, peptizing agent kneading into plastic, extrusion, drying；（2）By step（1）The mixed solution of the unsaturated spray impregnation of phosphoric acid of dried carrier and ammonium oxalate, carrier after dipping carries out heated sealed processing, processing pressure is the self-generated pressure under air-proof condition, treatment temperature is 120 160 DEG C, processing time is 6 12 hours, and alumina support is made through drying, roasting in the carrier after processing；（3）Step（2）The aluminum oxide dipping active component of preparation, is made residuum hydrogenating and metal-eliminating catalyst alumina support after dipping through drying, roasting.This method can improve the activity stability of residuum hydrogenating and metal-eliminating catalyst.
Description
Technical field
The present invention relates to a kind of preparation method of residuum hydrogenating and metal-eliminating catalyst, it is steady to relate in particular to a kind of high activity
The preparation method of qualitative residuum hydrogenating and metal-eliminating catalyst.
Background technology
The main function of residuum hydrogenating and metal-eliminating catalyst is that to remove the various metals that residual oil is included including nickel, vanadium miscellaneous
Matter, reduce its adverse effect to downstream catalyst and following process device.During residual hydrogenation, nickel, vanadium are to vulcanize
The form deposition of thing on a catalyst, these deposit blocking catalyst ducts, causes catalyst inactivation.Therefore residual hydrogenation takes off
The metal removal activity and receiving metal ability of metallic catalyst are related to the service cycle of residual hydrogenation equipment.
CN1289640A discloses a kind of preparation method of carried catalyst for hydrogenation and demetalation.The preparation side of the catalyst
Method includes taking macropore δ and/or θ phase alumina carrier, is put into and sprays in rolling pot, by group VIB metallic compound and/or the VIIIth race
Metallic compound is configured to ammonia solution or the aqueous solution, is uniformly sprayed with atomizing type on carrier, and the catalyst after spraying is direct
It is sent into the roaster that temperature is 300-450 DEG C, is then gradually heating to 460-550 DEG C again, constant temperature 1-5 is small in the presence of the air
When, catalyst activity component prepared by this method is uniformly distributed in carrier surface.But during HDM, catalyst
Outer surface is easily deposited on catalyst surface with the metal such as metal function, nickel, vanadium first and causes catalyst inactivation, can thus make
The active component utilization rate of catalytic inner reduces.
CN102641739A discloses a kind of hydrogenation catalyst of the equal distribution gradient of alkalinous metal and active metal component concentration
Agent and preparation method thereof.The patent is being sprayed by preparing diluter active metal solution and alkalinous metal solution or deionized water
During leaching, denseer active metal solution and alkalinous metal solution saturation sprayed carrier are progressively added；It is or different by preparing
The active metal solution and alkali metal soln of concentration, are soaked from low to high by active metal maceration extract and alkali metal soln concentration
Stain is on carrier；Or with alkali concentration relatively low solution or deionized water dipping, in dipping process progressively to add alkalinous metal dense
High solution is spent into maceration extract；Drying and roasting；The relatively low solution of active metal concentrations or deionized water dipping, dipping process are used again
In progressively add the higher solution of active metal concentrations into maceration extract；Or alkalinous metal is immersed in after active metal dipping.
Although catalyst activity component prepared by this method is in non-uniform Distribution, i.e. catalyst external surface active component content is higher, interior
Portion's active component content is relatively low.But because outer surface activity is higher, easily cause reaction violent, cause outer surface duct block and
Make catalyst inactivation.
The content of the invention
In view of the shortcomings of the prior art, the present invention provides a kind of system of high-activity stable residuum hydrogenating and metal-eliminating catalyst
Preparation Method.
A kind of preparation method of residuum hydrogenating and metal-eliminating catalyst, comprises the following steps：
（1）By expanding agent, boehmite dry glue powder, extrusion aid, peptizing agent kneading into plastic, extrusion, drying；
（2）By step（1）The mixed solution of the unsaturated spray impregnation of phosphoric acid of dried carrier and ammonium oxalate, phosphoric acid and grass
The mass ratio of sour ammonium is 3:1-7:1, the mass concentration of ammonium ion is 0.6%-1.2% in mixed solution, every time unsaturated spray leaching
Stain amount is not higher than step（1）The 80% of dried carrier water absorption, the carrier after dipping carry out heated sealed processing, processing pressure
Power is the self-generated pressure under air-proof condition, and treatment temperature is 120-160 DEG C, and processing time is 6-12 hours, the carrier after processing
Alumina support is made through drying, roasting；
（3）Step（2）The aluminum oxide of preparation impregnates active component, and residual hydrogenation, which is made, through drying, roasting after dipping takes off gold
Metal catalyst alumina support.
The inventive method step（1）Described in expanding agent can be carbon powder, starch etc., preferably carbon powder, expanding agent
Addition be boehmite dry glue powder weight 3%-5%.Described extrusion aid can be sesbania powder, starch, Methyl cellulose
Element, preferably sesbania powder, addition are the 3%-5% of boehmite dry glue powder weight.Described peptizing agent can be formic acid, second
One or more of mixing in acid, citric acid, nitric acid, addition is the 3%-10% of boehmite dry glue powder weight, depending on last
Depending on molding effect.
The inventive method step（2）The mass ratio of middle phosphoric acid and ammonium oxalate is 4:1-6:1, the matter of ammonium ion in mixed solution
Amount concentration is 0.8%-1.0%, and unsaturated spray pickup is not higher than step every time（1）The 70% of dried carrier water absorption, place
It is 130-150 DEG C to manage temperature, and processing time is 8-10 hours.
The inventive method step（2）In add appropriate methanol in the forward direction system of heated sealed processing, methanol plus
It is step to enter amount（1）The 15wt%-30wt% of middle boehmite dry glue powder weight.During follow-up heated sealed, methanol
Steam, to being handled under mixed atmosphere carrier, is enhanced inside and outside carrier with the mixed gases volatilized after carrier calcination
Nature difference, hence it is evident that improve activity stability.
The inventive method step（2）Described in unsaturated spray dipping be carried out in two steps, unsaturated spray leaching for the first time
The dosage of mixed solution is step during stain（1）The 50%-80% of middle boehmite dry glue powder saturated water adsorptive value, preferably 60%-70%,
The dosage of mixed solution is step during second of unsaturated spray dipping（1）Middle boehmite dry glue powder saturated water adsorptive value
20%-50%, preferably 30%-40%.
The inventive method step（3）Described in maceration extract be water-soluble containing group vib and/or group vib metallic compound
Liquid；Wherein group vib metallic compound is the one or more in ammonium molybdate, ammonium paramolybdate, ammonium metatungstate or ammonium tungstate.VIII
Metallic compound is one kind in nickel chloride, nickel nitrate, nickel sulfate, nickel acetate, cobalt chloride, cobalt nitrate, cobaltous sulfate or cobalt acetate
It is or several；The content of group vib metallic compound is calculated as 1-40g/100ml, group VIII metal by corresponding oxide in maceration extract
The content of compound is calculated as 0.1-20g/100ml by corresponding oxide, and the concentration of metallic compound can be according to production in maceration extract
Product need to adjust accordingly.
Step in the inventive method（3）Active component is impregnated using unsaturated spray step impregnation.Unsaturated spray for the first time
The dosage of maceration extract is rapid during leaching dipping（2）The 10%-40% of middle alumina support water absorption, preferably 20%-30%.In maceration extract
The content of group vib metallic compound is calculated as 3-6g/100ml by corresponding oxide, and the content of group VIII metallic compound presses phase
Oxide is answered to be calculated as 0.3-0.8g/100ml；The dosage of maceration extract is rapid during second of unsaturated spray dipping（2）Middle aluminum oxide
The 30%-60% of carrier water absorption, preferably 40%-50%, the content of group vib metallic compound is calculated as by corresponding oxide in maceration extract
6-9g/100ml, the content of group VIII metallic compound are calculated as 0.8-1.2g/100ml by corresponding oxide；Third time insatiable hunger
The dosage of maceration extract is rapid when being impregnated with spray（2）The 20%-50% of middle alumina support water absorption, preferably 30%-40%, maceration extract
The content of middle group vib metallic compound is calculated as 9-12g/100ml by corresponding oxide, and the content of group VIII metallic compound is pressed
Corresponding oxide is calculated as 1.2-1.5g/100ml.Repeatedly total dosage of maceration extract is at least the full of alumina support during spray dipping
And water absorption.
Drying described in the inventive method dries 1-10 hours under the conditions of being 80 DEG C -120 DEG C.Described roasting process is
In 500 DEG C of -650 DEG C of roasting 2-4 hours.
In the prior art, technical staff does one's utmost to pursue physico-chemical property inside and outside aluminum oxide during alumina support is prepared
It is consistent.For the pore structure of aluminum oxide, researcher wishes the pore volume of aluminum oxide, aperture inside and outside aluminum oxide in uniform point
Cloth.Therefore expanding agent is added by way of kneading in the preparation process of aluminum oxide.Oxidation with identical physico-chemical property
Aluminium is considered as a kind of important indicator of excellent carrier, be fact proved for most of catalytic reaction strictly favourable.
It is unsaturated using suitable solution in the preparation process of residual oil catalyst for demetalation but the result of study of inventor shows
Oxide impregnation aluminium is sprayed, uneven modification is carried out to alumina support, to carrying alumina inside and outside physico-chemical property such as pore volume, aperture
Differential modification is carried out, the activity stability of residuum hydrogenating and metal-eliminating catalyst can be significantly improved.
Embodiment
The effect of the present invention and effect are further illustrated with reference to embodiment, but is not limited to following examples.
Embodiment 1
It is 0.85ml/g, specific surface area 190m to weigh pore volume2/ g, water absorption rate are 1ml/g boehmite dry glue powder
（Shenyang Catalyst Plant produces, aluminum oxide contents on dry basis 70%）100 grams, with 5 grams of carbon powders, 5 grams of sesbania powders are well mixed, and are added
It is uniform dissolved with the aqueous solution kneading of 8 grams of nitric acid in right amount, a diameter of 1.8mm cloverleaf pattern bar is extruded on screw rod banded extruder, in
120 DEG C dry 3 hours.Dried carrier is put into spray rolling pot, under rotary state, with load of the atomizing type into rolling pot
Body unsaturation sprays 80ml and contains 1.6 grams of ammonium oxalate, and the solution that 8 grams of phosphoric acid sprays above-mentioned carrier, the matter of ammonium ion in solution
It is 0.6% to measure concentration, and the mass ratio of phosphoric acid and ammonium oxalate is 5:1.Carrier after spraying is placed in autoclave to be added in 130 DEG C of sealings
Heat 8 hours, then carrier is dried 5 hours in 80 DEG C.Dried carrier continues to be put into spray rolling pot, in rotary state
Under, above-mentioned solution 40ml is sprayed with carrier unsaturation of the atomizing type into rolling pot.Carrier after spraying be placed in autoclave in
140 DEG C of heated sealeds 10 hours, then carrier is dried 5 hours in 80 DEG C.Dried carrier is calcined at a temperature of 650 DEG C
4 hours obtained alumina supports.Weigh above-mentioned 100 grams of alumina support to be put into spray rolling pot, under rotary state, with atomization
Carrier spray dipping MoO of the mode into rolling pot3Concentration is 4g/100ml（Molybdenum source comes from ammonium molybdate）, NiO concentration is 0.5g/
100ml（Nickel source comes from nickel chloride）Active metal aqueous solution 10ml；Then MoO is used3Concentration is 7g/100ml（Molybdenum source comes from molybdenum
Sour ammonium）, NiO concentration is 0.8g/100ml（Nickel source comes from nickel chloride）Active metal aqueous solution 40ml continue spray oxide impregnation
Alumina supporter；Finally use MoO3Concentration is 9g/100ml（Molybdenum source comes from ammonium molybdate）, NiO concentration is 1.3g/100ml（Nickel source comes from
Nickel chloride）Active metal aqueous solution 50ml continue spray oxide impregnation alumina supporter.Rear material is sprayed to dry 5 hours in 80 DEG C,
Dried material is calcined 4 hours obtained Hydrodemetalation catalyst C1 at a temperature of 650 DEG C, MoO in catalyst3Content is
7.5wt%, NiO content are 1.0wt%, and remaining is alumina support.
Embodiment 2
With embodiment 1, when simply spraying phosphoric acid with ammonium oxalate solution, spray dipping contains ammonium oxalate 1.5 with 50ml for the first time
Gram, the unsaturated spray dipping of solution that 10.5 grams of phosphoric acid（The mass concentration of ammonium ion is 0.9% in solution, phosphoric acid and oxalic acid
The mass ratio of ammonium is 7:1）, the temperature of sealing heat treatment for the first time is 120 DEG C, and processing time is 10 hours, second of spray leaching
The stain unsaturated spray dipping of the above-mentioned solution of 30ml.The temperature of second of sealing heat treatment is 150 DEG C, and processing time is 6 hours,
During spray dipping active metal, spray dipping uses 30ml MoO for the first time3Concentration is 5g/100ml（Molybdenum source comes from ammonium molybdate）,
NiO concentration is 0.3g/100ml（Nickel source comes from nickel chloride）The active metal aqueous solution dipping.Second of spray dipping 30ml
MoO3Concentration is 8g/100ml（Molybdenum source comes from ammonium molybdate）, NiO concentration is 1.0g/100ml（Nickel source comes from nickel chloride）Activity
Aqueous metal solution impregnates.40mlMoO is used during third time spray dipping3Concentration is 10g/100ml（Molybdenum source comes from ammonium molybdate）, NiO
Concentration is 1.2g/100ml（Nickel source comes from nickel chloride）The active metal aqueous solution dipping.Hydrodemetalation catalyst C2 is made,
MoO in catalyst3Content is 8wt%, and NiO contents are 0.85wt%, and remaining is alumina support.
Embodiment 3
With embodiment 1, when simply spraying phosphoric acid with ammonium oxalate solution, spray dipping contains ammonium oxalate 2.4 with 60ml for the first time
Gram, the unsaturated spray dipping of solution that 7.2 grams of phosphoric acid（The mass concentration of ammonium ion is 1.2% in solution, phosphoric acid and oxalic acid
The mass ratio of ammonium is 3:1）, the temperature of sealing heat treatment for the first time is 160 DEG C, and processing time is 6 hours, second of spray dipping
With the unsaturated spray dipping of the above-mentioned solution of 20ml.The temperature of second of sealing heat treatment is 130 DEG C, and processing time is 12 hours.
During spray dipping active metal, dipping 20mlMoO is sprayed for the first time3Concentration is 6g/100ml（Molybdenum source comes from ammonium molybdate）, NiO
Concentration is 0.8g/100ml（Nickel source comes from nickel chloride）The active metal aqueous solution dipping.Second of spray dipping 60ml
MoO3Concentration is 9g/100ml（Molybdenum source comes from ammonium molybdate）, NiO concentration is 0.9g/100ml（Nickel source comes from nickel chloride）Activity
Aqueous metal solution impregnates.20mlMoO is used during third time spray dipping3Concentration is 11g/100ml（Molybdenum source comes from ammonium molybdate）, NiO
Concentration is 1.4g/100ml（Nickel source comes from nickel chloride）The active metal aqueous solution dipping.Hydrodemetalation catalyst C3 is made,
MoO in catalyst3Content is 8.5wt%, and NiO contents are 0.6wt%, and remaining is alumina support.
Embodiment 4
With embodiment 1, when simply spraying phosphoric acid with ammonium oxalate solution, spray dipping contains ammonium oxalate 1.9 with 70ml for the first time
Gram, the unsaturated spray dipping of solution that 7.6 grams of phosphoric acid（The mass concentration of ammonium ion is 0.8% in solution, phosphoric acid and oxalic acid
The mass ratio of ammonium is 4:1）, during heat treatment, add 15 grams of methanol in autoclave, second of spray dipping with the above-mentioned solution of 50ml not
Saturation spray dipping, during heat treatment, adds 20 grams of methanol in autoclave.During spray dipping active metal, spray impregnates for the first time
Use 40mlMoO3Concentration is 3g/100ml（Molybdenum source comes from ammonium molybdate）, NiO concentration is 0.7g/100ml（Nickel source comes from nickel chloride）
The active metal aqueous solution dipping.The temperature of second of sealing heat treatment is 140 DEG C, and processing time is 12 hours.Second of spray
Leaching dipping uses 50ml MoO3Concentration is 6g/100ml（Molybdenum source comes from ammonium molybdate）, NiO concentration is 1.2g/100ml（Nickel source comes from
Nickel chloride）The active metal aqueous solution dipping.30mlMoO is used during third time spray dipping3Concentration is 12g/100ml（Molybdenum source is come
From ammonium molybdate）, NiO concentration is 1.5g/100ml（Nickel source comes from nickel chloride）The active metal aqueous solution dipping.It is de- that hydrogenation is made
Metallic catalyst C4, MoO in catalyst3Content is 7.5wt%, and NiO contents are 1.1wt%, and remaining is alumina support.
Embodiment 5
With embodiment 1, when being simply heat-treated, 30 grams of methanol are added in autoclave, second of spray dipping is above-mentioned with 40ml
The unsaturated spray dipping of solution, during heat treatment, 25 grams of methanol are added in autoclave.Hydrodemetalation catalyst C5, catalysis is made
MoO in agent3Content is 7.5wt%, and NiO contents are 1.0wt%, and remaining is alumina support.
Comparative example 1
This comparative example with example 1, simply by same amount of phosphoric acid and ammonium oxalate solution when carrier is molded with the side of kneading
Formula, which is added in carrier, is made contrast Hydrodemetalation catalyst C6.
Comparative example 2
This comparative example with example 1, simply by same amount of phosphoric acid and ammonium oxalate solution after carrier shaping to satisfy in equal volume
It is added to the mode of dipping in carrier and contrast Hydrodemetalation catalyst C7 is made.
Embodiment 5
The Hydrodemetalation catalyst that the present embodiment is prepared to examples detailed above and comparative example carries out activity rating, respectively urges
Agent activity.Raw material oil nature and evaluation process conditions are shown in Tables 1 and 2, and the Activity evaluation for operating 200h is shown in Table 3.
Table 1
Table 2
Table 3
There is the Hydrodemetalation catalyst that it can be seen from the data of table 3 prepared by the present invention higher HDM to live
Property.
Activity rating is carried out to the catalyst obtained by above-described embodiment and comparative example, the temperature rise for running 5000h is shown in Table 4.
The reaction temperature lift-off value of table 4
Find out from the result of table 4, after reaction 5000 hours, using Hydrodemetalation catalyst provided by the invention, in order to
High demetallization per is kept, required reaction temperature increase rate is far smaller than comparative catalyst, and this illustrates hydrogenation provided by the invention
Catalyst for demetalation has higher activity stability.
Claims (15)
- A kind of 1. preparation method of residuum hydrogenating and metal-eliminating catalyst, it is characterised in that：Comprise the following steps：（1）By expanding agent, boehmite dry glue powder, extrusion aid, peptizing agent kneading into plastic, extrusion, drying；（2）By step（1）The mixed solution of the unsaturated spray impregnation of phosphoric acid of dried carrier and ammonium oxalate, phosphoric acid and ammonium oxalate Mass ratio be 3:1-7:1, the mass concentration of ammonium ion is 0.6%-1.2% in mixed solution, every time unsaturated spray pickup Not higher than step（1）The 80% of dried carrier saturated water adsorptive value, the carrier after dipping carry out heated sealed processing, processing pressure Power is the self-generated pressure under air-proof condition, and treatment temperature is 120-160 DEG C, and processing time is 6-12 hours, the carrier after processing Alumina support is made through drying, roasting；（3）Step（2）The alumina support of preparation impregnates active component, and residual hydrogenation, which is made, through drying, roasting after dipping takes off gold Metal catalyst alumina support；Wherein, step（2）Described in unsaturated spray dipping be carried out in two steps, mixed for the first time during unsaturated spray dipping molten The dosage of liquid is step（1）The 60%-70% of middle boehmite dry glue powder saturated water adsorptive value, when second of unsaturated spray impregnates The dosage of mixed solution is step（1）The 30%-40% of middle boehmite dry glue powder saturated water adsorptive value.
- 2. according to the method for claim 1, it is characterised in that：Step（1）Described in expanding agent be carbon powder or starch, expand The addition of hole agent is the 3%-5% of boehmite dry glue powder weight.
- 3. according to the method for claim 1, it is characterised in that：Step（1）Described in extrusion aid for sesbania powder, starch or Methylcellulose, addition are the 3%-5% of boehmite dry glue powder weight.
- 4. according to the method for claim 1, it is characterised in that：Step（1）Described in peptizing agent for formic acid, acetic acid, lemon One or more of mixing in lemon acid, nitric acid, addition are the 3%-10% of boehmite dry glue powder weight.
- 5. according to the method for claim 1, it is characterised in that：Step（2）The mass ratio of middle phosphoric acid and ammonium oxalate is 4:1- 6:1, the mass concentration of ammonium ion is 0.8%-1.0% in mixed solution, and unsaturated spray pickup is not higher than step every time（1）It is dry 70% of carrier water absorption after dry, treatment temperature are 130-150 DEG C, and processing time is 8-10 hours.
- 6. according to the method for claim 1, it is characterised in that：Step（2）In in the forward direction system of heated sealed processing Appropriate methanol is added, the addition of methanol is step（1）The 15wt%-30wt% of middle boehmite dry glue powder weight.
- 7. according to the method for claim 1, it is characterised in that：Step（3）Middle maceration extract is to contain group vib and/or VIII The aqueous solution of race's metallic compound.
- 8. according to the method for claim 7, it is characterised in that：Group vib metallic compound be ammonium molybdate, ammonium paramolybdate, partially One or more in ammonium tungstate or ammonium tungstate.
- 9. according to the method for claim 7, it is characterised in that：Group VIII metal compound is nickel chloride, nickel nitrate, sulfuric acid One or more in nickel, nickel acetate, cobalt chloride, cobalt nitrate, cobaltous sulfate or cobalt acetate.
- 10. according to the method for claim 7, it is characterised in that：The content of group vib metallic compound is by corresponding in maceration extract Oxide is calculated as 1-40g/100ml, and the content of group VIII metallic compound is calculated as 0.1-20g/100ml by corresponding oxide.
- 11. according to the method for claim 1, it is characterised in that：Step（3）Active component is impregnated using unsaturated spray point Step dipping.
- 12. according to the method for claim 11, it is characterised in that：The dosage of maceration extract when unsaturated spray impregnates for the first time For step（2）The 10%-40% of middle alumina support water absorption, the content of group vib metallic compound presses corresponding oxidation in maceration extract Thing is calculated as 3-6g/100ml, and the content of group VIII metallic compound is calculated as 0.3-0.8g/100ml by corresponding oxide.
- 13. according to the method for claim 11, it is characterised in that：The dosage of maceration extract during second of unsaturated spray dipping For step（2）The 30%-60% of middle alumina support water absorption, the content of group vib metallic compound presses corresponding oxidation in maceration extract Thing is calculated as 6-9g/100ml, and the content of group VIII metallic compound is calculated as 0.8-1.2g/100ml by corresponding oxide.
- 14. according to the method for claim 11, it is characterised in that：The dosage of maceration extract when the unsaturated spray of third time impregnates For step（2）The 20%-50% of middle alumina support water absorption, the content of group vib metallic compound presses corresponding oxidation in maceration extract Thing is calculated as 9-12g/100ml, and the content of group VIII metallic compound is calculated as 1.2-1.5g/100ml by corresponding oxide.
- 15. according to the method for claim 1, it is characterised in that：Drying dries 1-10 hours under the conditions of being 80 DEG C -120 DEG C, It is roasted in 500 DEG C of -650 DEG C of roasting 2-4 hours.
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| CN111821987B (en) * | 2019-04-17 | 2022-07-08 | 中国石油化工股份有限公司 | Preparation method of hydrodenitrogenation catalyst |
| CN111821989B (en) * | 2019-04-17 | 2022-07-12 | 中国石油化工股份有限公司 | Residual oil hydrodenitrogenation catalyst and preparation method thereof |
| CN111821964B (en) * | 2019-04-17 | 2022-07-12 | 中国石油化工股份有限公司 | Carrier and catalyst for hydrodenitrogenation and preparation method thereof |
| CN116139871A (en) * | 2023-01-17 | 2023-05-23 | 金浦新材料股份有限公司 | Special macromolecular catalyst for special amine and preparation method and application thereof |
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