CN102441437A - Preparation methods for macroporous alumina carrier and hydrodemetallization catalyst - Google Patents
Preparation methods for macroporous alumina carrier and hydrodemetallization catalyst Download PDFInfo
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Abstract
The invention discloses preparation methods for a macroporous alumina carrier and a hydrodemetallization catalyst. The preparation method for the macroporous alumina carrier includes the following steps: (1) dry pseudoboehmite gel powder is hydrothermally processed under high pressure; (2) the dry pseudoboehmite gel powder obtained in step 1 is kneaded into a plastic, and pore-expanding agent is added in step 1 or step 2; (3) the plastic obtained in step 2 is shaped, the shaped material is dried and baked, and thereby the macroporous alumina carrier is obtained. The impregnation method is adopted to prepare the hydrodemetallization catalyst. The hydrodemetallization catalyst prepared by the method has large pore volume and pore diameter, centrally distributed pores, moderate mechanical strength and high activity and activity stability.
Description
Technical field
The present invention relates to the preparation method of a kind of macropore alumina supporter and Hydrodemetalation catalyst.
Background technology
In recent years, crude oil heaviness and poor qualityization are on the rise, and especially weigh, metal impurities such as nickel, vanadium equal size raise day by day in the residual oil.These elements are present in the raw material with metal-organic form usually.In PETROLEUM PROCESSING (residual hydrogenation cracking, hydrodesulfurization etc.) process; These metallo-organic compounds can decompose, and metallic element then is deposited on the inside and outside surface of catalyst, on the one hand; Possible blocking catalyst duct; Cause catalysqt deactivation, can cause bed pressure drop to raise fast on the other hand again, make device frequent shutdowns and catalyst changeout more.Therefore, in order to guarantee the long-term normal operation of process units, protect the activity of downstream catalyst bed, these metal impurities must be removed.It is the main means that remove metal impurities wherein that these oil products are carried out hydrotreatment.Wherein Hydrodemetalation catalyst is the key of hydroprocessing technique.Heavily, residuum hydrogenating and metal-eliminating catalyst generally uses the bigger aluminium oxide in aperture to be carrier, is active component with VIII family and/or VI B family metallic element.The bore dia of aluminium oxide and commercial alumina that is generally used for preparing hydrotreating catalyst is less; Can not satisfy the needs of preparation heavy oil, residuum hydrogenating and metal-eliminating catalyst; Therefore, must in the preparing carriers process, adopt the way of " reaming " to increase its aperture.
CN1160602A discloses a kind of macropore alumina supporter that is suitable as the Hydrodemetalation catalyst carrier and preparation method thereof; The pore volume of this macropore alumina supporter is 0.8～1.2 a milliliter/gram; Can several bore dias be 15～20 nanometers; Bulk density is 0.5～0.6 grams per milliliter, and specific area is 110～200 meters
2/ gram.The preparation method of this macropore alumina supporter comprises boehmite dry glue powder and water or aqueous solution; Be kneaded into plastic; The plastic that obtains is extruded into bar on banded extruder; Dry and roasting obtains product, be characterized in, in said process, also added Flammable Solid Class 4.1 particle expanding agent with can with phosphorous, the silicon of boehmite or aluminium oxide generation chemical action or the expanding agent of boron compound.
Chinese patent ZL92112511.9 proposes to pinch boehmite mixed, add Ludox in the extrusion process can play the reaming effect.In addition, in alumina support, adding simultaneously silicon and phosphorus compound, also can to play the reaming effect of reaming effect, particularly phosphorus compound more obvious.This expanding agent and boehmite generation chemical action are so can be described as the chemical enlargement agent.
CN1206037A discloses a kind of residuum hydrogenating and metal-eliminating catalyst and preparation method thereof, and this catalyst is an active component with VIII family and/or VI B family metallic element, loads on a kind of large-pore alumina carrier.The pore volume of this carrier is 0.80～1.20 a milliliter/gram (mercury injection method), and specific area is 110～200 meters
2/ gram can several bore dias be 15～20 nanometers, and bulk density is 0.50～0.60 gram/millimeter.The preparation method of this residuum hydrogenating and metal-eliminating catalyst is in the boehmite kneading process; Add physics expanding agent and chemical enlargement agent simultaneously; Mix and pinch into plastic, extruded moulding, dry, roasting makes carrier; Again with the spray impregnation method with active constituent loading to carrier, make catalyst through dry, roasting.
US4448896 discloses a kind of preparation method of residuum hydrogenating and metal-eliminating catalyst, and this catalyst is an active component with at least a VIII family and/or VI B family metallic element, loads on a kind of large-pore alumina carrier.The specific area of this aluminium oxide is 100～350 meters
2/ gram, preferred 200～300 meters
2/ gram, pore volume be 0.5～1.5 milliliter/gram, preferred 0.7～1.2 milliliter/gram, the aperture be the pore volume in the hole of 3.75～100 nanometers account for total pore volume 90%.The preparation method of this residuum hydrogenating and metal-eliminating catalyst is with boehmite and carbon powder is mixed pinches evenly; Moulding, drying; Roasting makes alumina support in oxygen containing atmosphere, dipping VIII family and VI B family active metal component on this carrier then, or with boehmite, carbon powder and contain VIII family and the compound of VI B family active metal component mix pinch even; Moulding, drying, roasting makes Hydrodemetalation catalyst in oxygen containing atmosphere.
In sum, prior art for preparing weight, residuum hydrogenating and metal-eliminating catalyst method are: (1) preparation has bigger pore volume, aperture, pore distribution concentration, the alumina support of suitable mechanical strength.(2) through the impregnating method with VIII family and/or VI B family metallic element active constituent loading on alumina support.Wherein alumina support prepares simple usually use physics expanding agent or chemical enlargement agent reaming in the process, or uses physics expanding agent and chemical enlargement agent reaming simultaneously.When simple use physics expanding agent prepared alumina support, often the expanding agent consumption was big in order to reach desirable reaming effect, and there is the pore size distribution disperse in carrier, does not concentrate shortcomings such as bad mechanical strength.The simple peptization property variation of using chemical enlargement agent meeting to make boehmite, thus operation brings difficulty to extruded moulding.In addition, when using the chemical enlargement agent in a large number, also can make the relatively disperse of pore size distribution of institute's carrier.Use physics expanding agent and chemical enlargement agent simultaneously; Can bring into play the synergy of two kinds of expanding agents, reduce its each plant demand, can overcome certain negative effect; But preparation process more complicated; The addition of two kinds of expanding agents difficulty reaches ideal matching, and in addition, the pore distribution concentration property of carrier needs further to improve.
Summary of the invention
Not enough to prior art; The present invention provides a kind of to have than large pore volume and aperture; The pore size distribution of concentrating, the alumina support of moderate mechanical strength and the preparation method of Hydrodemetalation catalyst, the Hydrodemetalation catalyst of preparation has greater activity and activity stability.
The preparation method of macropore alumina supporter of the present invention comprises following process:
(1) gets the boehmite dry glue powder and carry out the pressurized thermal water processing;
(2) with step (1) gained boehmite dry glue powder, mix and pinch into plastic, in step (1) or step (2), add expanding agent;
(3) with the moulding of step (2) gained plastic, article shaped is dry, roasting, obtains the macropore oxidation carrier.
The described pressurized thermal water of step (1) is handled and can in suitable high-tension apparatus, be carried out; Like airtight autoclave etc., the hydrothermal treatment consists temperature is 100～300 ℃, preferred 150～250 ℃; Hydrothermal treatment consists pressure is the equipment self-generated pressure under the hydrothermal treatment consists temperature, and the pressurized thermal water processing time is 1～5 hour.The heat treated boehmite dry glue powder of pressure (hydraulic) water prepares the wet stock that process obtains for the boehmite dry glue powder; Also can be to carry out the pressurized thermal water processing after commercially available dry material replenishes suitable quantity of water; Amount of water is generally 20%～200% of boehmite dry glue powder butt weight, is preferably 50%～100%.
The described expanding agent of step (2) is a carbon powder, can be the commercially available prod, also can be that ethene carbon powder commonly used, channel black powder, high wear-resistant carbon black powder etc. are gone up in industry, and preferably granularity is 20～40 μ m.The addition of expanding agent is equivalent to 3%～10% of boehmite butt weight, and preferably 6%～8%.Boehmite can be a kind of boehmite dry glue powder, also can be the boehmite dry glue powder mixture of several kinds of distinct methods preparations.Smooth for moulding, can add extrusion aid and peptizing agent by this area routine techniques, can in step (1) or step (2), add, extrusion aid can be one or more in starch, methylcellulose, the sesbania powder.Peptizing agent is meant organic acid such as formic acid, acetate, citric acid, malonic acid etc., also can be in the various acid of making peptizing agent commonly used such as inorganic acid such as nitric acid, hydrochloric acid etc. one or more.
Can in step (1) and/or step (2), add required adjuvant component as required, one or more of auxiliary agent such as F, Si, Ti, Zr, P, B etc., the kind of auxiliary agent and content are confirmed by the needs that make.
The described dry run of step (3) be generally 100～130 ℃ dry 1～10 hour down, perhaps, be warming up to 100～130 ℃ then, dry 1～10 hour earlier 60～70 ℃ of oven dry 2～3 hours.The temperature of said roasting is 600～750 ℃, and roasting time is 2～4 hours.
Among the preparation method of Hydrodemetalation catalyst of the present invention, be carrier, adopt infusion process supported active metal component Mo or/and Ni obtains final Hydrodemetalation catalyst through super-dry and roasting then with the macropore alumina supporter of method for preparing.
Among the Hydrodemetalation catalyst preparation method; Dipping can adopt saturated infusion process; Also can adopt unsaturated infusion process; The solution that contains Mo can be a kind of or mixture in ammonium molybdate and the ammonium paramolybdate, and the solution that contains Ni can be one or more in nickel nitrate, nickel acetate and the basic nickel carbonate.
Dry run behind the dipping active metal component is generally at 80～140 ℃ to descend dry 1～5 hour, and roasting process is generally 500～600 ℃ of following roastings 1～5 hour.
The pore volume of the Hydrodemetalation catalyst of the inventive method preparation is 0.7～1.50ml/g, and specific area is 150.0～250.0m
2/ g, bore dia be the hole of 10～20 nanometers account for total pore volume 70%～90%, crushing strength 130～160N/cm.Hydrodemetalation catalyst is formed, in catalyst weight, and MoO
3Be 1.0～14.0w%, be preferably 4.0～10.0w%, NiO is 0.5～5.0w%, is preferably 1.0～3.0w%.Hydrodemetalation catalyst provided by the invention can be used for various petroleum distillate HDM processes, the special HDM process that is suitable for weight, residual oil fully.
Technical essential of the present invention is: in the preparation process of alumina support, the boehmite dry glue powder is carried out pressurized thermal water and handle, cooperate a small amount of expanding agent, make required macropore alumina supporter, and then make required Hydrodemetalation catalyst.
Propose to adopt the method that presoma boehmite pressurized thermal water is handled and adding physics expanding agent combines to prepare macropore alumina supporter among the present invention; Overcome and used physics expanding agent and/or chemical enlargement agent to cause the carrier bad mechanical strength easily, the shortcoming that pore size distribution is not concentrated in the prior art for preparing alumina support process.
According to said method the alumina support of preparation has following characteristics:
(1) carrier has bigger pore volume and aperture, pore distribution concentration;
(2) because physics expanding agent consumption is little, make carrier have moderate mechanical strength, bulk density and concentrated pore size distribution.
(3) need not in the preparing carriers to use the chemical enlargement agent, make aluminium oxide have peptization property preferably.
(4) to prepare the alumina support technical process simple for the inventive method, and physics expanding agent consumption is little, and raw material sources are wide, and production cost is low.
The specific embodiment
Provide a kind of concrete preparation method of Hydrodemetalation catalyst of the present invention below: (1) takes by weighing a certain amount of boehmite dry glue powder and puts into polytetrafluoroethylcontainer container; Add an amount of water; The autoclave sealing places baking oven to heat, and the control programming rate is 10 ℃ of min
-1, constant temperature 3～5h after temperature rises to 150～300 ℃ reduces to room temperature after naturally cooling to room temperature or step-down then, filters 110～130 ℃ of dry 1h in back.Dried boehmite fully mixes with carbon powder and extrusion aid, adds an amount of peptizing agent aqueous solution, mixes and pinches evenly, forms the plasticity material, through the banded extruder extrusion molding.Strip wet feed after the moulding through 100～130 ℃ dry 1～3 hour down, dried article shaped was made alumina support in 2～4 hours in 600～750 ℃ roasting temperature.(2) take by weighing an amount of above-mentioned carrier, add an amount of Mo-Ni-NH
3Solution (contains MoO
312.0wt%, NiO 3.0wt%) flooded 2 hours, the elimination redundant solution, 120 ℃ of oven dry made Hydrodemetalation catalyst of the present invention in 5 hours at 550 ℃ of roasting temperatures again.
Instance 1-8 explains the preparation method of the used alumina support of catalyst provided by the invention.
Instance 1
Take by weighing boehmite dry glue powder (Shenyang Catalyst Plant produces, alumina dry basic weight amount content 65%) 200g and place autoclave, add the 200ml deionized water, the autoclave sealing places baking oven to heat, and the control programming rate is 10 ℃ of min
-1, constant temperature 3h after temperature rises to 180 ℃ naturally cools to room temperature then, filters 120 ℃ of dry 1h of back filter cake.Dried boehmite and 3g concentration are that nitric acid, 14g carbon powder, 4g sesbania powder and the 150g deionized water of 65 heavy % mixes; On the screw rod banded extruder, be extruded into the cloverleaf pattern bar of diameter 1.8mm; In 120 ℃ of oven dry 3 hours; In 700 ℃ roasting temperature 3 hours, obtaining the present invention provided catalyst used alumina support B1 with dried article shaped.
Instance 2
With instance 1, constant temperature 4h after just the pressurized thermal water treatment temperature rises to 110 ℃, the deionized water addition is 40ml, obtaining the present invention provides catalyst used alumina support B2.
Instance 3
With instance 1, constant temperature 2h after just the pressurized thermal water treatment temperature rises to 300 ℃, the deionized water addition is 300ml, obtaining the present invention provides catalyst used alumina support B3.
Instance 4
With instance 1, just the addition of carbon powder is 6g, obtains carrier B 4 provided by the invention.
Instance 5
With instance 1, just the addition of carbon powder is 20g, and obtaining the present invention provides catalyst used alumina support B5.
Instance 6
With instance 1, constant temperature 1h after just the pressurized thermal water treatment temperature rises to 180 ℃ is cooled to room temperature with cooling water to autoclave, and obtaining the present invention provides catalyst used alumina support B6.
Instance 7
With instance 1, constant temperature 5h after just the pressurized thermal water treatment temperature rises to 180 ℃, the cooling of decompression back does not need drying directly to carry out the carrier forming step, and obtaining the present invention provides catalyst used alumina support B7.
Instance 8
(Shandong Qilu Petroleum Chemical Corporation Institute produces to take by weighing boehmite dry glue powder 200; Aluminium oxide butt content 70%) g; With 3g concentration be that nitric acid, 14g carbon powder, 4g sesbania powder and the 150g deionized water of 65 heavy % mixes; Carry out pressurized thermal water according to the method for instance 1 and handle, then through moulding, drying, roasting, obtaining the present invention provides catalyst used alumina support B8.
Comparative Examples 1
The preparation method of the existing used alumina support of Hydrodemetalation catalyst of this Comparative Examples explanation.
This Comparative Examples is the alumina support by the method preparation of describing among the CN1160602A.
Take by weighing Chinese Qilu Petroleum Chemical Corporation Institute and prepare boehmite dry glue powder 300g (moisture 78g); Take by weighing granular size again and be 30 microns carbon black 18g and extrusion aid sesbania powder 10g; Mix, add the solution that is made into by 2.0g phosphoric acid and 400g water, mix and pinch into plastic; On banded extruder, be extruded into
little; Drying is 4 hours under 120 ℃, then 900 ℃ of following roastings 2 hours, makes alumina support B9.
Comparative Examples 2
The preparation method of the existing used alumina support of Hydrodemetalation catalyst of this Comparative Examples explanation.
This Comparative Examples is the alumina support by the method preparation of describing among the CN1768946A.
Take by weighing the thin water aluminum oxide dry glue powder of plan and (contain gibbsite＜3wt%, Al
2O
3Contents on dry basis is 68wt%) 200g, extrusion aid sesbania powder 6g and water 230ml.Fully mix, mediate; Add wheat flour 28g (being equivalent to intend the 14wt% of thin water aluminum oxide dry glue powder amount) then; Mix pinch even extruded moulding
air drying and spend the night after; Dried 3 hours down in 110 ℃, drying sample is placed high temperature furnace, be warming up to 400 ℃ with 100 ℃/speed at one hour rating; Then with 80 ℃/speed at one hour rating be warming up to 830 ℃ and under this temperature constant temperature calcining 2.0 hours, make alumina support B10.
Above-mentioned instance and Comparative Examples gained carrier character are seen table 1:
Table 1 carrier character
Pore size distribution refers to that the pore volume of certain diameter range endoporus in the carrier accounts for the percentage of total pore volume.
The result of table 1 shows, in the prior art, uses the prepared alumina support of physics expanding agent merely, and the pore volume of bore dia between 10～20nm only accounts for 55% of whole pore volume, pore size distribution disperse, mechanical strength low (about 85N/cm).Alumina support pore size distribution and the mechanical strength of using physics expanding agent and chemical enlargement agent to make simultaneously make moderate progress, and the pore volume of bore dia between 10～20nm accounts for 65% of whole pore volume, and mechanical strength is 98N/cm.And embodiment 1～8, the used alumina support of catalyst promptly provided by the invention, the aperture is bigger; Can a few aperture＞15nm, and pore distribution concentration, the pore volume of bore dia between 10～20nm accounts for 81～86% of whole pore volumes; Mechanical strength is good, about 140N/cm.
Instance 9-16
Following instance is explained the preparation of Hydrodemetalation catalyst provided by the invention.
Take by weighing each 100 gram of alumina support of instance 1-8 preparation, add 150ml Mo-Ni-NH
3Solution (contains MoO
312.0wt%, NiO3.0wt%) dipping is 2 hours, the elimination redundant solution, 120 ℃ of oven dry again 550 ℃ of roasting temperatures 5 hours, obtain containing the Hydrodemetalation catalyst C1-C8 of alumina support of the present invention.The character of catalyst C1-C8 is listed in the table 2.
Comparative Examples 3-4
The preparation of following Comparative Examples explanation reference Hydrodemetalation catalyst.
Take by weighing each 100 gram of alumina support of Comparative Examples 1 and 2 preparations, add Mo-Ni-NH
3Solution 150ml (contains MoO
312.0wt%, NiO3.0wt%) dipping is 2 hours, the elimination redundant solution, 120 ℃ of oven dry again 550 ℃ of roasting temperatures 5 hours, obtain containing the Hydrodemetalation catalyst C9-C10 of Comparative Examples alumina support.The character of catalyst C9-C10 is listed in the table 2.
Table 2 catalyst property
Instance 17-24
Following instance is explained the catalytic performance of Hydrodemetalation catalyst provided by the invention.
With the listed decompression residuum of table 3 is raw material; The catalytic performance of the catalyst C1-C8 of evaluation example 9-16 preparation on 200 milliliters hydrogenation reaction device; Catalyst is the bar of long 2-3 millimeter, and the catalyst loading amount is 100 milliliters, and reaction temperature is 385 ℃; The hydrogen dividing potential drop is 15.6 MPas, and liquid hourly space velocity (LHSV) is 1.0 hours
-1, hydrogen to oil volume ratio is 800, reacts and measures the content that generates each impurity in the oil after 200 hours, calculates removal efficiency, evaluation result is seen table 4.
Comparative Examples 5-6
The catalytic performance of following Comparative Examples explanation reference Hydrodemetalation catalyst.
Be raw material with the listed decompression residuum of table 3 equally; On 100 milliliters hydrogenation reaction device, estimate the catalyst C9 of Comparative Examples 3,4 preparations, the catalytic performance of C10; Catalyst is the bar of long 2-3 millimeter, and the catalyst loading amount is 200 milliliters, and reaction temperature is 385 ℃; The hydrogen dividing potential drop is 15.6 MPas, and liquid hourly space velocity (LHSV) is 1.0 hours
-1, hydrogen to oil volume ratio is 800, reacts and measures the content that generates each impurity in the oil after 200 hours, calculates removal efficiency, evaluation result is seen table 4.
Table 3 feedstock oil character
Project content
S，wt％ 4.65
N，wt％ 0.29
Ni，μg/g 45
V，μg/g 148
CCR，wt％ 18
Each routine catalyst hydrogenation performance comparison of table 4
Find out that by table 4 data it is active that catalyst provided by the invention has higher HDM, also has higher hydrodesulfurization and hydrogenation to take off the activity of carbon residue.
Instance 25
This instance continues the catalytic performance of explanation Hydrodemetalation catalyst provided by the invention.
Press the catalytic performance of the method evaluate catalysts C1 of instance 17, react after 200 hours, proceed reaction, and improve reaction temperature at any time, to keep total demetallization per constant, the reaction temperature lift-off value that reacts after 5000 hours is as shown in table 5.
Comparative Examples 7
This Comparative Examples continues the catalytic performance of the existing contrast of explanation Hydrodemetalation catalyst.
The method of pressing instance 25 is estimated the catalytic performance of comparative catalyst C9, and the reaction temperature lift-off value that reacts after 5000 hours is as shown in table 5.
Table 5 reaction temperature lift-off value
Find out from the result of table 5; React after 5000 hours, adopt Hydrodemetalation catalyst provided by the invention, in order to keep total demetallization per constant; Reaction temperature has only improved 15 ℃; And adopt when having Hydrodemetalation catalyst now, reaction temperature has improved 25 ℃, and this explains that Hydrodemetalation catalyst provided by the invention has higher activity stability.
Claims (10)
1. the preparation method of a macropore alumina supporter is characterized in that comprising following process:
(1) gets the boehmite dry glue powder and carry out the pressurized thermal water processing;
(2) with step (1) gained boehmite dry glue powder, mix and pinch into plastic, in step (1) or step (2), add expanding agent;
(3) with the moulding of step (2) gained plastic, article shaped is dry, roasting, obtains the macropore oxidation carrier.
2. according to the described method of claim 1; It is characterized in that: the described pressurized thermal water treatment temperature of step (1) is 100～300 ℃; Preferred 150～250 ℃, hydrothermal treatment consists pressure is the equipment self-generated pressure under the hydrothermal treatment consists temperature, and the pressurized thermal water processing time is 1～5 hour.
3. according to claim 1 or 2 described methods; It is characterized in that: the heat treated boehmite dry glue powder of pressure (hydraulic) water prepares the wet stock that process obtains for the boehmite dry glue powder; Perhaps dry material carries out the pressurized thermal water processing after replenishing suitable quantity of water; Amount of water is 20%～200% of a boehmite dry glue powder butt weight, is preferably 50%～100%.
4. according to the described method of claim 1, it is characterized in that: the described expanding agent of step (2) is a carbon powder, and granularity is 20～40 μ m.
5. according to claim 1 or 4 described methods, it is characterized in that: the addition of expanding agent is equivalent to 3%～10% of boehmite butt weight, and preferably 6%～8%.
6. according to the described method of claim 1, it is characterized in that: in step (1) or step (2), add extrusion aid and peptizing agent.
7. according to the described method of claim 1, it is characterized in that: in step (1) and/or step (2), add adjuvant component, auxiliary agent is one or more among F, Si, Ti, Zr, P, the B.
8. according to the described method of claim 1, it is characterized in that: the described dry run of step (3) for 100～130 ℃ dry 1～10 hour down, perhaps, be warming up to 100～130 ℃ then, dry 1～10 hour earlier 60～70 ℃ of oven dry 2～3 hours; The temperature of said roasting is 600～750 ℃, and roasting time is 2～4 hours.
9. the preparation method of a Hydrodemetalation catalyst; Macropore alumina supporter with the said method preparation of the arbitrary claim of claim 1 to 8 is a carrier; Adopt infusion process supported active metal component Mo or/and Ni obtains final Hydrodemetalation catalyst through super-dry and roasting then.
10. Hydrodemetalation catalyst, the pore volume that it is characterized in that Hydrodemetalation catalyst is 0.7～1.50ml/g, specific area is 150.0～250.0m
2/ g, bore dia be the hole of 10～20 nanometers account for total pore volume 70%～90%, crushing strength 130～160N/cm.
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