CN106040283B - A kind of catalyst for demetalation carrier and preparation method thereof - Google Patents
A kind of catalyst for demetalation carrier and preparation method thereof Download PDFInfo
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- CN106040283B CN106040283B CN201610374401.2A CN201610374401A CN106040283B CN 106040283 B CN106040283 B CN 106040283B CN 201610374401 A CN201610374401 A CN 201610374401A CN 106040283 B CN106040283 B CN 106040283B
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- calcium chloride
- aluminum oxide
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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
-
- 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
Abstract
The present invention discloses a kind of catalyst for demetalation carrier and preparation method thereof, belongs to catalyst technical field.Catalyst carrier of the present invention is the catalyst for demetalation carrier of hydrated glass chlorination calcium complexes.The catalyst carrier of the present invention is not required to additionally add expanding agent in preparation process, it is easy to operate to be easy to industrialize, by desulfurization, denitrogenation and the demetallated removal efficiency height of catalyst prepared by the catalyst carrier of the present invention, mechanical strength and anti-pressure and abrasion-proof intensity are all relatively good, it is suitable for heavy oil, demetallated commercial Application in residual hydrogenation.
Description
Technical field
The present invention relates to catalyst fields, and in particular to a kind of catalyst for demetalation carrier and preparation method thereof.
Background technology
With the scarcity of crude oil heaviness, the development of in poor quality and crude resources in world wide, greatly develops and mix refining
Or catalytic cracking (FCC) technology and the thermal cracking technology such as coking of full refining residual oil are particularly important, wherein FCC techniques at
For the maximally efficient technique of light materialization of heavy oil.
In FCC techniques, when being catalyzed using residual hydrogenation, residual oil flow velocity is fast, due to containing a large amount of gold in feed residue
The impurity such as category (such as nickel, vanadium), sulphur, nitrogen and carbon residue have larger molecular weight, and average grain diameter is larger, the small easy plugging hole in aperture
Road, Kong Rong little reduce the residence time of heavy oil in the catalyst, reduce the removal efficiency of metal.Thus it is easy to cause the work of catalyst
Property quickly reduce and inactivate, and the pore structure of catalyst is determined by the carrier for constituting catalyst, and therefore, preparation is with large hole
Hold and the carrier of larger aperture is the key that prepare residual oil hydrocatalyst.
Those skilled in the art have been devoted to seek a kind of large hole hold and the catalyst carrier of larger aperture for
Residual oil hydrocatalyst.Thus a kind of urging for the low sodium Ludox of addition is disclosed in 92112511.9 A of Chinese patent literature CN
Agent carrier, the prior art are increased the Kong Rong of carrier by extruded moulding, pore size distribution are made more to concentrate, although on carrier by
Hole is set to melt in reaching for addition larger, after testing 0.55~0.65mL/g of Kong Rongda, but its average pore size is smaller, easy plugging hole
Road is not suitable for the hydrogenation process of heavy oil, residual oil bigger molecule reactant.
Disclosed in 1206037 A of Chinese patent literature CN it is a kind of by physics expanding agent and chemical enlargement agent addition in oxygen
Active component is loaded into supported catalyst carrier in the method for dipping after change alumina supporter, by the catalyst obtained by the carrier
0.80~1.20mL/g of Kong Rongwei, specific surface area is 110~200m2/g, and it is 15~20nm that can squeeze aperture, and bulk density is
0.50~0.60g/mL, although the catalyst carrier disclosed in the prior art has large hole appearance and larger aperture, it is needed
Expanding agent is added on alumina support, and the additional addition of expanding agent can close original aluminium oxide duct, and then can lead
The problems such as pore road collapses.
In heavy oil or residual hydrogenation catalytic field, other than the Kong Rong and aperture that require catalyst carrier are sufficiently large, by urging
The intensity of catalyst prepared by agent carrier is also to consider the vital factor of catalyst carrier properties quality.Chinese patent
1249208 A of document CN disclose a kind of macropore alumina supporter and preparation method thereof, by different route systems in the prior art
The one or more of standby boehmite dry glue powder are mixed with carbon powder, surface reactive material, by water, peptizing agent and are helped crowded
The effect extrusion molding of agent, then carrier is obtained after drying, roasting, the alumina support prepared can be used as hydrogenation catalyst
Carrier, especially suitable for big molecular impurity such as nickel, vanadium, the higher feedstock oil of arsenic equal size or Heavy oil hydrogenation catalyst
Carrier.However since the prior art is during preparation, 650-950 DEG C of high-temperature roasting is needed, support oxide is easily led to
Sintering phenomenon occurs, 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 mobile formation lattice defect in turn of heat of ion, or because the insertion of foreign ion makes the chemical shape of component
State changes and finally influences the activity of catalyst.
Invention content
Therefore, the technical problem to be solved in the present invention is to overcome the catalyst removed in the prior art in residual hydrogenation to carry
Body aperture blocks duct compared with little Yi, and need to additionally add expanding agent can close original aluminium oxide duct and then hole can be caused to say
Now collapse and high-temperature roasting and cause support oxide be sintered and lattice defect eventually lead to by its gained catalyst work
Property difference defect, to provide a kind of catalyst for demetalation carrier and preparation method thereof.
For this purpose, technical scheme is as follows：
A kind of catalyst for demetalation carrier of hydrated glass-chlorination calcium complexes.
Under normal temperature condition, using 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 parts by weight are：8~20 parts of waterglass, 10~30 parts of calcium chloride, 0.5~5 part of emulsification function extrusion aid,
40~85 parts of the mixture of 5~75 parts of molecular sieve and Si oxide and aluminum oxide.
The raw material components parts by weight are：10 parts of waterglass, 15 parts of calcium chloride, 0.5 part of emulsification function extrusion aid, molecular sieve
70 parts of the mixture of 5 parts and Si oxide and aluminum oxide.
The emulsification function extrusion aid is extrusion aid H；The molecular sieve is MCM-41 molecular sieves, the Si oxide and aluminium
Hopcalite is one or more of boehmite, aluminum oxide dry glue powder, SB powder.
The calcium chloride is calcium chloride powder.
The modulus of water glass is 3.1~3.4.Waterglass within the scope of the modulus is in the reactivity that can guarantee catalyst
Matter, degree of reaction and thermal discharge react premature aging that is too fast and leading to carrier in suitable degree.
The emulsification function extrusion aid is one or more of Ludox, polyvinyl alcohol, sesbania powder and natural gum.
A kind of preparation method of catalyst for demetalation carrier, is as follows：
(1) progress of Si oxide, aluminum oxide and molecular sieve is dry-mixed to uniform, obtain the first mixture；
(2) emulsification function extrusion aid and the first mixture are subjected to wet mixing to uniform, obtain the second mixture；
(3) water is added into waterglass and is prepared into the liquid soluble glass that solid content is 20~80wt%, is then mixed second
It closes object and is added in the liquid soluble glass and carry out wet mixing to uniform, obtain third mixture；
(4) water is added into calcium chloride and is prepared into the calcium chloride water that mass fraction is 10~70%, then by third
Mixture, which is added in the calcium chloride water, carries out wet mixing to uniform, obtains the 4th mixture；
(5) by the 4th mixture extrusion forming, up to catalyst for demetalation carrier after drying；
Step (1)-(4) carry out under normal temperature condition.
Drying in step (5) is to be warming up to 200 DEG C of dry 1~10h.
The shape of extrusion forming in step (5) is column or bunge bedstraw herb type, length 3-5cm.Above-mentioned demetalization catalysis
The application of agent carrier.
The addition of calcium chloride makes calcium chloride and waterglass produce synergistic effect solidifying to optimize waterglass in the present invention
The performance of glue, improves the pore structure and intensity of sodium silicate gel, and then keeps its gelatification stronger, and is rendered as short range and has
Sequence, long-range unordered microstructure, and with the gel state of the different morphologies such as fibrous, netted and microgranular, to removing slag
Metal has good deposition in oil.The present invention is due to and being adulterated wherein using Si oxide and aluminum oxide as carrier
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 all carries out under normal temperature condition, therefore
It will not cause support oxide that sintering phenomenon occurs, and then the aperture of carrier, specific surface area, specific pore volume can be caused to reduce, also not
It can cause the heat of ion mobile because of high-temperature roasting and then form lattice defect, or because of the insertion of foreign ion, make component
Chemical state changes and eventually affects the activity of catalyst.
The catalyst for demetalation carrier of the present invention, MCM-41 molecular sieves used itself have mutually independent ten-ring hole
Road system, half supercage structure of twelve-ring supercage, supercage and hexatomic ring is contained in system, and the pore passage structure of this complexity makes
MCM-41 molecular sieves have higher specific surface area and excellent adsorption capacity；The addition of waterglass-calcium chloride has solidifying well
Glue acts on, the gel state of presentation, is short-range order, long-range unordered microstructure, has fibrous, netted and microgranular etc.
Different morphologies have good deposition for metal in removing residual oil；The addition of extrusion aid H, can be in effective protection carrier
Al2O3Influence to waterglass-calcium chloride can play good emulsification.Si oxide and aluminum oxide carry in the present invention
It complements each other, cooperates between body and waterglass, calcium chloride, each active constituent of emulsification function extrusion aid H, MCM-41 molecular sieve
It comes into force and makes the catalyst for demetalation carrier of the present invention has to integrate effective specific surface and pore structure, high mechanical strength, 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 following advantages that：
(1) catalyst for demetalation carrier provided by the invention at spherical shape or is in strip or other shapes conducive to catalyst,
It can be revised according to the requirement of product, it is easy to operate, it is easily mastered.
(2) the demetallated removal efficiency of catalyst prepared by catalyst for demetalation carrier provided by the invention be 60% with
On, up to 95%, and there is higher anti-pressure and abrasion-proof intensity.
(3) catalyst for demetalation carrier provided by the invention has comprehensive effective specific surface and pore structure, and by this hair
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 invention is not required to additionally add expanding agent in preparation process, easy to operate to be easy to industry
Change, the desulfurization of catalyst, denitrogenation and the demetallated removal efficiency prepared by the catalyst carrier of the present invention is high, mechanical strength and
Anti-pressure and abrasion-proof intensity is all relatively good.
Specific implementation mode
It is to preferably further understand the present invention to provide following embodiments, it is not limited to the best embodiment party
Formula is not construed as limiting present disclosure and protection domain, anyone under the inspiration of the present invention or by the present invention and its
The feature of his prior art be combined and obtain it is any with the present invention it is same or similar as product, all fall within the present invention
Within protection domain.
Specific experiment step or condition person are not specified in embodiment, according to routine experiment described in document in the art
The operation of step or condition can carry out.Reagents or instruments used without specified manufacturer, being can be by acquisition purchased in market
Conventional reagent product.
The molecular sieve used in each embodiment in the present invention is MCM-41 molecular sieves, other molecular sieves of the prior art
It can realize that the goal of the invention of the present invention, each embodiment in the present invention do not constitute limiting the scope of the invention.
The solid content of liquid soluble glass in the present invention refers to the effective quantity of waterglass.
The modulus of 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 Weifang beach Chemical Co., Ltd., and specifications and models are anhydrous calcium chloride；
MCM-41 molecular sieves are available commercially from Shanghai Heng Ye molecular sieves limited liability company；
Boehmite is available commercially from Liaoning Haitai development in science and technology Co., Ltd；
Aluminum oxide dry glue powder is available commercially from Liaoning Haitai development in science and technology Co., Ltd；
SB powder (active oxidation alumina gel) is available commercially from Liaoning Haitai development in science and technology Co., Ltd；
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 liability company of emblem Wanwei High-new Technology Co., specifications and models PVA17-99；
Sesbania powder is available commercially from one hundred emerging bio tech ltd of Wuhan；
Natural gum is available commercially from ploughshare natural gum industry Products Co., Ltd of Zhongshan city,
Embodiment 1
The catalyst for demetalation carrier of the present embodiment, including the following raw material component：
Waterglass 10kg, calcium chloride 10kg, extrusion aid H 1.5kg, MCM-41 molecular sieves 75kg.
The catalyst for demetalation carrier of embodiment is prepared with the following method：
It is as follows：
(1) the MCM-41 molecular sieves weighed according to selected weight and extrusion aid H are subjected to dry-mixed 30min, and mixed
Uniformly, the first mixture is spare；
(2) suitable quantity of water will be added in the waterglass weighed according to selected weight to be prepared into solid content is that 25wt% waterglass is molten
Then the first mixture obtained in step (1) is added in the water glass solution and carries out wet mixing 30min, and mixes equal by liquid
Even, manufactured second mixture is spare；
(3) it is 20% calcium chloride that suitable water will be added in the calcium chloride weighed according to selected weight and be prepared into mass fraction
Then the second mixture obtained in step (2) is added in the calcium chloride water and carries out wet mixing 10min by aqueous solution, and
It is uniformly mixed, manufactured third mixture is spare；
(4) the third mixture obtained in step (3) is squeezed into bunge bedstraw herb type, then length 5mm is carried out at 120 DEG C
Dry 5h is to get the catalyst for demetalation carrier.
Embodiment 2
The catalyst for demetalation carrier of the present embodiment, including the following raw material component：
Waterglass 25kg, calcium chloride powder 10kg, extrusion aid are Ludox H 3kg, MCM-41 molecular sieves 20kg, Si oxide
With the mixture 40kg of aluminum oxide (for boehmite).
The catalyst for demetalation carrier of embodiment is prepared with the following method：
It is as follows：
(1) Si oxide, aluminum oxide and MCM-41 molecular sieves will be weighed according to selected weight carries out dry-mixed 30min, and
It is uniformly mixed, the first mixture is spare；
(2) extrusion aid H and the first mixture will be weighed according to selected weight and carries out dry-mixed 20min, and will be uniformly mixed, and obtain the
Two mixtures are spare；
(3) it is that 20wt% waterglass is molten that will weigh addition suitable quantity of water in waterglass according to selected weight and be prepared into solid content
Then the second mixture obtained in step (2) is added in the water glass solution and carries out wet mixing 30min, and mixes equal by liquid
Even, manufactured third mixture is spare；
(4) it is 50% calcium chloride that suitable water will be added in the calcium chloride weighed according to selected weight and be prepared into mass fraction
Then the third mixture obtained in step (3) is added in the calcium chloride water and carries out wet mixing 15min by aqueous solution, and
It is uniformly mixed, manufactured 4th mixture is spare；
(5) the 4th mixture obtained in step (4) is squeezed into stripe shape, then length 5mm is carried out dry at 120 DEG C
5h is to get the catalyst for demetalation carrier.
Embodiment 3
The catalyst for demetalation carrier of the present embodiment, including the following raw material component：
Waterglass 20kg, calcium chloride powder 30kg, extrusion aid H (for polyvinyl alcohol) 5kg, MCM-41 molecular sieves 10kg, silica
The mixture 40kg of compound and aluminum oxide (for aluminum oxide dry glue powder).
The catalyst for demetalation carrier of the present embodiment is prepared with the following method：
It is as follows：
(1) Si oxide, aluminum oxide and MCM-41 molecular sieves are weighed according to selected weight and carries out dry-mixed 20min, and mixed
It closes uniformly, it is spare to obtain the first mixture；
(2) it weighs extrusion aid H according to selected weight and the first mixture carries out dry-mixed 20min, and be uniformly mixed, obtain second
Mixture is spare；
(3) waterglass is weighed according to selected weight, and suitable quantity of water is added thereto and is prepared into solid content 30wt% liquid waters
Then the second mixture obtained in step (2) is added in water glass solution and carries out wet mixing 50min, and is uniformly mixed by glass,
Manufactured third mixture is spare；
(4) calcium chloride is weighed according to selected weight, and suitable water is added thereto and is prepared into 30% chlorination of mass fraction
Then the third mixture obtained in step (3) is added in the calcium chloride water and carries out wet mixing 5min by calcium aqueous solution, and
It is uniformly mixed, manufactured 4th mixture is spare；
(5) the 4th mixture obtained in step (4) is squeezed into bunge bedstraw herb type, then length 5mm is carried out at 120 DEG C
Dry 5h is to get the catalyst for demetalation carrier.
Embodiment 4
The catalyst for demetalation carrier of the present embodiment, including the following raw material component：
Waterglass 15kg, calcium chloride powder 17kg, extrusion aid H (for sesbania powder) 2kg, MCM-41 molecular sieves 60kg, silicon oxidation
The mixture 60kg (SB powder) of object and aluminum oxide.
The catalyst for demetalation carrier of the present embodiment is prepared with the following method：
It is as follows：
(1) Si oxide, aluminum oxide and MCM-41 molecular sieves that are weighed according to selected weight are carried out dry-mixed
25min, and be uniformly mixed, it is spare to obtain the first mixture；
(2) extrusion aid H and the first mixture will be weighed according to selected weight and carries out dry-mixed 25min, and will be uniformly mixed, and obtain the
Two mixtures are spare；
(3) it is that 40wt% waterglass is molten that will weigh addition suitable quantity of water in waterglass according to selected weight and be prepared into solid content
Then the second mixture obtained in step (2) is added in the water glass solution and carries out wet mixing 50min, and mixes equal by liquid
Even, manufactured third mixture is spare；
(4) it is 60% calcium chloride that suitable water will be added in the calcium chloride weighed according to selected weight and be prepared into mass fraction
Then the third mixture obtained in step (3) is added in the calcium chloride water and carries out wet mixing 5min, and mixes by aqueous solution
It closes uniformly, manufactured 4th mixture is spare；
(5) the 4th mixture obtained in step (4) is squeezed into bunge bedstraw herb type, then length 5mm is carried out at 120 DEG C
Dry 5h is to get the catalyst for demetalation carrier.
Embodiment 5
The catalyst for demetalation carrier of the present embodiment, including the following raw material component：
Waterglass 8kg, calcium chloride 20kg, extrusion aid H (natural gum) 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 prepared with the following method：
It is as follows：
(1) Si oxide, aluminum oxide and MCM-41 molecular sieves that are weighed according to selected weight are carried out dry-mixed
20min, and be uniformly mixed, it is spare to obtain the first mixture；
(2) extrusion aid H and the first mixture will be weighed according to selected weight and carries out dry-mixed 20min, and will be uniformly mixed, and obtain the
Two mixtures are spare；
(3) it is that 80wt% waterglass is molten that will weigh addition suitable quantity of water in waterglass according to selected weight and be prepared into solid content
Then the second mixture obtained in step (2) is added in the water glass solution and carries out wet mixing 50min, and mixes equal by liquid
Even, manufactured third mixture is spare；
(4) it is 70% calcium chloride that suitable water will be added in the calcium chloride weighed according to selected weight and be prepared into mass fraction
Then the third mixture obtained in step (3) is added in the calcium chloride water and carries out wet mixing 5min, and mixes by aqueous solution
It closes uniformly, manufactured 4th mixture is spare；
(5) the 4th mixture obtained in step (4) is squeezed into bunge bedstraw herb type, then length 5mm is carried out at 120 DEG C
Dry 5h is to get the catalyst for demetalation carrier.
Embodiment 6
The catalyst for demetalation carrier of the present embodiment, including the following raw material component：
Waterglass 10kg, calcium chloride 15kg, extrusion aid H (natural gum) 0.5kg, MCM-41 molecular sieve 5kg, Si oxide and aluminium
Hopcalite 70kg (SB powder and alumina dry glue powder mixture).
The catalyst for demetalation carrier of the present embodiment is prepared with the following method：
It is as follows：
(1) Si oxide, aluminum oxide and MCM-41 molecular sieves that are weighed according to selected weight are carried out dry-mixed
20min, and be uniformly mixed, it is spare to obtain the first mixture；
(2) extrusion aid H and the first mixture will be weighed according to selected weight and carries out dry-mixed 20min, and will be uniformly mixed, and obtain the
Two mixtures are spare；
(3) it is that 40wt% waterglass is molten that will weigh addition suitable quantity of water in waterglass according to selected weight and be prepared into solid content
Then the second mixture obtained in step (2) is added in the water glass solution and carries out wet mixing 50min, and mixes equal by liquid
Even, manufactured third mixture is spare；
(4) it is 10% chlorination that suitable water will be added in the calcium chloride weighed according to selected weight and be prepared into mass fraction
Then the third mixture obtained in step (3) is added in the calcium chloride water and carries out wet mixing 5min by calcium aqueous solution, and
It is uniformly mixed, manufactured 4th mixture is spare；
(5) the 4th mixture obtained in step (4) is squeezed into bunge bedstraw herb type, then length 5mm is carried out at 120 DEG C
Dry 5h is to get the catalyst for demetalation carrier.
Embodiment 7
The catalyst for demetalation carrier of the present embodiment, including the following raw material component：
Waterglass 5kg, calcium chloride 31kg, extrusion aid H (natural gum) 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 prepared with the following method：
It is as follows：
(1) Si oxide, aluminum oxide and MCM-41 molecular sieves that are weighed according to selected weight are carried out dry-mixed
20min, and be uniformly mixed, it is spare to obtain the first mixture；
(2) extrusion aid H and the first mixture will be weighed according to selected weight and carries out dry-mixed 20min, and will be uniformly mixed, and obtain the
Two mixtures are spare；
(3) it is that 30wt% waterglass is molten that will weigh addition suitable quantity of water in waterglass according to selected weight and be prepared into solid content
Then the second mixture obtained in step (2) is added in the water glass solution and carries out wet mixing 50min, and mixes equal by liquid
Even, manufactured third mixture is spare；
(4) it is 20% calcium chloride that suitable water will be added in the calcium chloride weighed according to selected weight and be prepared into mass fraction
Then the third mixture obtained in step (3) is added in the calcium chloride water and carries out wet mixing 5min, and mixes by aqueous solution
It closes uniformly, manufactured 4th mixture is spare；
(5) the 4th mixture obtained in step (4) is squeezed into bunge bedstraw herb type, then length 5mm is carried out at 120 DEG C
Dry 5h is to get the catalyst for demetalation carrier.
Comparative example 1
The catalyst for demetalation carrier of the present embodiment, including the following raw material component：
The mixture of waterglass 0.5kg, calcium chloride 10kg, MCM-41 molecular sieve 40kg, Si oxide and aluminum oxide
40kg。
The catalyst for demetalation carrier of embodiment is prepared with the following method：
It is as follows：
(1) Si oxide, aluminum oxide and MCM-41 molecular sieves that are weighed according to selected weight are carried out dry-mixed
30min, and be uniformly mixed, the first mixture is spare；
(2) suitable quantity of water will be added in the waterglass weighed according to selected weight and is prepared into 10% water glass solution, then will
The first mixture obtained in step (1), which is added in the water glass solution, carries out wet mixing 10min, and is uniformly mixed, manufactured
Second mixture is spare；
(3) suitable water will be added in the calcium chloride weighed according to selected weight and is prepared into 15% calcium chloride water, so
The second mixture obtained in step (2) is added in the calcium chloride water afterwards and carries out wet mixing 5min, and is uniformly mixed, is made
At third mixture it is spare；
(4) the third mixture obtained in step (3) is squeezed into bunge bedstraw herb type, then length 4mm is carried out at 120 DEG C
Dry 5h is to get the catalyst for demetalation carrier.
Comparative example 2
The catalyst for demetalation carrier of the present embodiment, including the following raw material component：
The mixture of waterglass 20kg, calcium chloride 40kg, emulsification function extrusion aid H 5kg, Si oxide and aluminum oxide
40kg。
The catalyst for demetalation carrier of embodiment is prepared with the following method：
It is as follows：
(1) Si oxide weighed according to selected weight, aluminum oxide and extrusion aid H are subjected to dry-mixed 30min, and
It is uniformly mixed, the first mixture is spare；
(2) suitable quantity of water will be added in the waterglass weighed according to selected weight and is prepared into 15% water glass solution, then will
The first mixture obtained in step (1), which is added in the water glass solution, carries out wet mixing 20min, and is uniformly mixed, manufactured
Second mixture is spare；
(3) suitable water will be added in the calcium chloride weighed according to selected weight and is prepared into 30% calcium chloride water, so
The second mixture obtained in step (2) is added in the calcium chloride water afterwards and carries out wet mixing 15min, and is uniformly mixed,
Manufactured third mixture is spare；
(4) the third mixture obtained in step (3) is squeezed into bunge bedstraw herb type, then length 5mm is carried out at 120 DEG C
Dry 5h is to get the catalyst for demetalation carrier.
Experimental example
It processes to obtain catalyst using the carrier of preparation, metal removal test, Kong Rong and specific surface area is carried out to catalyst
Test：
The embodiment 1-3 of the phase homogenous quantities and comparative example 1-2 carriers prepared are immersed in same volume and concentration respectively
In active component aqueous solution, active component be account for the carrier quality 3% cobalt and 0.5% molybdenum, catalyst is prepared.
It measures 100ml Catalyst packings to enter in the small-sized evaluating apparatus of fixed bed residual hydrocracking, be carried out with reduced crude
Reaction evaluating, reaction pressure 8mPa, air speed 2h-1, measured and generated in oil using plasma emission spectrum (AES/ICP) method
The content of nickel, vanadium and other metals (iron, calcium, sodium) calculates metal extrusion rate, is as a result listed in table 1.
Metal removal rate=1- [generating metal (nickel, vanadium, other) content in oil]/[metallic nickel in feedstock oil, vanadium, other]
Content] × 100%
Catalyst metals removal efficiency obtained by examples detailed above the results are shown in Table 1：
The basic performance table of 1 catalyst of table
By test result it can be seen that using sial as carrier, calcium chloride, waterglass, MCM-41 molecular sieves are added in carrier
And auxiliary agent can significantly improve the demetalization efficiency that carrier prepares catalyst.And obviously embody the carrier have it is basic
Feature, and there is higher anti-pressure and abrasion-proof intensity.And the 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.
The above embodiments are merely examples for clarifying the description, and does not limit the embodiments.For institute
For the those of ordinary skill in category field, other various forms of variations or change can also be made on the basis of the above description
It is dynamic.There is no necessity and possibility to exhaust all the enbodiments.And obvious variation extended from this or change
Dynamic still within the protection scope of the invention obvious, the above embodiments are merely examples for clarifying the description,
And it does not limit the embodiments.For those of ordinary skill in the art, may be used also on the basis of the above description
To make other variations or changes in different ways.There is no necessity and possibility to exhaust all the enbodiments.And thus
The obvious changes or variations extended out are still within the protection scope of the invention.
Claims (5)
1. a kind of catalyst for demetalation carrier of hydrated glass-chlorination calcium complexes, which is characterized in that
Under normal temperature condition, using aluminum oxide as carrier, waterglass, calcium chloride, emulsification function are added in the carrier of aluminum oxide
Extrusion aid, molecular sieve and obtain；
Raw material components parts by weight are：8~20 parts of waterglass, 10~30 parts of calcium chloride, 0.5~5 part of emulsification function extrusion aid, molecule
40~85 parts of the mixture of 5~75 parts of sieve and aluminum oxide；
The emulsification function extrusion aid is extrusion aid H, one kind or several in Ludox, polyvinyl alcohol, sesbania powder and natural gum
Kind；The molecular sieve is MCM-41 molecular sieves, and the mixture of the aluminum oxide is boehmite, aluminum oxide dry glue powder, SB
One or more of powder；
The modulus of water glass is 3.1~3.4.
2. catalyst carrier according to claim 1, which is characterized in that the raw material components parts by weight are：Waterglass 10
Part, 15 parts of calcium chloride, 0.5 part of emulsification function extrusion aid, 5 parts of molecular sieve and aluminum oxide 70 parts of mixture.
3. catalyst carrier according to claim 2, which is characterized in that the calcium chloride is calcium chloride powder.
4. a kind of preparation method of catalyst for demetalation carrier as described in any one of claims 1-3, is as follows：
（1）Aluminum oxide and molecular sieve progress is dry-mixed to uniform, obtain the first mixture；
（2）Emulsification function extrusion aid and the first mixture are subjected to wet mixing to uniform, obtain the second mixture；
（3）Water is added into waterglass and is prepared into the liquid soluble glass that solid content is 20~80wt%, then adds the second mixture
Enter to carry out wet mixing in the liquid soluble glass to uniform, obtains third mixture；
（4）Water is added into calcium chloride and is prepared into the calcium chloride water that mass fraction is 10~70%, then by third mixture
It is added in the calcium chloride water and carries out wet mixing to uniform, obtain the 4th mixture；
（5）By the 4th mixture extrusion forming, up to catalyst for demetalation carrier after drying；
Step（1）-（4）Carried out under normal temperature condition；
Step（5）In drying be warming up to 200 DEG C of dry 1~10h.
5. according to the method described in claim 4, it is characterized in that, step（5）In extrusion forming shape be column or four
Leaf grass type, length 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 |
| CN104138765A (en) * | 2014-07-10 | 2014-11-12 | 浙江海洲制药有限公司 | Solid base catalyst, preparation of solid base catalyst as well as application of solid base catalyst to preparation of guaifenesin |
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