CN106040283A - Demetalization catalyst carrier and preparation method thereof - Google Patents
Demetalization catalyst carrier and preparation method thereof Download PDFInfo
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- CN106040283A CN106040283A CN201610374401.2A CN201610374401A CN106040283A CN 106040283 A CN106040283 A CN 106040283A CN 201610374401 A CN201610374401 A CN 201610374401A CN 106040283 A CN106040283 A CN 106040283A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/041—Mesoporous materials having base exchange properties, e.g. Si/Al-MCM-41
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/03—Catalysts comprising molecular sieves not having base-exchange properties
- B01J29/0308—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
- C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
- C10G45/06—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof
- C10G45/08—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof in combination with chromium, molybdenum, or tungsten metals, or compounds thereof
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
- C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
- C10G45/12—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing crystalline alumino-silicates, e.g. molecular sieves
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/20—After treatment, characterised by the effect to be obtained to introduce other elements in the catalyst composition comprising the molecular sieve, but not specially in or on the molecular sieve itself
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/70—Catalyst aspects
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Dispersion Chemistry (AREA)
- Materials Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a demetalization catalyst carrier and a preparation method thereof and belongs to the technical field of catalysts. The catalyst carrier is a demetalization catalyst carrier of water-containing glass-calcium chloride compound. In the preparation process of the catalyst carrier, a pore-enlarging agent does not need to be added additionally, operation is simple, and industrialization is achieved easily; due to the fact that the desulfuration rate, the denitrification rate and the demetalization rate of the catalyst prepared from the catalyst carrier are high, mechanical strength, compressive strength and wear-resisting strength are good, and the demetalization catalyst carrier is suitable for industrial application of demetalization in heavy oil and residual oil hydrogenation processes.
Description
Technical field
The present invention relates to catalyst field, be specifically related to a kind of catalyst for demetalation carrier and preparation method thereof.
Background technology
Along with the development of crude oil heaviness, in poor quality in world wide, and the scarcity of crude resources, greatly develop and mix refining
Or the thermal cracking technology such as catalytic cracking (FCC) technology and coking etc. entirely refining residual oil is particularly important, wherein FCC technique has become
For the technique that light materialization of heavy oil is maximally efficient.
In FCC technique, when using residual hydrogenation catalysis, residual oil flow velocity is fast, owing to containing substantial amounts of gold in feed residue
Belonging to the impurity such as (such as nickel, vanadium etc.), sulfur, nitrogen and carbon residue, have larger molecular weight, mean diameter is relatively big, the little easy plugging hole in aperture
Road, the pore volume little reduction heavy oil time of staying in the catalyst, reduces the removal efficiency of metal.Thus it is easily caused the work of catalyst
Property quickly reduce and inactivate, and the pore structure of catalyst be by constitute catalyst carrier determine, therefore, preparation there is large hole
Hold and the carrier of larger aperture is the key preparing residual oil hydrocatalyst.
Those skilled in the art be devoted to seek always a kind of large hole hold and larger aperture catalyst carrier for
Residual oil hydrocatalyst.Thus Chinese patent literature CN 92112511.9 A discloses and a kind of add urging of low sodium Ludox
Agent carrier, the prior art increases the pore volume of carrier by extruded moulding, makes pore size distribution more concentrate, although on its carrier by
In add reach and make Kong Rong relatively big, pore volume reaches 0.55～0.65mL/g after testing, but its average pore size is less, easy plugging hole
Road is not suitable for heavy oil, residual oil compared with the hydrogenation process of macromolecular reaction thing.
Chinese patent literature CN 1206037 A discloses one physics expanding agent and chemical enlargement agent are added on oxygen
Active component is loaded to supported catalyst carrier, by the catalyst of this carrier gained with the method for dipping after changing alumina supporter
Pore volume be 0.80～1.20mL/g, specific surface area is 110～200m2/g, and can squeeze aperture is 15～20nm, and bulk density is
0.50～0.60g/mL, although the catalyst carrier disclosed in the prior art has large hole and holds and larger aperture, but it needs
Expanding agent is added on alumina support, and the extra interpolation of expanding agent can close original aluminium oxide duct, and then can lead
There is problems such as subsiding in pore road.
At heavy oil or residual hydrogenation catalytic field, in addition to pore volume and aperture except requiring catalyst carrier are sufficiently large, by urging
The intensity of catalyst prepared by agent carrier is also to consider the vital factor that catalyst carrier properties is good and bad.Chinese patent
Document CN 1249208 A discloses a kind of macropore alumina supporter and preparation method thereof, by difference route system in the prior art
One or more of standby boehmite dry glue powder mix with carbon powder, surfactant, by water, peptizer and help crowded
The effect extrusion molding of agent, then after drying, roasting, i.e. prepare carrier, its alumina support prepared can be used as hydrogenation catalyst
Carrier, be particularly well-suited to the higher raw oil of macromole impurity such as nickel, vanadium, arsenic equal size or Heavy oil hydrogenation catalyst
Carrier.Yet with the prior art during preparation, need 650-950 DEG C of high-temperature roasting, be easily caused support oxide
Sintering phenomenon occurring, and then the aperture of carrier, specific surface area, specific pore volume can be caused to reduce, catalyst activity declines therewith；Simultaneously
High-temperature roasting also results in the heat of ion and moves and then form lattice defect, or because the embedding of foreign ion makes the chemical shape of component
State changes and finally affects the activity of catalyst.
Summary of the invention
Therefore, the technical problem to be solved in the present invention is to overcome the catalyst removing in residual hydrogenation in prior art to carry
Body aperture relatively little Yi blocks duct, need to additionally add expanding agent and can close original aluminium oxide duct and then duct can be caused to go out
Now subside, and high-temperature roasting and cause support oxide sintering and lattice defect ultimately result in by the work of its gained catalyst
Property difference defect, thus provide a kind of catalyst for demetalation carrier and preparation method thereof.
To this end, technical scheme is as follows:
A kind of catalyst for demetalation carrier of hydrated glass-calcium chloride complex.
Under normal temperature condition, with Si oxide and aluminum oxide as carrier, add in the carrier of Si oxide and aluminum oxide
Enter waterglass, calcium chloride, emulsification function extrusion aid, molecular sieve and obtain.
Raw material components weight portion is: waterglass 8～20 parts, calcium chloride 10～30 parts, emulsification function extrusion aid 0.5～5 parts,
Molecular sieve 5～75 parts and the mixture 40 of Si oxide and aluminum oxide～85 parts.
Described raw material components weight portion is: waterglass 10 parts, 15 parts of calcium chloride, emulsification function extrusion aid 0.5 part, molecular sieve
5 parts and 70 parts of the mixture of Si oxide and aluminum oxide.
Described emulsification function extrusion aid is extrusion aid H；Described molecular sieve is MCM-41 molecular sieve, described Si oxide and aluminum
Hopcalite is one or more in boehmite, aluminum oxide dry glue powder, SB powder.
Described calcium chloride is calcium chloride powder.
Described modulus of water glass is 3.1～3.4.Waterglass in the range of this modulus can guarantee that catalyst reactivity
Matter, degree of reaction and thermal discharge cause the premature aging of carrier in suitable degree to avoid reacting too fast.
Described emulsification function extrusion aid is one or more in Ludox, polyvinyl alcohol, sesbania powder and natural gum.
The preparation method of a kind of catalyst for demetalation carrier, specifically comprises the following steps that
(1) carry out Si oxide, aluminum oxide and molecular sieve being dry mixed to uniformly, obtain the first mixture；
(2) emulsification function extrusion aid and the first mixture are carried out wet mixing to uniformly, obtain the second mixture；
(3) in waterglass, add water and be prepared as the liquid soluble glass that solid content is 20～80wt%, then mix second
Compound add described in liquid soluble glass in carry out wet mixing to uniformly, obtain the 3rd mixture；
(4) in calcium chloride, add water and be prepared as the calcium chloride water that mass fraction is 10～70%, then by the 3rd
Mixture adds in described calcium chloride water and carries out wet mixing to uniformly, obtains the 4th mixture；
(5) by extruded for the 4th mixture, catalyst for demetalation carrier is the most i.e. obtained；
Step (1)-(4) are all carried out under normal temperature condition.
Being dried as being warmed up to 200 DEG C dry 1～10h in step (5).
Extruded in step (5) is shaped as column or Herba Galii Bungei type, a length of 3-5cm.Above-mentioned demetalization is catalyzed
The application of agent carrier.
In the present invention, the addition of calcium chloride makes calcium chloride and waterglass create synergism thus optimizes waterglass and coagulate
The performance of glue, improves pore structure and the intensity of sodium silicate gel, and then makes its gelatification higher, and is rendered as short range and has
Sequence, the most unordered microstructure, and there is threadiness, the gel state of the different morphologies such as netted and microgranular, to removing slag
In oil, metal has good deposition.Due to the fact that it is with Si oxide and aluminum oxide as carrier, and adulterate wherein
The catalyst carrier of other compositions, carrier Si oxide and aluminum oxide after drying can harden(ing)by itself, have higher viscous
Knotting strength and holding shapeliness.The whole preparation process of catalyst carrier of the present invention is all carried out, therefore under normal temperature condition
It is not result in support oxide generation sintering phenomenon, and then the aperture of carrier, specific surface area, specific pore volume can be caused to reduce, the most not
The heat that can cause ion because of high-temperature roasting moves and then forms lattice defect, or because of the embedding of foreign ion, makes component
Chemical state changes and eventually affects the activity of catalyst.
The catalyst for demetalation carrier of the present invention, the MCM-41 molecular sieve of use itself has separate ten-ring hole
Road system, contains half supercage structure of twelve-ring supercage, supercage and hexatomic ring in system, the pore passage structure of this complexity makes
MCM-41 molecular sieve has higher specific surface area and excellent absorbability；The addition of waterglass-calcium chloride, has the most solidifying
Glue effect, the gel state presented, for short-range order, the most unordered microstructure, there is threadiness, netted and microgranular etc.
Different morphologies, has good deposition for metal in removing residual oil；The addition of extrusion aid H, can effectively protect in carrier
Al2O3Impact on waterglass-calcium chloride, can play good emulsification.In the present invention, Si oxide and aluminum oxide carry
Complement each other between body, and waterglass, calcium chloride, the emulsification function extrusion aid each active component of H, MCM-41 molecular sieve, collaborative
Coming into force so that the catalyst for demetalation carrier of the present invention has comprehensive effective ratio surface and pore structure, mechanical strength is high, and by
Catalyst activity obtained by carrier of the present invention significantly improves.The technology of the present invention compared with prior art, has the advantage that
(1) the catalyst for demetalation carrier that the present invention provides, the beneficially globulate of catalyst or be in strip or other shape,
Can revise according to the requirement of product, simple to operate, it is easily mastered.
(2) the demetallated removal efficiency of catalyst prepared by the catalyst for demetalation carrier that the present invention provides be 60% with
On, up to 95%, and there is higher anti-pressure and abrasion-proof intensity.
(3) the catalyst for demetalation carrier that the present invention provides has comprehensive effective ratio surface and pore structure, and by this
Catalyst activity obtained by bright carrier significantly improves, and is suitable for heavy oil, demetallated commercial Application in residual hydrogenation.
(4) catalyst carrier of the present invention is not required to additionally add expanding agent in preparation process, simple to operate be prone to industry
Change, the catalyst carrier of the present invention desulfurization of the catalyst prepared, denitrogenation and demetallated removal efficiency are high, mechanical strength and
Anti-pressure and abrasion-proof intensity is relatively good.
Detailed description of the invention
Thering is provided following embodiment is to preferably be further appreciated by the present invention, it is not limited to described optimal embodiment party
Formula, is not construed as limiting present disclosure and protection domain, anyone under the enlightenment of the present invention or by the present invention and its
Product as any and present invention that the feature of his prior art is combined and draws is same or like, all falls within the present invention's
Within protection domain.
Unreceipted specific experiment step or condition person in embodiment, according to the normal experiment described by the document in this area
The operation of step or condition can be carried out.Agents useful for same or instrument unreceipted production firm person, be can by city available from
Conventional reagent product.
The molecular sieve used in each embodiment in the present invention is MCM-41 molecular sieve, and other molecular sieves of prior art are also
Can realize the goal of the invention of the present invention, each embodiment in the present invention is not intended that limiting the scope of the invention.
The solid content of the liquid soluble glass in the present invention refers to the effective dose of waterglass.
The modulus of the waterglass in the present invention is 3.1-3.4.
Reagent source explanation in the embodiment of the present invention:
Waterglass is available commercially from Shenyang Research Institute of Foundry, and specifications and models are 908 waterglass；
Calcium chloride is available commercially from beach, Weifang Chemical Co., Ltd., and specifications and models are anhydrous calcium chloride；
MCM-41 molecular sieve is available commercially from Shanghai Heng Ye molecular sieve limited company；
Boehmite is available commercially from Liaoning Haitai development in science and technology company limited；
Aluminum oxide dry glue powder is available commercially from Liaoning Haitai development in science and technology company limited；
SB powder (active oxidation alumina gel) is available commercially from Liaoning Haitai development in science and technology company limited；
Ludox is available commercially from Xinghua City Condar auxiliary reagent factory, and specifications and models are 40% Ludox；
Polyvinyl alcohol is available commercially from material limited company of emblem Wanwei High-new Technology Co., and specifications and models are PVA17-99；
Sesbania powder is available commercially from emerging bio tech ltd, Wuhan one hundred；
Natural gum is available commercially from Zhongshan city ploughshare natural gum industry Products Co., Ltd,
Embodiment 1
The catalyst for demetalation carrier of the present embodiment, including following raw material components:
Waterglass 10kg, calcium chloride 10kg, extrusion aid H 1.5kg, MCM-41 molecular sieve 75kg.
The catalyst for demetalation carrier of embodiment is adopted and is prepared with the following method:
Specifically comprise the following steps that
(1) the described MCM-41 molecular sieve weighed according to selected weight and extrusion aid H are carried out being dry mixed 30min, and mix
Uniformly, the first mixture is standby；
(2) add suitable quantity of water according to selected weight in the waterglass that will weigh being prepared as solid content is that 25wt% waterglass is molten
Liquid, then adds the first mixture obtained in step (1) and carries out wet mixing 30min in described water glass solution, and mix all
Even, the second mixture made is standby；
(3) add appropriate water according to selected weight in the calcium chloride that will weigh being prepared as mass fraction is 20% calcium chloride
Aqueous solution, then adds the second mixture obtained in step (2) in described calcium chloride water and carries out wet mixing 10min, and
Mix homogeneously, the 3rd mixture made is standby；
(4) the 3rd mixture obtained in step (3) is squeezed into Herba Galii Bungei type, length 5mm, then carries out at 120 DEG C
It is dried 5h, obtains described catalyst for demetalation carrier.
Embodiment 2
The catalyst for demetalation carrier of the present embodiment, including following raw material components:
Waterglass 25kg, calcium chloride powder 10kg, extrusion aid are Ludox H 3kg, MCM-41 molecular sieve 20kg, Si oxide
Mixture 40kg (for boehmite) with aluminum oxide.
The catalyst for demetalation carrier of embodiment is adopted and is prepared with the following method:
Specifically comprise the following steps that
(1) Si oxide, aluminum oxide and MCM-41 molecular sieve will be weighed according to selected weight and carry out being dry mixed 30min, and
Mix homogeneously, the first mixture is standby；
(2) extrusion aid H will be weighed according to selected weight and the first mixture will carry out being dry mixed 20min, and mix homogeneously, obtain
Two mixture are standby；
(3) will weigh according to selected weight and waterglass add suitable quantity of water to be prepared as solid content be that 20wt% waterglass is molten
Liquid, then adds the second mixture obtained in step (2) and carries out wet mixing 30min in described water glass solution, and mix all
Even, the 3rd mixture made is standby；
(4) add appropriate water according to selected weight in the calcium chloride that will weigh being prepared as mass fraction is 50% calcium chloride
Aqueous solution, then adds the 3rd mixture obtained in step (3) in described calcium chloride water and carries out wet mixing 15min, and
Mix homogeneously, the 4th mixture made is standby；
(5) the 4th mixture obtained in step (4) is squeezed into stripe shape, length 5mm, then carries out being dried at 120 DEG C
5h, obtains described catalyst for demetalation carrier.
Embodiment 3
The catalyst for demetalation carrier of the present embodiment, including following raw material components:
Waterglass 20kg, calcium chloride powder 30kg, extrusion aid H (for polyvinyl alcohol) 5kg, MCM-41 molecular sieve 10kg, silica
The mixture 40kg (for aluminum oxide dry glue powder) of compound and aluminum oxide.
The catalyst for demetalation carrier of the present embodiment is adopted and is prepared with the following method:
Specifically comprise the following steps that
(1) weigh Si oxide, aluminum oxide and MCM-41 molecular sieve according to selected weight and carry out being dry mixed 20min, and mix
Close uniformly, obtain the first mixture standby；
(2) weigh extrusion aid H according to selected weight and the first mixture carries out being dry mixed 20min, and mix homogeneously, obtain second
Mixture is standby；
(3) weigh waterglass according to selected weight, and be added thereto to suitable quantity of water and be prepared as solid content 30wt% liquid water
Glass, then adds the second mixture obtained in step (2) in water glass solution and carries out wet mixing 50min, and mix homogeneously,
The 3rd mixture made is standby；
(4) weigh calcium chloride according to selected weight, and be added thereto to appropriate water and be prepared as mass fraction 30% chlorination
Calcium aqueous solution, then adds the 3rd mixture obtained in step (3) in described calcium chloride water and carries out wet mixing 5min, and
Mix homogeneously, the 4th mixture made is standby；
(5) the 4th mixture obtained in step (4) is squeezed into Herba Galii Bungei type, length 5mm, then carries out at 120 DEG C
It is dried 5h, obtains described catalyst for demetalation carrier.
Embodiment 4
The catalyst for demetalation carrier of the present embodiment, including following raw material components:
Waterglass 15kg, calcium chloride powder 17kg, extrusion aid H (for sesbania powder) 2kg, MCM-41 molecular sieve 60kg, silicon aoxidize
The mixture 60kg (SB powder) of thing and aluminum oxide.
The catalyst for demetalation carrier of the present embodiment is adopted and is prepared with the following method:
Specifically comprise the following steps that
(1) the described Si oxide weighed according to selected weight, aluminum oxide and MCM-41 molecular sieve are dry mixed
25min, and mix homogeneously, obtain the first mixture standby；
(2) extrusion aid H will be weighed according to selected weight and the first mixture will carry out being dry mixed 25min, and mix homogeneously, obtain
Two mixture are standby；
(3) will weigh according to selected weight and waterglass add suitable quantity of water to be prepared as solid content be that 40wt% waterglass is molten
Liquid, then adds the second mixture obtained in step (2) and carries out wet mixing 50min in described water glass solution, and mix all
Even, the 3rd mixture made is standby；
(4) add appropriate water according to selected weight in the calcium chloride that will weigh being prepared as mass fraction is 60% calcium chloride
Aqueous solution, then adds the 3rd mixture obtained in step (3) in described calcium chloride water and carries out wet mixing 5min, and mix
Closing uniformly, the 4th mixture made is standby；
(5) the 4th mixture obtained in step (4) is squeezed into Herba Galii Bungei type, length 5mm, then carries out at 120 DEG C
It is dried 5h, obtains described catalyst for demetalation carrier.
Embodiment 5
The catalyst for demetalation carrier of the present embodiment, including following raw material components:
Waterglass 8kg, calcium chloride 20kg, extrusion aid H (gummy) 4kg, MCM-41 molecular sieve 75kg, Si oxide and alumina
The mixture 85kg (boehmite and alumina dry glue powder mixture) of compound.
The catalyst for demetalation carrier of the present embodiment is adopted and is prepared with the following method:
Specifically comprise the following steps that
(1) the described Si oxide weighed according to selected weight, aluminum oxide and MCM-41 molecular sieve are dry mixed
20min, and mix homogeneously, obtain the first mixture standby；
(2) extrusion aid H will be weighed according to selected weight and the first mixture will carry out being dry mixed 20min, and mix homogeneously, obtain
Two mixture are standby；
(3) will weigh according to selected weight and waterglass add suitable quantity of water to be prepared as solid content be that 80wt% waterglass is molten
Liquid, then adds the second mixture obtained in step (2) and carries out wet mixing 50min in described water glass solution, and mix all
Even, the 3rd mixture made is standby；
(4) add appropriate water according to selected weight in the calcium chloride that will weigh being prepared as mass fraction is 70% calcium chloride
Aqueous solution, then adds the 3rd mixture obtained in step (3) in described calcium chloride water and carries out wet mixing 5min, and mix
Closing uniformly, the 4th mixture made is standby；
(5) the 4th mixture obtained in step (4) is squeezed into Herba Galii Bungei type, length 5mm, then carries out at 120 DEG C
It is dried 5h, obtains described catalyst for demetalation carrier.
Embodiment 6
The catalyst for demetalation carrier of the present embodiment, including following raw material components:
Waterglass 10kg, calcium chloride 15kg, extrusion aid H (gummy) 0.5kg, MCM-41 molecular sieve 5kg, Si oxide and aluminum
Hopcalite 70kg (SB powder and alumina dry glue powder mixture).
The catalyst for demetalation carrier of the present embodiment is adopted and is prepared with the following method:
Specifically comprise the following steps that
(1) the described Si oxide weighed according to selected weight, aluminum oxide and MCM-41 molecular sieve are dry mixed
20min, and mix homogeneously, obtain the first mixture standby；
(2) extrusion aid H will be weighed according to selected weight and the first mixture will carry out being dry mixed 20min, and mix homogeneously, obtain
Two mixture are standby；
(3) will weigh according to selected weight and waterglass add suitable quantity of water to be prepared as solid content be that 40wt% waterglass is molten
Liquid, then adds the second mixture obtained in step (2) and carries out wet mixing 50min in described water glass solution, and mix all
Even, the 3rd mixture made is standby；
(4) add appropriate water according to selected weight in the calcium chloride that will weigh being prepared as mass fraction is 10% chlorination
Calcium aqueous solution, then adds the 3rd mixture obtained in step (3) in described calcium chloride water and carries out wet mixing 5min, and
Mix homogeneously, the 4th mixture made is standby；
(5) the 4th mixture obtained in step (4) is squeezed into Herba Galii Bungei type, length 5mm, then carries out at 120 DEG C
It is dried 5h, obtains described catalyst for demetalation carrier.
Embodiment 7
The catalyst for demetalation carrier of the present embodiment, including following raw material components:
Waterglass 5kg, calcium chloride 31kg, extrusion aid H (gummy) 6kg, MCM-41 molecular sieve 4kg, Si oxide and alumina
The mixture 35kg (SB powder and alumina dry glue powder mixture) of compound.
The catalyst for demetalation carrier of the present embodiment is adopted and is prepared with the following method:
Specifically comprise the following steps that
(1) the described Si oxide weighed according to selected weight, aluminum oxide and MCM-41 molecular sieve are dry mixed
20min, and mix homogeneously, obtain the first mixture standby；
(2) extrusion aid H will be weighed according to selected weight and the first mixture will carry out being dry mixed 20min, and mix homogeneously, obtain
Two mixture are standby；
(3) will weigh according to selected weight and waterglass add suitable quantity of water to be prepared as solid content be that 30wt% waterglass is molten
Liquid, then adds the second mixture obtained in step (2) and carries out wet mixing 50min in described water glass solution, and mix all
Even, the 3rd mixture made is standby；
(4) add appropriate water according to selected weight in the calcium chloride that will weigh being prepared as mass fraction is 20% calcium chloride
Aqueous solution, then adds the 3rd mixture obtained in step (3) in described calcium chloride water and carries out wet mixing 5min, and mix
Closing uniformly, the 4th mixture made is standby；
(5) the 4th mixture obtained in step (4) is squeezed into Herba Galii Bungei type, length 5mm, then carries out at 120 DEG C
It is dried 5h, obtains described catalyst for demetalation carrier.
Comparative example 1
The catalyst for demetalation carrier of the present embodiment, including following raw material components:
Waterglass 0.5kg, calcium chloride 10kg, MCM-41 molecular sieve 40kg, Si oxide and the mixture of aluminum oxide
40kg。
The catalyst for demetalation carrier of embodiment is adopted and is prepared with the following method:
Specifically comprise the following steps that
(1) the described Si oxide weighed according to selected weight, aluminum oxide and MCM-41 molecular sieve are dry mixed
30min, and mix homogeneously, the first mixture is standby；
(2) waterglass that will weigh according to selected weight adds suitable quantity of water and is prepared as 10% water glass solution, then will
The the first mixture described water glass solution of addition obtained in step (1) carries out wet mixing 10min, and mix homogeneously, makes
Second mixture is standby；
(3) calcium chloride that will weigh according to selected weight adds appropriate water and be prepared as 15% calcium chloride water, so
After the second mixture obtained in step (2) added in described calcium chloride water carry out wet mixing 5min, and mix homogeneously, system
The 3rd mixture become is standby；
(4) the 3rd mixture obtained in step (3) is squeezed into Herba Galii Bungei type, length 4mm, then carries out at 120 DEG C
It is dried 5h, obtains described catalyst for demetalation carrier.
Comparative example 2
The catalyst for demetalation carrier of the present embodiment, including following raw material components:
Waterglass 20kg, calcium chloride 40kg, emulsification function extrusion aid H 5kg, Si oxide and the mixture of aluminum oxide
40kg。
The catalyst for demetalation carrier of embodiment is adopted and is prepared with the following method:
Specifically comprise the following steps that
(1) the described Si oxide weighed according to selected weight, aluminum oxide and extrusion aid H are carried out being dry mixed 30min, and
Mix homogeneously, the first mixture is standby；
(2) waterglass that will weigh according to selected weight adds suitable quantity of water and is prepared as 15% water glass solution, then will
The the first mixture described water glass solution of addition obtained in step (1) carries out wet mixing 20min, and mix homogeneously, makes
Second mixture is standby；
(3) calcium chloride that will weigh according to selected weight adds appropriate water and be prepared as 30% calcium chloride water, so
After the second mixture that will obtain in step (2) add in described calcium chloride water and carry out wet mixing 15min, and mix homogeneously,
The 3rd mixture made is standby；
(4) the 3rd mixture obtained in step (3) is squeezed into Herba Galii Bungei type, length 5mm, then carries out at 120 DEG C
It is dried 5h, obtains described catalyst for demetalation carrier.
Experimental example
The carrier processing using preparation obtains catalyst, and catalyst is carried out metal removal test, pore volume and specific surface area
Test:
Carrier prepared by embodiment 1-3 and comparative example 1-2 of equal in quality is immersed in respectively same volume and concentration
In active component aqueous solution, its active component is to account for cobalt and the molybdenum of 0.5% of described carrier quality 3%, prepares catalyst.
Measure 100ml Catalyst packing to enter in the small-sized evaluating apparatus of fixed bed residual hydrocracking, carry out with reduced crude
Reaction evaluating, reaction pressure is 8mPa, and air speed is 2h-1, use plasma emission spectrum (AES/ICP) method to measure and generate in oil
Nickel, vanadium and the content of other metal (ferrum, calcium, sodium), calculate metal extrusion rate, and result is listed in table 1.
Metal removal rate=1-[generating metal in oil (nickel, vanadium, other) content]/[metallic nickel in raw oil, vanadium, other]
Content] × 100%
The catalyst metals removal efficiency of examples detailed above gained the results are shown in Table 1:
The key property table of table 1 catalyst
Can be seen that with sial as carrier by test result, carrier adds calcium chloride, waterglass, MCM-41 molecular sieve
And auxiliary agent can significantly improve carrier and prepare the demetalization efficiency of catalyst.And substantially embody that this carrier possessed basic
Feature, and there is higher anti-pressure and abrasion-proof intensity.And described catalyst for demetalation carrier removing impurities matter gold prepared by the present invention
Belong to efficiency and be up to 95%, and there is higher specific surface area and pore size.
Above-described embodiment is only for clearly demonstrating example, and not restriction to embodiment.For institute
For the those of ordinary skill in genus field, change or the change of other multi-form can also be made on the basis of the above description
Dynamic.Here without also cannot all of embodiment be given exhaustive.And the obvious change thus extended out or change
Dynamic still in obvious among the protection domain of the invention, above-described embodiment is only for clearly demonstrating example,
And not restriction to embodiment.For those of ordinary skill in the field, the most also may be used
To make other changes in different forms.Here without also cannot all of embodiment be given exhaustive.And thus
That is extended out obviously changes or changes among still in the protection domain of the invention.
Claims (11)
1. the catalyst for demetalation carrier of hydrated glass-calcium chloride complex.
Catalyst carrier the most according to claim 1, it is characterised in that under normal temperature condition, with Si oxide and aluminum oxidation
Thing is carrier, adds waterglass, calcium chloride, emulsification function extrusion aid, molecular sieve in the carrier of Si oxide and aluminum oxide
And obtain.
Catalyst carrier the most according to claim 2, it is characterised in that raw material components weight portion is: waterglass 8～20
Part, calcium chloride 10～30 parts, emulsification function extrusion aid 0.5～5 parts, molecular sieve 5～75 parts and Si oxide and aluminum oxide
Mixture 40～85 parts.
Catalyst carrier the most according to claim 3, it is characterised in that described raw material components weight portion is: waterglass 10
Part, 15 parts of calcium chloride, emulsification function extrusion aid 0.5 part, 5 parts of molecular sieve and the mixture 70 of Si oxide and aluminum oxide
Part.
Catalyst carrier the most according to claim 4, it is characterised in that described emulsification function extrusion aid is extrusion aid H；Institute
Stating molecular sieve is MCM-41 molecular sieve, and the mixture of described Si oxide and aluminum oxide is boehmite, alumina dry glue
One or more in powder, SB powder.
Catalyst carrier the most according to claim 5, it is characterised in that described calcium chloride is calcium chloride powder.
Catalyst carrier the most according to claim 6, it is characterised in that described modulus of water glass is 3.1～3.4.
Catalyst carrier the most according to claim 7, it is characterised in that described emulsification function extrusion aid H is Ludox, gathers
One or more in vinyl alcohol, sesbania powder and natural gum.
9. a preparation method for catalyst for demetalation carrier, specifically comprises the following steps that
(1) carry out Si oxide, aluminum oxide and molecular sieve being dry mixed to uniformly, obtain the first mixture；
(2) emulsification function extrusion aid and the first mixture are carried out wet mixing to uniformly, obtain the second mixture；
(3) in waterglass, add water and be prepared as the liquid soluble glass that solid content is 20～80wt%, then by the second mixture
Liquid soluble glass described in addition carries out wet mixing to uniformly, obtain the 3rd mixture；
(4) in calcium chloride, add water and be prepared as the calcium chloride water that mass fraction is 10～70%, then mix the 3rd
Thing adds in described calcium chloride water and carries out wet mixing to uniformly, obtains the 4th mixture；
(5) by extruded for the 4th mixture, catalyst for demetalation carrier is the most i.e. obtained；
Step (1)-(4) are all carried out under normal temperature condition.
Method the most according to claim 9, it is characterised in that in step (5) be dried for be warmed up to 200 DEG C be dried 1～
10h。
11. according to the method described in claim 9 or 10, it is characterised in that extruded in step (5) is shaped as column
Or Herba Galii Bungei type, a length of 3-5cm.
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| CN1086534A (en) * | 1992-11-05 | 1994-05-11 | 中国石油化工总公司抚顺石油化工研究院 | A kind of heavy-oil hydrogenation denitrification catalyst |
| EP1046390A1 (en) * | 1999-04-20 | 2000-10-25 | Calgon Corporation | Compositions and methods for cleaning and removing contaminants from hair |
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| CN1086534A (en) * | 1992-11-05 | 1994-05-11 | 中国石油化工总公司抚顺石油化工研究院 | A kind of heavy-oil hydrogenation denitrification catalyst |
| EP1046390A1 (en) * | 1999-04-20 | 2000-10-25 | Calgon Corporation | Compositions and methods for cleaning and removing contaminants from hair |
| CN102950012A (en) * | 2011-08-29 | 2013-03-06 | 中国石油化工股份有限公司 | Preparation method of hydrogenation catalyst |
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