CN106622262B - A kind of hydrogenation protecting agent and its preparation method and application - Google Patents
A kind of hydrogenation protecting agent and its preparation method and application Download PDFInfo
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- CN106622262B CN106622262B CN201510724482.XA CN201510724482A CN106622262B CN 106622262 B CN106622262 B CN 106622262B CN 201510724482 A CN201510724482 A CN 201510724482A CN 106622262 B CN106622262 B CN 106622262B
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Abstract
The present invention relates to a kind of hydrogenation protecting agent; the protective agent contains active metal component and modified hydrogen at-ing catalyst carrier; the modified hydrogen at-ing catalyst carrier includes the metal promoter and acid additive of carrier and load on the carrier; the metal promoter and acid additive are in layer distributed on the carrier; shell is metal promoter; stratum nucleare is acid additive; the metal promoter is group ia metal component and/or group iia metal component, and the acid additive is selected from least one of F, P and B component.The present invention also provides the preparation method and application of above-mentioned hydrogenation protecting agent.By using hydrogenation protecting agent of the invention, comprehensive metal removal effect can be obtained, and the hydrogenation protecting agent is not easy to form carbon distribution, activity and high stability in the application of heavy-oil hydrogenation processing.
Description
Technical field
The present invention relates to a kind of hydrogenation protecting agent and its preparation method and application.
Background technique
The utilization rate that deep processing not only contributes to improve heavy oil is carried out to the heavy oil including residual oil, alleviates the energy and supplies
The nervous trend answered, while can also reduce environmental pollution, reach the clean utilization of the energy.Compared with distillate, heavy oil such as slag
The metal atom contents such as nickel (Ni), vanadium (V), iron (Fe) and calcium (Ca) in oil etc. are high；And iron is inclined in some naphthenic acid contents
It can be concentrated in heavy oil in the form of iron naphthenate in high heavy oil.The metal impurities such as Ni, V, Fe, Ca are during residual hydrogenation
Catalyst bed fouling, blocking is easily caused to be forced to stop work since pressure drop is excessive so as to cause device.Solve this problem
Effective way first is that filling has protective agent (i.e. hydrogenation protecting agent) with hydrogenation efficiency on hydrogenation catalyst top.However it is existing
With the presence of hydrogenation protecting agent metal removal activity it is not high enough, and W metal and V etc. easily deposition cause catalyst aperture blocking, urge
Agent activity cannot mutually be utilized effectively, the shortcomings that so as to cause catalyst activity reduction.
Summary of the invention
The purpose of the present invention is being to overcome, existing hydrogenation protecting agent demetalization is low and metal is easily deposited on catalyst
The defect in aperture provides a kind of can be realized comprehensive metal removal effect and is not easy to form the hydrogenation protecting agent of carbon distribution and its preparation
Methods and applications.
To achieve the goals above, the present invention provides a kind of hydrogenation protecting agent, the protective agent contain active metal component and
Modified hydrogen at-ing catalyst carrier, which is characterized in that the modified hydrogen at-ing catalyst carrier includes carrier and is supported on the carrier
On metal promoter and acid additive, the metal promoter and acid additive are in layer distributed on the carrier, and shell is gold
Belong to auxiliary agent, stratum nucleare is acid additive, and the metal promoter is group ia metal component and/or group iia metal component, the acid
Property auxiliary agent be selected from least one of F, P and B component；And
The active metal component contains at least one group VIII metal component and at least one vib metals group
Point, it is counted by metal oxide and on the basis of protectant total weight, the content of the group VIII metal component is greater than 0
Weight % and it is less than or equal to 1 weight %, the content of the vib metals component is greater than 0 weight % and is less than or equal to 6 weights
Measure %.
The present invention also provides the preparation methods of above-mentioned hydrogenation protecting agent, wherein this method comprises:
(1) carrier Jing Guo hydro-thermal process is provided with to the metal promoter chemical combination of the metal promoter in alkaline containing
It is impregnated in first solution of object, is then dried, obtain the carrier that load has the metal promoter；
(2) carrier of the metal promoter helps in acid containing the acidity for being provided with the acid additive above-mentioned load
It is impregnated in second solution of immunomodulator compounds, is then dried and roasts, obtain the modified hydrogen at-ing catalyst carrier；
(3) the modified hydrogen at-ing catalyst carrier is molten in the third containing the compound for being provided with the active metal component
It is impregnated in liquid, is then dried and roasts.
The present invention also provides application of the above-mentioned hydrogenation protecting agent in heavy-oil hydrogenation processing.
By using hydrogenation protecting agent of the invention, comprehensive metal can be obtained in the application of heavy-oil hydrogenation processing
Removal effect, and the hydrogenation protecting agent is not easy to form carbon distribution, activity and high stability.
Other features and advantages of the present invention will the following detailed description will be given in the detailed implementation section.
Specific embodiment
Detailed description of the preferred embodiments below.It should be understood that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to restrict the invention.
The present invention provides a kind of hydrogenation protecting agent, which contains active metal component and modified hydrogen at-ing catalyst carries
Body, which is characterized in that the modified hydrogen at-ing catalyst carrier includes the metal promoter and acid of carrier and load on the carrier
Property auxiliary agent, the metal promoter and acid additive are in layer distributed on the carrier, and shell is metal promoter, stratum nucleare be acidity
Auxiliary agent, the metal promoter are group ia metal component and/or group iia metal component, and the acid additive is selected from F, P and B
At least one of component；And
The active metal component contains at least one group VIII metal component and at least one vib metals group
Point, it is counted by metal oxide and on the basis of protectant total weight, the content of the group VIII metal component is greater than 0
Weight % and it is less than or equal to 1 weight %, the content of the vib metals component is greater than 0 weight % and is less than or equal to 6 weights
Measure %.
According to the present invention, although working as the content of the group VIII metal component and containing for the vib metals component
Amount within the above range, can be good thus to obtain metal removal effect and be not easy to form the active metal of the hydrogenation protecting agent of carbon distribution
Component, in order to obtain the more excellent protective agent of property, under preferable case, in terms of metal oxide and with the protective agent
Total weight on the basis of, the content of the group VIII metal component is 0.1-0.9 weight %.Under preferable case, the Section VI B
The content of race's metal component is 0.1-5 weight %.
Wherein, the group VIII metal component refers to that the hydrogenation protecting agent in heavy-oil hydrogenation processing contains group VIII
Metallic element, or can be described as the group VIII metal that modified hydrogen at-ing catalyst supported on carriers has in heavy-oil hydrogenation processing
Element can be as group VIII metal component of the invention commonly used in as the hydrogenation protecting agent in heavy-oil hydrogenation processing
Active metal component group VIII metallic element, under preferable case, the group VIII metal component be selected from Co and/or
Ni。
Wherein, the vib metals component refers to that the hydrogenation protecting agent in heavy-oil hydrogenation processing contains group VIB
Metallic element, or can be described as the vib metals that modified hydrogen at-ing catalyst supported on carriers has in heavy-oil hydrogenation processing
Element can be as vib metals component of the invention commonly used in as the hydrogenation protecting agent in heavy-oil hydrogenation processing
Active metal component vib metals element, under preferable case, vib metals group is selected from Mo and/or W.
According to the present invention, since the hydrogenation protecting agent passes through in the carrier loaded active metal of modified hydrogen at-ing catalyst
By prepared by roasting, therefore, above-mentioned active metal component is in the hydrogenation protecting agent usually with metal oxygen after component
The form of compound exists, and the present invention is also not limited to this certainly, and the active metal component is also possible in addition to oxide
The form of the compound of the offer active metal component in addition exists.
It wherein, can be CoO as the metal oxide form of Co, the metal oxide form as Ni can be NiO,
Metal oxide form as Mo can be MoO3, the metal oxide form as W can be WO3。
Wherein, the compound of the offer Co other than CoO for example can be cobalt carbonate (CoCO3), cobalt nitrate (CoNO3)、
Cobalt acetate (Co (AcO)3), basic cobaltous carbonate (2CoCO3·3Co(OH)2·H2) and cobalt chloride (CoCl O2) one of or it is more
Kind.
Wherein, the compound of the offer Ni other than NiO for example can be nickelous carbonate (NiCO3), nickel nitrate (NiNO3)、
Nickel acetate (Ni (AcO)3), basic nickel carbonate (NiCO3·2Ni(OH)2·4H2) and nickel chloride (NiCl O2) one of or it is more
Kind.
Wherein, in addition to MoO3The compound of offer Mo in addition for example can be ammonium molybdate ((NH4)2MoO4), ammonium paramolybdate
((NH4)6Mo7O24), ammonium dimolybdate ((NH4)2Mo2O7) and ammonium tetramolybdate ((NH4)2Mo4O13) one of or it is a variety of.
Wherein, in addition to WO3The compound of offer W in addition for example can be ammonium tungstate ((NH4)10W12O41), ammonium metatungstate
((NH4)6H2W12O40) and one of ethyl ammonium metatungstate or a variety of.
According to the present invention, metal promoter compound will provide the metal promoter, and the metal promoter refers to I A
Metallic element in race and/or group iia, wherein group ia metal is preferably one of Li, Na and K or a variety of, Section II A
Race's metal is preferably Mg and/Ca, thus, metal promoter of the invention is preferably one of Li, Na, K, Mg and Ca or a variety of.
Wherein, the metal promoter compound for providing Li for example can be lithium nitrate and/or lithium sulfate.
Wherein, the metal promoter compound for providing Na for example can be sodium nitrate and/or sodium sulphate.
Wherein, the metal promoter compound for providing K for example can be potassium nitrate and/or potassium sulfate.
Wherein, the metal promoter compound for providing Mg for example can be magnesium nitrate and/or magnesium chloride.
Wherein, provide the metal promoter compound of Ca for example can for one of calcium nitrate, calcium chloride and calcium acetate or
It is a variety of.
According to the present invention, the acid additive is derived from the acid additive compound, and the acid additive refers to selecting
From at least one of F, P and B element.
Wherein, the acid additive compound for providing F for example can be ammonium fluoride, ammonium acid fluoride, hydrofluoric acid, sodium fluoride and fluorine
Change one of calcium or a variety of.
Wherein, the acid additive compound for providing P for example can be phosphoric acid, Diammonium phosphate (DAP), sodium dihydrogen phosphate and di(2-ethylhexyl)phosphate
One of hydrogen potassium is a variety of.
Wherein, the acid additive compound for providing B for example can be one of boric acid, metaborate and borate or more
Kind.
According to the present invention, it should be noted that " shell is metal promoter, and stratum nucleare is acid additive " refers to metal promoter master
It is distributed in shell, can have and be distributed in stratum nucleare on a small quantity；And acid additive is mainly distributed on stratum nucleare, can also have and be distributed on a small quantity
Shell.Due to SEM-EDX (Scanning Electron Microscope-Energy Dispersive Spectrometry)
The numerical value of the every bit constituent content radially measured in characterization result along modified catalyst supports particle and the point element content phase
It is mutually corresponding, although the size of the numerical value may not represent the real content of the point element, it is able to reflect the point element content
Just.In order to indicate that metal promoter and acid additive introduce distribution factor σ along the regularity of distribution of carrier radial direction.The distribution factor
σ is that (R is particle radius to auxiliary agent, with modified hydrogen at-ing catalyst with the ratio of concentration at center on a certain position of carrier granular
It is starting point at carrier granular center).Wherein, concentration of the auxiliary agent on a certain position of carrier granular refers to SEM-EDX characterization knot
The average value that nearby (position deviation≤20nm) 20 numerical points count in the position in fruit, auxiliary agent is at the center of carrier granular
Concentration refer in SEM-EDX characterization result being averaged near central point (position deviation≤20nm) 20 numerical points numerations
Value.If σ > 1, show that the content of auxiliary agent at that point is higher than corresponding additive at modified hydrogen at-ing catalyst carrier granular center and contains
Amount；If σ=1, show that the content of auxiliary agent at that point contains with corresponding additive at modified hydrogen at-ing catalyst carrier granular center
It measures identical；If σ < 1, show the content of auxiliary agent at that point lower than corresponding additive at modified hydrogen at-ing catalyst carrier granular center
Content.Wherein, in the modified hydrogen at-ing catalyst carrier, the distribution factor of the metal promoter of carrier granular outer layer (shell)
σ > 1, and the distribution factor σ < 1 of the acid additive of carrier granular outer layer (shell).
The present invention is not particularly limited the thickness of the shell and stratum nucleare, for example, the thickness of the shell can be
0.1-5mm, preferably 0.1-4mm, more preferably 0.1-2.5mm；The thickness of the stratum nucleare can be 0.1-5mm, preferably
0.1-4mm, more preferably 0.15-3.5mm.Wherein, the thickness of the shell refers to distribution factor σ >=2 of the metal promoter
Partial thickness, and the stratum nucleare thickness refers to the thickness of 1 part 0.5≤σ of distribution factor < of acid additive.In the present invention
In, the thickness of the shell and stratum nucleare is measured using SEM-EDX method, specifically, is randomly selected 30 modified hydrogen at-ing catalysts and is carried
Body simultaneously measures its cross section and partial size with SEM, is obtained respectively along each modified hydrogen at-ing catalyst carrier radial scan with EDX later
The radial distribution of metal promoter component and the thickness for obtaining the part σ >=2, taking the arithmetic mean of instantaneous value of above-mentioned thickness is institute of the present invention
The thickness for the shell stated；And acid additive component is obtained along each modified hydrogen at-ing catalyst carrier radial scan respectively with EDX
Radial distribution and the thickness for obtaining 1 part 0.5≤σ <, taking the arithmetic mean of instantaneous value of above-mentioned thickness is stratum nucleare of the present invention
Thickness.
The present invention is not particularly limited the content of the metal promoter and acid additive, but in order to enable is changed by described
Property catalyst carrier for hydrgenating made of hydrogenation catalyst shown in hydrogenation reaction better denitrification activity and carbon residue removing live
Property, it is preferable that the content of the metal promoter in terms of metal oxide is 0.1-15 weight %, further preferably 0.2-12
Weight %, more preferably 0.3-8 weight %, most preferably 1-3 weight %.Preferably, described in terms of tri- kinds of elements of F, P and B
The content of acid additive be 0.1-15 weight %, further preferably 0.2-12 weight %, more preferably 0.3-8 weight %, most
Preferably 1-2 weight %.Wherein, " content of the acid additive in terms of tri- kinds of elements of F, P and B " refers to the acid additive
Weight measured using the total weight of tri- kinds of elements of F, P and B as representative, wherein when the acid additive does not include F, P
When with one of tri- kinds of elements of B or two kinds, " content of the acid additive in terms of tri- kinds of elements of F, P and B " is also included
Such case, only removing naturally not includes that usually First Astronautic Research Institute for Measurement and Test states the content of acid additive to that member.
According to the present invention, the type of the carrier can be the conventional selection of this field, for example, can be aluminium oxide,
It can be the mixture of at least one of aluminium oxide and silica, titanium oxide and zirconium oxide.Wherein, the aluminium oxide for example can be with
For at least one of gama-alumina, η-aluminium oxide, θ-aluminium oxide, δ-aluminium oxide and χ-aluminium oxide.In addition, the carrier can
Think cloverleaf pattern, butterfly, cylinder, hollow cylindrical, quatrefoil, five shapes such as leaf, spherical.
According to the present invention, the hydrogenation protecting agent can also contain the adjuvant component of other this fields routine, such as Si.
The present invention also provides the preparation methods of above-mentioned hydrogenation protecting agent, this method comprises:
(1) carrier Jing Guo hydro-thermal process is provided with to the metal promoter chemical combination of the metal promoter in alkaline containing
It is impregnated in first solution of object, is then dried, obtain the carrier that load has the metal promoter；
(2) carrier of the metal promoter helps in acid containing the acidity for being provided with the acid additive above-mentioned load
It is impregnated in second solution of immunomodulator compounds, is then dried and roasts, obtain the modified hydrogen at-ing catalyst carrier；
(3) the modified hydrogen at-ing catalyst carrier is molten in the third containing the compound for being provided with the active metal component
It is impregnated in liquid, is then dried and roasts.
According to the present invention, the modified hydrogen at-ing catalyst carrier has been made in above-mentioned steps (1) and (2).
Wherein, in step (1), although as long as the carrier is first carried out hydro-thermal process before carried metal auxiliary agent
(carrier is added to the water and is heated), and for alkalinity and will be incited somebody to action containing the control of the solution of metal promoter compound
Metal promoter and acid additive can be realized along the diameter of the carrier for acidity in solution control containing acid additive compound
It is in layer distributed to direction, but in order to further increase the controllability of preparation process and repeatability, it is preferable that the hydro-thermal process
Condition include: temperature be 50-200 DEG C (further preferably 60-180 DEG C, more preferably 70-150 DEG C), the time be 5-30 it is small
When (further preferably 8-28 hours, more preferably 10-24 hours).
Wherein, the metal promoter and the acid additive are as hereinbefore defined, the metal promoter compound and
Acid additive compound is also as hereinbefore defined, and details are not described herein.
Wherein, first solution is alkaline, can be made using the alkaline matter of this field routine described first molten
Liquid is in alkalinity, such as can use one of ammonium hydroxide, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate etc. or a variety of, comes
So that first solution is alkalinity.Under preferable case, the pH value of first solution is 7.5-11, more preferably 8-11.
Wherein, second solution is acid, and the usual acid additive compound enables to second solution
In acidity, but when second solution does not show as acidity, institute can be made using the acidic materials of this field routine
The second solution is stated in acidity, such as one of hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid etc. or a variety of can be used.Under preferable case,
The pH value of second solution is 2-6.5, more preferably 4-6.
The present invention is not particularly limited the type of solvent in first solution, can for it is existing it is various can be in alkali
Property under the conditions of dissolve the inertia liquid of the metal promoter compound, for example, can be selected from water, alcohol (such as methanol, ethyl alcohol
Deng), ether (such as ether), one of aldehyde (such as formaldehyde) and ketone (such as acetone) or a variety of.In addition, in first solution
Metal promoter compounds content can be 10-20 grams per liter.
The present invention is not particularly limited the type of solvent in second solution, can for it is existing it is various can be in acid
Property under the conditions of dissolve the inertia liquid of the acid additive compound, for example, can be selected from water, alcohol (such as methanol, ethyl alcohol
Deng), ether (such as ether), one of aldehyde (such as formaldehyde) and ketone (such as acetone) or a variety of.In addition, described contain the second solution
Middle acid additive compounds content can be 10-20 grams per liter.
According to the present invention, described in the preparation process for the modified hydrogen at-ing catalyst carrier that step (1) and (2) provide
In the modified hydrogen at-ing catalyst carrier that the dosage of carrier and the first solution and the second solution makes, with the modified hydrogenation catalyst
On the basis of the total weight of agent carrier, the content of the metal promoter in terms of metal oxide is preferably 0.1-15 weight %, into
One step is preferably 0.2-12 weight %, more preferably 0.3-8 weight %, most preferably 1-3 weight %；With tri- kinds of elements of F, P and B
The content of the acid additive of meter is preferably 0.1-15 weight %, further preferably 0.2-12 weight %, more preferably
0.3-8 weight %, most preferably 1-2 weight %.
The type of the carrier can be the conventional selection of this field, for example, can be aluminium oxide, or aluminium oxide
With the mixture of at least one of silica, titanium oxide and zirconium oxide.Wherein, the aluminium oxide for example can for gama-alumina,
At least one of η-aluminium oxide, θ-aluminium oxide, δ-aluminium oxide and χ-aluminium oxide.Above-mentioned carrier can be commercially available,
It can be according to well known to a person skilled in the art various methods to be prepared.For example, alumina support can be by by aluminium oxide
Precursor roasting, make its be converted into gama-alumina, η-aluminium oxide, θ-aluminium oxide, δ-aluminium oxide and χ-aluminium oxide at least one
Kind obtains.Optionally, before firing and/or later, first aluminium oxide precursor can be formed, is suitble to practical behaviour to prepare
Shape (such as spherical shape, sheet, bar shaped) required for making.The molding can be carried out according to the method for this field routine, such as be rolled
Ball, pressed disc method and extrusion method etc..In forming process, such as during extruded moulding, in order to guarantee it is molding smoothly into
Row, can be added water, extrusion aid and/or peptizing agent, and be optionally added expanding agent into the aluminium oxide precursor, then squeeze out
Molding, is dried later and roasts.The extrusion aid, the type of peptizing agent and expanding agent and dosage are those skilled in the art
It is known, for example, common extrusion aid can be in sesbania powder, methylcellulose, starch, polyvinyl alcohol and polyethanol at least
One kind, the peptizing agent can be organic acid and/or organic acid, and the expanding agent can be starch, synthetic cellulose, polymeric alcohol
At least one of with surfactant.Wherein, the synthetic cellulose is preferably hydroxymethyl cellulose, methylcellulose, second
At least one of base cellulose and hydroxyl fiber fat alcohol polyethylene ether.The polymeric alcohol is preferably polyethylene glycol, poly- propyl alcohol
At least one of with polyvinyl alcohol.The surfactant is preferably fat alcohol polyethylene ether, fatty alkanol amide and its derivative
At least one of object, the propylene alcohol copolymer that molecular weight is 200-10000 and maleic acid copolymer.Item drying will be squeezed out
Condition generally includes: drying temperature can be 40-350 DEG C, preferably 100-200 DEG C；Drying time can be 1-24 hours, excellent
It is selected as 2-12 hours.The condition of extrusion item roasting after drying is generally included: maturing temperature can be 350-1000 DEG C, preferably
It is 600-950 DEG C；Calcining time can be 1-10 hours, preferably 2-6 hours.In addition, the aluminium oxide precursor can be selected
From at least one of hibbsite, monohydrate alumina, amorphous hydroted alumina etc..The carrier can be clover
Shape, butterfly, cylinder, hollow cylindrical, quatrefoil, five shapes such as leaf, spherical.
According to the present invention, the condition of dipping described in step (1) and step (2) is not particularly limited, two steps
Immersion condition can be identical or different, as long as metal promoter and acid additive is enabled to load on the carrier, example
Such as, it is 20-300 DEG C (preferably 40-100 DEG C, more preferably 40-80 DEG C) that the condition of dipping, which includes: temperature, and the time is that 1-20 is small
When (preferably 1-6 hours, more preferably 1-3 hours).
The above dipping can be carried out using the dipping method of this field routine, for example, can be excessive liquid dipping, hole is satisfied or
Method infusion process.
According to the present invention, drying described in step (1) and step (2) can be vacuum drying.The condition of the drying is equal
Can be the conventional selection of this field, for example, in step (1), dry condition may include: temperature be 30-300 DEG C (preferably
It is 50-300 DEG C, more preferably 100-250 DEG C), the time is that (preferably 2-18 hours, more preferably 3-10 was small in 1-20 hours
When).
For example, in step (2), dry condition may include: temperature be 80-200 DEG C (preferably 80-180 DEG C, it is more excellent
It is selected as 80-150 DEG C), the time is 1-10 hours (preferably 2-8 hours, more preferably 2-6 hours).
According to the present invention, the present invention is not particularly limited the condition of the roasting in step (2), for example, step (2)
In, the condition of roasting includes: that temperature is 300-900 DEG C (preferably 300-800 DEG C, more preferably 400-600 DEG C), time 1-
10 hours (preferably 2-8 hours, more preferably 2-6 hours).
According to the present invention, in step (3), the compound of the offer active metal component including metal oxide
Described as described above, details are not described herein.The modified hydrogen at-ing catalyst carrier and the offer activity gold
The dosage for belonging to the compound of component makes in resulting hydrogenation protecting agent, in terms of metal oxide and with protectant gross weight
On the basis of amount, the content of the group VIII metal component is greater than 0 weight % and is less than or equal to 1 weight %, the group VIB gold
The content for belonging to component is greater than 0 weight % and is less than or equal to 6 weight %.Preferably, the modified hydrogen at-ing catalyst carrier and described
The dosage for providing the compound of the active metal component makes in resulting hydrogenation protecting agent, in terms of metal oxide and with institute
On the basis of stating protectant total weight, the content of the group VIII metal component is 0.1-0.9 weight %, the group VIB
The content of metal component is 0.1-5 weight %.
According to the present invention, the solvent in the third solution can be the various solvents of this field routine, such as can be
One of water, alcohol (such as methanol, ethyl alcohol etc.), ether (such as ether), aldehyde (such as formaldehyde) and ketone (such as acetone) are a variety of.
According to the present invention, to the dipping in step (3), there is no particular limitation, can be living using the load of this field routine
Property metal component immersion condition, for example, in step (3), it is 15-40 DEG C that the condition of dipping, which may include: temperature, time 1-
6 hours.The dipping can be carried out using the dipping method of this field routine, such as can be that excessive liquid dipping, hole is full or method is soaked
Stain method.
According to the present invention, to the drying in step (3), there is no particular limitation, can be soaked using the conventional drying in this field
After stain plus hydrogen carrier condition, for example, in step (3), dry condition may include: temperature be 100-250 DEG C (preferably
100-140 DEG C), the time is 1-10 hours (preferably 1-6 hours).
According to the present invention, to the roasting in step (3), there is no particular limitation, hydrogen can be added to protect using this field routine
The roasting condition of agent is protected, for example, the condition of roasting may include: that temperature is 360-500 DEG C of (preferably 360- in step (3)
450 DEG C), the time is 1-10 hours (preferably 2-6 hours).
According to the present invention, above-mentioned preparation method can also include that hydrogenation protecting agent is loaded helping for upper other this fields routine
Agent component, such as Si.Such adjuvant component can be introduced into the hydrogenation protecting agent in the method for this field routine, such as can
With the introducing when preparing carrier, can the introducing when preparing modified hydrogen at-ing catalyst carrier, can be in supported active metals component
When introduce, alternatively, before supported active metals component, individually by the solution containing the compound for being provided with adjuvant component and modification
Catalyst carrier for hydrgenating carries out immersive contact, and (dipping, dry and roasting condition can be using above for the mode of drying and roasting
In the condition recorded of any one place carry out), to this present invention, there is no particular limitation.
The present invention also provides application of the above-mentioned hydrogenation protecting agent in heavy-oil hydrogenation processing.
The process of the heavy-oil hydrogenation processing is the process of this field routine, wherein the hydrotreating reaction condition example
It such as can be with are as follows: temperature is 300-550 DEG C (preferably 330-480 DEG C), and hydrogen partial pressure is 4-20MPa (preferably 6-18MPa), volume
Air speed is 0.1-3h-1(preferably 0.15-2h-1), hydrogen to oil volume ratio 200-2500 (preferably 300-2000).
Wherein, the device of the hydrotreating can it is any be enough to make feedstock oil at hydrotreating reaction conditions with add
It is carried out in the catalytic reactor of hydrogen protective agent, for example, anti-in the fixed bed reactors, moving-burden bed reactor or ebullated bed
It answers in device and carries out.
According to the conventional method in this field, the hydrogenation protecting agent before the use, usually can in presence of hydrogen,
Presulfurization is carried out with sulphur, hydrogen sulfide or containing sulfur feedstock at a temperature of 140-370 DEG C, this presulfurization can carry out outside device
In-situ sulphiding in device, the active metal component that it is loaded is converted into metal sulfide component.
Hydrogenation protecting agent provided by the invention can be used alone, and can also use with other catalyst combinations, the present invention
The hydrogenation protecting agent of offer can heavy-oil hydrogenation processing application in obtain higher and comprehensive metal removal rate, so as to for
Subsequent technique (such as catalytic cracking process) provides qualified feedstock oil.Also, protective agent provided by the invention is at heavy-oil hydrogenation
There is lower coke content, so as to extend the operation cycle of device after reason.
The present invention will be described in detail by way of examples below.
In following embodiment and comparative example, the distribution of metal promoter and acid additive and the thickness use of shell and stratum nucleare
SEM-EDX method is measured, wherein shell thickness refers to the thickness of the part distribution factor σ >=2 of metal promoter, stratum nucleare thickness
Refer to the thickness of 1 part 0.5≤σ of distribution factor < of acid additive.
Wherein, the content of active metal component uses Xray fluorescence spectrometer measurement (all appts is Japanese in catalyst
3271 type Xray fluorescence spectrometer of Liue electrical machinery Industrial Co., Ltd, specific method are shown in petrochemical analysis method RIPP133-
90)。
Preparation example 1
Weighing the dry glue powder that 1000 grams of Chang Ling catalyst plants produce, (butt is 71 weight %, wherein boehmite content
For 68 weight %, hibbsite content is 5 weight %, and surplus is amorphous alumina) and 30 grams of sesbania powder (Henan Lankao
Sesbania gum factory product) and be uniformly mixed, the aqueous solution of 1200 milliliters of nitric acid containing 28g is added later, is squeezed on plunger type bar extruder
The cylindrical bar for being 1.8mm at outer diameter.Then cylindrical bar wet bar is 4 hours dry at 120 DEG C, 3 are roasted at 960 DEG C
Hour, obtain carrier Z.It is obtained using BET method measurement, the Kong Rongwei 0.7mL/g of carrier Z, specific surface area 100m2/g。
Embodiment 1
The present embodiment is for illustrating hydrogenation protecting agent and preparation method thereof of the invention.
(1) the carrier Z for taking 200 grams of preparation examples 1 to prepare, first by carrier in 135 DEG C hydro-thermal process 12 hours, then will be through hydro-thermal
165 milliliters of temperature of carrier that treated are 40 DEG C containing 15 grams per liter Mg (NO3)2Aqueous solution (pH value 11) saturation dipping 1
Hour, it is 8 hours dry in 200 DEG C later, obtain the carrier that load has metal promoter；
(2) by obtained in step (1) load have the carrier of metal promoter 145 milliliters of temperature be 40 DEG C containing 10 grams/
Rise H3BO3Aqueous solution (pH value 6) in dipping 1 hour, it is then 3 hours dry in 120 DEG C, roast 3 hours, obtain then at 400 DEG C
To modified hydrogen at-ing catalyst carrier S Z1.
(3) 200 grams of carrier S Z1 are taken, with 210 milliliters of molybdenum oxides and basic cobaltous carbonate mixed solution (wherein, with MoO3Meter
The concentration of Mo element is 50 grams per liters, and the concentration of the Co element in terms of CoO is 10.3 grams per liters, and solvent is water) in room temperature (about 25
DEG C) under impregnate 1 hour, in 120 DEG C dry 2 hours, 420 DEG C roast 3 hours, obtain protective agent CSZ1.In protective agent CSZ1
The content of molybdenum oxide and cobalt oxide is listed in table 3.
Embodiment 2
The present embodiment is for illustrating hydrogenation protecting agent and preparation method thereof of the invention.
(1) the carrier Z for taking 200 grams of preparation examples 1 to prepare, first by carrier in 120 DEG C hydro-thermal process 20 hours, then will be through hydro-thermal
155 milliliters of temperature of carrier that treated are 50 DEG C containing 12 grams per liter KNO3Aqueous solution (pH value 10) saturation dipping it is 1 small
When, it is 6 hours dry in 100 DEG C later, obtain the carrier that load has metal promoter；
(2) by obtained in step (1) load have the carrier of metal promoter 135 milliliters of temperature be 50 DEG C containing 12 grams/
Rise H3PO4Aqueous solution (pH value 2) in dipping 1 hour, it is then 3 hours dry in 120 DEG C, roast 3 hours, obtain then at 400 DEG C
To modified hydrogen at-ing catalyst carrier S Z2.
(3) 200 grams of carrier S Z2 are taken, with 210 milliliters of molybdenum oxides and basic nickel carbonate mixed solution (wherein, with MoO3Meter
The concentration of 50 grams per liter of concentration of Mo element, the Ni element in terms of NiO is 10.3 grams per liters, and solvent is water) in room temperature (about 25 DEG C)
Lower dipping 1 hour is dried 2 hours in 120 DEG C, and 420 DEG C roast 3 hours, obtain protective agent CSZ2.Oxidation in protective agent CSZ2
The content of molybdenum and nickel oxide is listed in table 3.
Embodiment 3
The present embodiment is for illustrating hydrogenation protecting agent and preparation method thereof of the invention.
(1) the carrier Z for taking 200 grams of preparation examples 1 to prepare, first by carrier in 70 DEG C hydro-thermal process 24 hours, then will be through hydro-thermal
165 milliliters of temperature of carrier that treated are 80 DEG C containing 15 grams per liter Ca (NO3)2Aqueous solution (pH value 8) saturation dipping it is 1 small
When, it is 8 hours dry in 200 DEG C later, obtain the carrier that load has metal promoter；
(2) by obtained in step (1) load have the carrier of metal promoter 145 milliliters of temperature be 80 DEG C containing 10 grams/
Dipping 1 hour in the aqueous solution (pH value 4) of hydrofluoric acid is risen, it is then 3 hours dry in 120 DEG C, it is roasted 3 hours then at 400 DEG C,
Obtain modified hydrogen at-ing catalyst carrier S Z3.
(3) 200 grams of carrier S Z3 are taken, with 210 milliliters of molybdenum oxides and basic nickel carbonate mixed solution (wherein, with MoO3Meter
The concentration of Mo element is 25 grams per liters, and the concentration of the Ni element in terms of NiO is 5.3 grams per liters, and solvent is water) in room temperature (about 25 DEG C)
Lower dipping 1 hour is dried 2 hours in 120 DEG C, and 420 DEG C roast 3 hours, obtain protective agent CSZ3.Oxidation in protective agent CSZ3
The content of molybdenum and nickel oxide is listed in table 3.
Embodiment 4
The present embodiment is for illustrating hydrogenation protecting agent and preparation method thereof of the invention.
According to the method for embodiment 1, unlike, in step (1), (NO containing Mg3)2Aqueous solution pH value be 7.5, step
Suddenly (2) obtain modified hydrogen at-ing catalyst carrier S Z4.
(3) 200 grams of carrier S Z4 are taken, with 210 milliliters of molybdenum oxides and basic cobaltous carbonate mixed solution (wherein, with MoO3Meter
The concentration of Mo element is 12 grams per liters, and the concentration of the Co element in terms of CoO is 3.5 grams per liters, and solvent is water) in room temperature (about 25 DEG C)
Lower dipping 1 hour is dried 2 hours in 120 DEG C, and 420 DEG C roast 3 hours, obtain protective agent CSZ4.Oxidation in protective agent CSZ4
The content of molybdenum and cobalt oxide is listed in table 3.
Embodiment 5
The present embodiment is for illustrating hydrogenation protecting agent and preparation method thereof of the invention.
According to the method for embodiment 1, step (1) is identical, unlike, in step (2), contain H3BO3Aqueous solution pH value
It is 6.5, obtains modified hydrogen at-ing catalyst carrier S Z5.
(3) 200 grams of carrier S Z5 are taken, with 210 milliliters of molybdenum oxides and basic nickel carbonate mixed solution (wherein, with MoO3Meter
The concentration of Mo element is 30 grams per liters, and the concentration of the Ni element in terms of NiO is 5.1 grams per liters, and solvent is water) in room temperature (about 25 DEG C)
Lower dipping 1 hour is dried 2 hours in 120 DEG C, and 420 DEG C roast 3 hours, obtain protective agent CSZ5.Oxidation in protective agent CSZ5
The content of molybdenum and nickel oxide is listed in table 3.
Comparative example 1
(1) the carrier Z for taking 200 grams of preparation examples 1 to prepare is 120 DEG C containing 28 grams per liter Mg (NO with 160 milliliters of temperature3)2's
Aqueous solution (pH value 11) impregnates 1 hour, dries 8 hours then at 200 DEG C, then roasts 3 hours at 400 DEG C, obtain reference and change
Property catalyst carrier for hydrgenating DZ1.
According to the method for (3) the step of embodiment 1, the difference is that carrier S Z1 is substituted using carrier DZ1, to be protected
Protect agent CDZ1.The content of molybdenum oxide and cobalt oxide in protective agent CDZ1 is listed in table 3.
Comparative example 2
(1) the carrier Z for taking 200 grams of preparation examples 1 to prepare is 105 DEG C containing 25 grams per liter H with 155 milliliters of temperature3BO3It is molten
Liquid (pH value 6) impregnates 1 hour, dries then at 120 DEG C 4 hours, then roasts 3 hours at 400 DEG C, obtains that reference is modified plus hydrogen
Catalyst carrier DZ2.
According to the method for (3) the step of embodiment 2, carrier S Z2 is substituted using carrier DZ2, to obtain protective agent CDZ2.
The content of molybdenum oxide and nickel oxide in protective agent CDZ2 is listed in table 3.
Comparative example 3
Modified hydrogen at-ing catalyst carrier is prepared according to the method for (1) the step of embodiment 1 and (2), unlike, do not include
By carrier Z at 135 DEG C the step of hydro-thermal process 12 hours, but directly by the carrier Z of non-hydrothermal treatment (NO containing Mg3)2
Aqueous solution carry out saturation dipping, obtain reference modified hydrogen at-ing catalyst carrier DZ3.
According to the method for (3) the step of embodiment 3, the difference is that, carrier S Z3 is substituted using carrier DZ3, to be protected
Protect agent CDZ3.The content of molybdenum oxide and nickel oxide in protective agent CDZ3 is listed in table 3.
Comparative example 4
Modified hydrogen at-ing catalyst carrier is prepared according to the method for (1) the step of embodiment 1 and (2), unlike, contain Mg
(NO3)2Aqueous solution be in neutrality (pH value 7), obtain reference modified hydrogen at-ing catalyst carrier DZ4.
According to the method for (3) the step of embodiment 4, the difference is that, carrier S Z4 is substituted using carrier DZ4, to be protected
Protect agent CDZ4.The content of molybdenum oxide and cobalt oxide in protective agent CDZ4 is listed in table 3.
Comparative example 5
Modified hydrogen at-ing catalyst carrier is prepared according to the method for (1) the step of embodiment 1 and (2), unlike, contain H3BO3
Aqueous solution be in neutrality (pH value 7), obtain reference modified hydrogen at-ing catalyst carrier DZ5.
According to the method for (3) the step of embodiment 5, the difference is that, carrier S Z5 is substituted using carrier DZ5, to be protected
Protect agent CDZ5.The content of molybdenum oxide and nickel oxide in protective agent CDZ5 is listed in table 3.
Test case 1
Using SEM-EDX method to the thickness of Elemental redistribution and shell and stratum nucleare in modified hydrogen at-ing catalyst carrier granular
It is analyzed.Since the counting rate in SEM-EDX characterization result along carrier radial direction every bit is corresponded to each other with the point element content,
Although the size of counting rate may not represent the real content of the point element, the size of counting rate reflects the point element content
Just.Therefore, in order to indicate each element along carrier radial direction the regularity of distribution introduce distribution factor σ.Indicate auxiliary agent in particle with σ
On one position with the ratio between concentration at center (R is particle radius, using at modified hydrogen at-ing catalyst carrier granular center as starting point).Certain
Concentration is certain average value for putting (position deviation≤20nm) 20 numerical point counting rates nearby on one position；During concentration is at center
The average value of (position deviation≤20nm) 20 numerical point counting rates near heart point.If σ > 1, show that the point element content is higher than
At modified hydrogen at-ing catalyst carrier granular center；If σ=1, show the point element content and modified hydrogen at-ing catalyst carrier
It is identical at grain center；If σ < 1, show that the point element content is less than at modified hydrogen at-ing catalyst carrier granular center.Table 1 is to change
The relevant parameter of property catalyst carrier for hydrgenating, wherein the content of auxiliary agent is calculated according to inventory.Table 2 is that modified plus hydrogen is urged
The distribution factor of agent carrier at different locations.
Table 1
Table 2
| Number | SZ1 | SZ2 | SZ3 | SZ4 | SZ5 | DZ1 | DZ2 | DZ3 | DZ4 | DZ5 |
| R(mm) | 0.9 | 0.9 | 0.9 | 0.9 | 0.9 | 0.9 | 0.9 | 0.9 | 0.9 | 0.9 |
| σMg(R) | 2.58 | 1.97 | 2.81 | 1.04 | 1 | 1 | 2.69 | |||
| σMg(2/3R) | 1.96 | 1.65 | 2.01 | 0.98 | 1 | 1 | 1.88 | |||
| σMg(1/3R) | 1.35 | 1.35 | 1.57 | 1.02 | 1 | 1 | 1.63 | |||
| σK(R) | 2.54 | |||||||||
| σK(2/3R) | 2.13 | |||||||||
| σK(1/3R) | 1.52 | |||||||||
| ΣCa(R) | 2.79 | |||||||||
| ΣCa(2/3R) | 2.30 | |||||||||
| ΣCa(1/3R) | 1.16 | |||||||||
| σP(R) | 0.18 | |||||||||
| σP(2/3R) | 0.41 | |||||||||
| σP(1/3R) | 0.70 | |||||||||
| σB(R) | 0.25 | 0.21 | 0.36 | 0.99 | 1 | 0.33 | 1 | |||
| σB(2/3R) | 0.38 | 0.39 | 0.45 | 1.03 | 1 | 0.46 | 1 | |||
| σB(1/3R) | 0.89 | 0.91 | 0.49 | 0.96 | 1 | 0.92 | 1 | |||
| σF(R) | 0.31 | |||||||||
| σF(2/3R) | 0.45 | |||||||||
| σF(1/3R) | 0.87 |
By upper table 1 and 2 as can be seen that modified catalyst supports provided by the invention include carrier and are supported on the load
Metal promoter and acid additive on body, the metal promoter and acid additive are in layer distributed, shell on the carrier
For metal promoter, stratum nucleare is acid additive.
Table 3
Test case 2
The particle that above-mentioned hydrogenation protecting agent is broken into 2-3 millimeters of diameter is packed into heavy-oil hydrogenation fixed bed reactors respectively.
Reaction condition are as follows: 380 DEG C of reaction temperature, hydrogen partial pressure 14MPa, using inductive coupling plasma emission spectrograph (ICP-AES)
(instrument is U.S. PE company PE-5300 type plasma light quantity to the content of Ni, V and Fe in the oil of measurement hydrotreating front and back
Meter, specific method are shown in petrochemical analysis method RIPP124-90).Asphalitine and metal removal rate are calculated according to the following formula:
Protectant coke content is using the coke content after infrared absorption determining reaction on protective agent.
Feedstock oil be Ni constituent content be 54.3ppm, V element content is that 3.8ppm, Fe constituent content are 24.7ppm, Ca
Constituent content is the Shengli VR of 127ppm.
Table 4
| Protective agent | De- Ni rate % | De- V rate % | De- Fe rate % | De- Ca rate % | Coke content % |
| CSZ1 | 80.1 | 71.3 | 90.1 | 93.1 | 8.5 |
| CSZ2 | 81.1 | 70.2 | 89.9 | 92.6 | 8.8 |
| CSZ3 | 80.6 | 71.8 | 88.9 | 90.5 | 9.5 |
| CSZ4 | 78.3 | 69.1 | 87.5 | 89.6 | 10.3 |
| CSZ5 | 79.1 | 70 | 88.3 | 87.5 | 10 |
| CDZ1 | 76.6 | 68.4 | 86.7 | 86.1 | 11.3 |
| CDZ2 | 77.1 | 67.8 | 85.2 | 86.1 | 12.4 |
| CDZ3 | 77.1 | 65.9 | 83.4 | 85.7 | 13.6 |
| CDZ4 | 75.4 | 60.8 | 80.7 | 81.6 | 13.4 |
| CDZ5 | 76.3 | 62.8 | 81.9 | 83.4 | 14.5 |
From the results shown in Table 4, providing hydrogenation protecting agent by the present invention has preferable and comprehensive metal removal
Activity and it is not easy carbon distribution, wherein de- Ni rate can reach 78% or more, preferably can reach 80% or more；De- V rate can reach 69% with
On, it preferably can reach 70% or more；De- Fe rate can reach 87% or more, preferably can reach 88.5% or more；De- Ca rate can reach
87% or more, it preferably can reach 90% or more；As it can be seen that hydrogenation protecting agent provided by the present application can not only obtain higher metal
Removal effect, it is more praiseworthy, it enables to such as Ni, V, Fe and Ca various metals while all there is preferable removing effect
Fruit, to have the ability of removing metal comprehensively.In addition, the hydrogenation protecting agent of the application is not easy to form carbon distribution, in test case 2
Under hydroconversion condition, carbon deposition quantity can achieve 10.5% hereinafter, it is preferred that can achieve 9.5% or less.To provided by the invention
The great prospects for commercial application of hydrogenation protecting agent.
The preferred embodiment of the present invention has been described above in detail, still, during present invention is not limited to the embodiments described above
Detail within the scope of the technical concept of the present invention can be with various simple variants of the technical solution of the present invention are made, this
A little simple variants all belong to the scope of protection of the present invention.
It is further to note that specific technical features described in the above specific embodiments, in not lance
In the case where shield, can be combined in any appropriate way, in order to avoid unnecessary repetition, the present invention to it is various can
No further explanation will be given for the combination of energy.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally
The thought of invention, it should also be regarded as the disclosure of the present invention.
Claims (19)
1. a kind of hydrogenation protecting agent, the protective agent contain active metal component and modified hydrogen at-ing catalyst carrier, which is characterized in that
The modified hydrogen at-ing catalyst carrier includes the metal promoter and acid additive of carrier and load on the carrier, the metal
Auxiliary agent and acid additive are in layer distributed on the carrier, and shell is metal promoter, and stratum nucleare is acid additive, the metal promoted
Agent is group ia metal component and/or group iia metal component, and the acid additive is selected from least one of F, P and B group
Point；And
The active metal component contains at least one group VIII metal component and at least one vib metals component, with
The content of metal oxide meter and on the basis of protectant total weight, the group VIII metal component is greater than 0 weight
It measures % and is less than or equal to 1 weight %, the content of the vib metals component is greater than 0 weight % and is less than or equal to 6 weight %.
2. hydrogenation protecting agent according to claim 1, wherein in terms of metal oxide and with protectant total weight
On the basis of, the content of the group VIII metal component is 0.1-0.9 weight %, and the content of the vib metals component is
0.1-5 weight %.
3. hydrogenation protecting agent according to claim 2, wherein the group VIII metal component is selected from Co and/or Ni, the
Group vib metal component is selected from Mo and/or W.
4. hydrogenation protecting agent described in any one of -3 according to claim 1, wherein the modified hydrogen at-ing catalyst carrier
In, the shell with a thickness of 0.1-5mm, the stratum nucleare with a thickness of 0.1-5mm.
5. hydrogenation protecting agent described in any one of -3 according to claim 1, wherein with the modified hydrogen at-ing catalyst carrier
Total weight on the basis of, the content of the metal promoter in terms of metal oxide is 0.1-15 weight %, with tri- kinds of F, P and B
The content of the acid additive of element meter is 0.1-15 weight %.
6. hydrogenation protecting agent described in any one of -3 according to claim 1, wherein the carrier is aluminium oxide or oxidation
The mixture of at least one of aluminium and silica, titanium oxide and zirconium oxide；The aluminium oxide is gama-alumina, η-aluminium oxide, θ-
At least one of aluminium oxide, δ-aluminium oxide and χ-aluminium oxide.
7. the preparation method of hydrogenation protecting agent described in any one of claim 1-6, which is characterized in that this method comprises:
(1) carrier Jing Guo hydro-thermal process is provided with the metal promoter compound of the metal promoter in alkaline containing
It is impregnated in first solution, is then dried, obtain the carrier that load has the metal promoter；
(2) there is the carrier of the metal promoter acid containing the acid additive for being provided with the acid additive above-mentioned load
It closes and is impregnated in the second solution of object, be then dried and roast, obtain the modified hydrogen at-ing catalyst carrier；
(3) by the modified hydrogen at-ing catalyst carrier in the third solution containing the compound for being provided with the active metal component
It is impregnated, is then dried and roasts.
8. according to the method described in claim 7, wherein, the pH value of first solution is 7.5-11.
9. according to the method described in claim 8, wherein, the pH value of second solution is 2-6.5.
10. the method according to any one of claim 7-9, wherein in step (1), the condition of the hydro-thermal process
Include: temperature be 50-200 DEG C, the time be 5-30 hours.
11. according to the method described in claim 10, wherein, the immersion condition of step (1) and (2) is identical or different, dipping
Condition includes: that temperature is 20-300 DEG C；Time is 1-20 hours.
12. according to the method for claim 11, wherein the condition of dipping includes: that temperature is 40-100 DEG C；Time is 1-6
Hour.
13. in step (1), dry condition includes: that temperature is 30-300 DEG C according to the method described in claim 10, wherein,
Time is 1-20 hours.
14. in step (2), dry condition includes: that temperature is 80-200 DEG C according to the method described in claim 10, wherein,
Time is 1-10 hours.
15. according to the method described in claim 10, wherein, in step (2), the condition of roasting includes: that temperature is 300-900
DEG C, the time is 1-10 hours.
16. the method according to any one of claim 7-9 and 11-15, wherein in step (3), the item of the dipping
Part includes: that temperature is 15-40 DEG C, and the time is 1-6 hours.
17. according to the method for claim 16, wherein in step (3), dry condition includes: that temperature is 100-250
DEG C, the time is 1-10 hours.
18. according to the method for claim 16, wherein in step (3), the condition of roasting includes: that temperature is 360-500
DEG C, the time is 1-10 hours.
19. application of the hydrogenation protecting agent described in any one of -6 in heavy-oil hydrogenation processing according to claim 1.
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