CN106622261B - A kind of removal of ccr by hydrotreating catalyst and its preparation method and application - Google Patents
A kind of removal of ccr by hydrotreating catalyst and its preparation method and application Download PDFInfo
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- CN106622261B CN106622261B CN201510724477.9A CN201510724477A CN106622261B CN 106622261 B CN106622261 B CN 106622261B CN 201510724477 A CN201510724477 A CN 201510724477A CN 106622261 B CN106622261 B CN 106622261B
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Abstract
The present invention relates to a kind of removal of ccr by hydrotreating catalyst, the catalyst contains active metal component and modified hydrogen at-ing catalyst carrier, the modified hydrogen at-ing catalyst carrier is made by following methods, this method comprises: repeatedly successively being impregnated and being dried the carrier Jing Guo hydro-thermal process, and the desciccate obtained for the last time is roasted.The present invention also provides the preparation method and application of above-mentioned removal of ccr by hydrotreating catalyst.By using the removal of ccr by hydrotreating catalyst of the application, the hetero atoms such as higher nitrogen, sulphur removal efficiency and carbon residue removal efficiency can be obtained in the application of heavy-oil hydrogenation processing；Asphaltene removal effect also with higher simultaneously.
Description
Technical field
The present invention relates to a kind of removal of ccr by hydrotreating catalyst and its preparation method and application.
Background technique
It is the important reaction during residual hydrogenation that heavy-oil hydrogenation, which takes off carbon residue reaction, and the conversion ratio of carbon residue is residual hydrogenation work
One important indicator of skill.The high raw material of carbon residue can largely effect on the stable operation of heavy oil catalytically cracking equipment (RFCC device)
Property and product distribution.Reducing residual hydrogenation equipment and generating the carbon residue of oil will be helpful to improve residual hydrogenation and catalytic cracking combined
The economic benefit of device.
Carbon residue and condensed-nuclei aromatics content more than five rings in heavy oil and five rings are closely related.The forerunner owner of usual carbon residue
If being made of biggish condensed-nuclei aromatics in asphalitine and colloid.The essence of the de- carbon residue of residual hydrogenation is exactly the forerunner to carbon residue
Object is handled, and carbon residue precursor compound is reduced, and is reacted similar with the lighting of residual oil reaction.Therefore, catalyst is improved
Heavy-oil hydrogenation takes off carbon residue ability, other than improving catalyst to the hydrogenation capability of carbon residue predecessor, it is also necessary to properly increase catalysis
The acidity of agent is to promote being hydrocracked and open loop, isomerization reaction for macromolecular.
Summary of the invention
It is an object of the invention to overcome existing removal of ccr by hydrotreating catalyst that cannot have both preferable carbon residue removal activity
With the heteroatomic active defect such as denitrogenation, sulphur, providing one kind, can to have both preferable carbon residue removal activity and denitrogenation, sulphur etc. miscellaneous
Active removal of ccr by hydrotreating catalyst of atom and its preparation method and application.
To achieve the goals above, the present invention provides a kind of removal of ccr by hydrotreating catalyst, which contains active metal
Component and modified hydrogen at-ing catalyst carrier, wherein the modified hydrogen at-ing catalyst carrier is made by following methods, this method packet
Include: the carrier Jing Guo hydro-thermal process repeatedly successively impregnated and dried, and by the desciccate obtained for the last time into
Row roasting, wherein maceration extract used in each dipping process, which contains, is provided with identical or different acid additive compound, duplicate
Frequency n >=2, and as n >=3, during from (n-1)th dipping is impregnated into the 2nd time, dry temperature after impregnating each time
Than after adjacent preceding single-steeping, dry temperature is 20-150 DEG C high, and the dry time is more primary than before adjacent after impregnating each time
The dry time is 1-10 hours long after dipping；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 the total weight of the catalyst, the content of the group VIII metal component is 3-
15 weight %, the content of the vib metals component are 13-30 weight %.
The present invention also provides the preparation methods of above-mentioned removal of ccr by hydrotreating catalyst, this method comprises: the modification is added
Hydrogen catalyst carrier is impregnated in the solution containing the compound that is provided with the active metal component, be then dried and
Roasting.
The present invention also provides application of the above-mentioned removal of ccr by hydrotreating catalyst in heavy-oil hydrogenation processing.
By using the removal of ccr by hydrotreating catalyst of the application, can be obtained in the application of heavy-oil hydrogenation processing higher
The hetero atoms such as nitrogen, sulphur removal efficiency and carbon residue removal efficiency；Asphaltene removal effect also with higher simultaneously.
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 removal of ccr by hydrotreating catalyst, which contains active metal component and modified hydrogenation catalyst
Agent carrier, wherein the modified hydrogen at-ing catalyst carrier is made by following methods, this method comprises: will pass through hydro-thermal process
Carrier repeatedly successively impregnated and dried, and the desciccate obtained for the last time is roasted, wherein leaching every time
Maceration extract used in the process of stain, which contains, is provided with identical or different acid additive compound, duplicate frequency n >=2, and works as n >=3
When, during from (n-1)th dipping is impregnated into the 2nd time, dry temperature is than once soaking before adjacent after impregnating each time
Dry temperature is 20-150 DEG C high after stain, time of the dry time than drying after adjacent preceding single-steeping after impregnating each time
It is 1-10 hours long；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 the total weight of the catalyst, the content of the group VIII metal component is 3-
15 weight %, the content of the vib metals component are 13-30 weight %.
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 obtained the catalytic component of preferable denitrogenation, sulphur effect and de- carbon residue especially asphaltene removal,
In order to obtain the more excellent catalyst of property, under preferable case, in terms of metal oxide and with the total of the catalyst
On the basis of weight, the content of the group VIII metal component is 3.1-10 weight %.Under preferable case, the group VIB gold
The content for belonging to component is 13.1-28 weight %.
Wherein, the group VIII metal component refers to that the removal of ccr by hydrotreating catalyst in heavy-oil hydrogenation processing contains the
Group VIII metal element, or can be described as the group VIII metallic element having in modified hydrogen at-ing catalyst supported on carriers, make
It can be for group VIII metal component of the invention commonly used in as the removal of ccr by hydrotreating catalyst 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 removal of ccr by hydrotreating catalyst in heavy-oil hydrogenation processing contains
Vib metals element, or can be described as the vib metals element having in modified hydrogen at-ing catalyst supported on carriers, make
It can be for vib metals component of the invention commonly used in as the removal of ccr by hydrotreating catalyst in heavy-oil hydrogenation processing
The vib metals element of active metal component, under preferable case, vib metals group is selected from Mo and/or W.
According to the present invention, since the removal of ccr by hydrotreating catalyst is usually to have on modified hydrogen at-ing catalyst is carrier loaded
By prepared by roasting, therefore, above-mentioned active metal component is in the removal of ccr by hydrotreating catalyst after active metal component
In exist usually in the form of metal oxide, the present invention is also not limited to this certainly, and the active metal component can also be with
It is to exist in the form of the compound of the offer active metal component in addition to an oxide.
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.
Modified hydrogen at-ing catalyst carrier of the present invention is to be added as made from above-mentioned preparation process in the modification
In the preparation method of hydrogen catalyst carrier, the carrier after hydro-thermal process is negatively charged since density of surface hydroxyl increases, will
After it is immersed in maceration extract, the acid additive compound in maceration extract is easily enriched in the surface of carrier, and first time is soaked
After carrier drying after stain, density of surface hydroxyl is reduced, on carrier the position of hydroxy density maximum value along carrier radial direction
Direction is migrated toward carrier center, the acid additive chemical combination after being immersed in another maceration extract, in another maceration extract
Object, which is easy to be enriched in, is being impregnated into (n-1)th from the 2nd time as dipping time n >=3 positioned at the intracorporal hydroxy density maximum of load
It, can by temperature dry after control dipping with the dry time as dipping time gradually increases during secondary dipping
So that the position for carrying intracorporal hydroxy density maximum value is gradually migrated toward carrier center, and make to impregnate the dipping used every time in turn
Acid additive compound in liquid is adsorbed on the different location of carrier, and acid additive is finally obtained after roasting in layering
The modified hydrogen at-ing catalyst carrier of distribution.
According to the present invention, in the preparation method of the modified hydrogen at-ing catalyst carrier, the type of the carrier can be
The conventional selection of this field, for example, can be aluminium oxide, or in aluminium oxide and silica, titanium oxide and zirconium oxide extremely
A kind of few mixture.Wherein, the aluminium oxide for example can be gama-alumina, η-aluminium oxide, θ-aluminium oxide, δ-aluminium oxide
At least one of with χ-aluminium oxide.Above-mentioned carrier can be commercially available, can also be according to well known to those skilled in the art
Various methods be prepared.For example, alumina support can make it be converted into γ-oxygen by roasting aluminium oxide precursor
Change at least one of aluminium, η-aluminium oxide, θ-aluminium oxide, δ-aluminium oxide and χ-aluminium oxide and is prepared.Optionally, it is roasting
Before or after, first aluminium oxide precursor can be formed, with prepare shape required for being suitble to practical operation (as it is spherical,
Sheet, bar shaped etc.).The molding can be carried out according to the method for this field routine, such as rolling ball method, pressed disc method and extrusion method.
In forming process, such as during extruded moulding, in order to guarantee it is molding go on smoothly, can be to the aluminium oxide predecessor
Water, extrusion aid and/or peptizing agent are added in object, and is optionally added expanding agent, then extrusion molding is dried later and roasts
It burns.The extrusion aid, the type of peptizing agent and expanding agent and dosage are known to the skilled person, for example, common helping is crowded
Agent can be at least one of selected from sesbania powder, methylcellulose, starch, polyvinyl alcohol and polyethanol, and the peptizing agent can be with
For organic acid and/or organic acid, the expanding agent can in starch, synthetic cellulose, polymeric alcohol and surfactant extremely
Few one kind.Wherein, the synthetic cellulose is preferably hydroxymethyl cellulose, methylcellulose, ethyl cellulose and hydroxyl fiber
At least one of fat alcohol polyethylene ether.The polymeric alcohol be preferably in polyethylene glycol, poly- propyl alcohol and polyvinyl alcohol at least
It is a kind of.The surfactant is preferably fat alcohol polyethylene ether, fatty alkanol amide and its derivative, molecular weight 200-
At least one of 10000 propylene alcohol copolymer and maleic acid copolymer.The dry condition of item will be squeezed out to generally include: dry
Dry temperature can be 40-350 DEG C, preferably 100-200 DEG C；Drying time can be 1-24 hours, preferably 2-12 hours.It will
The condition of extrusion item roasting after drying generally includes: maturing temperature can be 350-1000 DEG C, preferably 600-950 DEG C；Roasting
Burning the time can be 1-10 hours, preferably 2-6 hours.In addition, the aluminium oxide precursor can selected from hibbsite,
At least one of monohydrate alumina, amorphous hydroted alumina etc..The carrier can for cloverleaf pattern, butterfly, cylinder,
Hollow cylindrical, quatrefoil, five shapes such as leaf, spherical.
According to the present invention, in the preparation method of the modified hydrogen at-ing catalyst carrier, the carrier needs first to carry out water
Heat treatment, the present invention is not particularly limited the condition of the hydro-thermal process, for example, the condition of the hydro-thermal process can wrap
Include: temperature is 50-200 DEG C (preferably 60-180 DEG C, more preferably 70-150 DEG C), and the time is 5-30 hours (preferably 8-28
Hour, more preferably 10-24 hours).
According to the present invention, it in the preparation method of the modified hydrogen at-ing catalyst carrier, needs the carrier of hydro-thermal process
It is repeatedly successively impregnated and is dried, wherein the type of acid additive compound in maceration extract used in each dipping process
May be the same or different, it is preferably different, the modified hydrogen at-ing catalyst carrier enabled in this way can converge it is a variety of not
The advantages of with acid additive.
According to the present invention, the type of the acid additive can be the conventional selection of this field, particularly preferably F, P and B
At least one of component.Although existing by F in the modified hydrogen at-ing catalyst carrier with simple substance form, P component and B group
It point is usually to exist in the form of its oxide, but the present invention is not limited thereto, and F, P and B as acid additive can also be with
To exist in the form of the acid additive compound for providing acid additive component.
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.
Under preferable case, in the modified hydrogen at-ing catalyst carrier, with the total weight of the modified hydrogen at-ing catalyst carrier
On the basis of, the content of the acid additive in terms of tri- kinds of elements of F, P and B is 0.1-15 weight %, more preferably 0.2-12 weight
% is measured, is still more preferably 0.3-8 weight %.Wherein, " content of the acid additive in terms of tri- kinds of elements of F, P and B "
Refer to that the weight of the acid additive is measured using the total weight of tri- kinds of elements of F, P and B as representative, wherein when the acid
When property auxiliary agent does not include one of tri- kinds of elements of F, P and B or two kinds, " acidity in terms of tri- kinds of elements of F, P and B is helped
The content of agent " also includes such case, and only removing naturally not includes that usually the First Astronautic Research Institute for Measurement and Test states acid additive to that member
Content.Therefore, the present invention preferably used by acid additive compound use so that, the acidity in modified hydrogen at-ing catalyst carrier
The content of auxiliary agent meets above-mentioned requirements.
According to the present invention, the type of solvent in the maceration extract is not particularly limited, can for it is existing it is various can
The inertia liquid of the acid additive compound is dissolved, for example, water, alcohol (such as methanol, ethyl alcohol etc.), ether can be selected from
At least one of (such as ether), aldehyde (such as formaldehyde) and ketone (such as acetone).In addition, every time in dipping maceration extract used
The content of acid additive compound may be the same or different, and be each independently 1-100 grams per liter, preferably 5-50
Grams per liter, more preferably 5-15 grams per liter.Further, the dosage of dipping maceration extract used can be identical every time, can also not
Together, and the carrier relative to 100g, the dosage for impregnating maceration extract used every time can be each independently 20-
200mL, preferably 50-100mL.The content range of such acid additive compound and the dosage of maceration extract can make above-mentioned
Modified hydrogen at-ing catalyst carrier in, on the basis of the total weight of the modified hydrogen at-ing catalyst carrier, with tri- kinds of members of F, P and B
Element meter the acid additive content be 0.1-15 weight %, more preferably 0.2-12 weight %, still more preferably for
0.3-8 weight %.
According to the present invention, in the preparation method of the modified hydrogen at-ing catalyst carrier, to the acid-base property of the maceration extract
It is not particularly limited, for example, maceration extract that can be acid, alkaline, neutral.Preferably, used by preceding n-1 dipping
Maceration extract is in acidity, and n-th impregnates used maceration extract in alkalinity.It is highly preferred that dipping used by preceding n-1 dipping
The pH value of liquid is 2-6.It is highly preferred that the pH value that n-th impregnates used maceration extract is 8-11.The present inventor's hair
It is existing, when by the acid-base property control of the maceration extract, layering of the more advantageous acid additive on carrier divides in the above preferred range
Cloth is more advantageous to raising catalysis so that the modified hydrogen at-ing catalyst carrier made is prepared into after removal of ccr by hydrotreating catalyst
Denitrogenation, sulphur activity, asphaltene removal activity and the raising carbon residue removal efficiency of agent.
Wherein, typically basic species are added into the maceration extract in the method that the maceration extract is adjusted to alkalinity
Matter, for example, at least one of ammonium hydroxide, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate etc..And contain in F, P and B at least
Maceration extract of compound a kind of itself may just present it is acid, can be with if not shown acid or acid degree is insufficient
Acidic materials (for example, at least one of hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid etc.) is added into the maceration extract with by the leaching
Stain liquid is adjusted to expected acidity.
According to the present invention, the number of the dipping can carry out reasonable according to obtained modified hydrogen at-ing catalyst carrier
Selection, but comprehensively consider from the effect of the complexity of preparation process and the modified hydrogen at-ing catalyst carrier obtained, it is preferable that
The number of the dipping is 2-3 times, i.e. n is preferably 2-3 times.
Wherein, as dipping time n=2, as long as using by the carrier of hydro-thermal process and after guaranteeing to impregnate first time
Carrier be dried and can make acid additive on carrier in layer distributed；As dipping time n >=3, as long as using warp
It crosses the carrier of hydro-thermal process and guarantees that condition dry after repeatedly impregnating meets above-mentioned specific condition and can make acid additive
It is in layer distributed on carrier.
However, usually, drying temperature is too high, it is unfavorable for the control of production process, it is too low, after dipping cannot being made
Carrier be able to abundant drying；And drying time is too long, is unfavorable for the raising of yield, too short, after cannot making dipping
Carrier is sufficiently dried, and therefore, combined factors from every side consider, it is preferable that as n >=3, are impregnated into from the 2nd time
During (n-1)th dipping, the dry temperature temperature drier than after adjacent preceding single-steeping is 30- high after impregnating each time
It is 120 DEG C, more preferably 30-80 DEG C high；The dry time is longer than the time of drying after adjacent preceding single-steeping after impregnating each time
It is 1-9 hours, more preferably 2-5 hours long.
According to the present invention, the drying condition after impregnating every time to last time is not particularly limited, and can use this field
The condition of carrier after conventional dry dipping, as long as can satisfy above-mentioned difference, for example, the leaching of different impregnation steps
Stain condition may be the same or different, and usual can be each independently 20-300 DEG C including dipping temperature, preferably
50-100℃；Dip time can be 1-20 hours, preferably 1-6 hours.
Under preferable case, after impregnating for the first time dry condition include: temperature be 30-300 DEG C (preferably 50-300 DEG C,
More preferably 100-250 DEG C, most preferably 100-150 DEG C), the time is 1-20 hours (preferably 2-18 hours, more preferably 3-
10 hours, most preferably 3-8 hours).Under preferable case, it is 30-300 that last time condition dry after impregnating, which includes: temperature,
DEG C (preferably 50-300 DEG C, more preferably 100-200 DEG C, most preferably 120-180 DEG C), the time be 1-20 hours (preferably
2-18 hours, more preferably 3-10 hours, most preferably 3-5 hours).In addition, in the present invention, the drying all can be true
Sky is dry.
According to the present invention, in the preparation method of the modified hydrogen at-ing catalyst carrier, to the condition of first roasting
Be not particularly limited, for example, roasting condition include: temperature be 300-900 DEG C (preferably 300-800 DEG C, more preferably
350-500 DEG C), the time is 1-10 hours (preferably 2-8 hours, more preferably 2-6 hours).
According to the present invention, the removal of ccr by hydrotreating catalyst 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 removal of ccr by hydrotreating catalyst, this method comprises: the modification is added
Hydrogen catalyst carrier is impregnated in the solution containing the compound that is provided with the active metal component, be then dried and
Roasting.
According to the present invention, the modified hydrogen at-ing catalyst carrier, the activity gold of the offer including metal oxide
Described in the compound of category component as described above, details are not described herein.The modified hydrogen at-ing catalyst carrier and described
The dosage for providing the compound of the active metal component makes in resulting removal of ccr by hydrotreating catalyst, in terms of metal oxide
And on the basis of the total weight of the catalyst, the content of the group VIII metal component is 3-15 weight %, the Section VI B
The content of race's metal component is 13-30 weight %.Preferably, the modified hydrogen at-ing catalyst carrier and the offer activity
The dosage of the compound of metal component makes in resulting removal of ccr by hydrotreating catalyst, in terms of metal oxide and with the catalysis
On the basis of the total weight of agent, the content of the group VIII metal component is 3.1-10 weight %, the vib metals component
Content be 13.1-28 weight %.
According to the present invention, the solvent in the above-mentioned solution containing the compound for being provided with the active metal component can be this
The various solvents of field routine, such as can be water, alcohol (such as methanol, ethyl alcohol etc.), ether (such as ether), aldehyde (such as formaldehyde)
With one of ketone (such as acetone) or a variety of.
According to the present invention, to the dipping in the preparation method of removal of ccr by hydrotreating catalyst, there is no particular limitation, can be with
Using the immersion condition of the supported active metals component of this field routine, for example, the condition of the dipping may include: that temperature is
15-40 DEG C, the time is 1-6 hours.The third dipping can be carried out using the dipping method of this field routine, such as can be
Excessive liquid dipping, hole is satisfied or method infusion process.
According to the present invention, to the drying in the preparation method of removal of ccr by hydrotreating catalyst, there is no particular limitation, can be with
Using the condition of the catalyst after the conventional dry dipping in this field, for example, it is 100- that the condition of the drying, which may include: temperature,
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 second roasting in the preparation method of removal of ccr by hydrotreating catalyst, there is no particular limitation,
It can be using the roasting condition of the removal of ccr by hydrotreating catalyst of this field routine, for example, the condition of the roasting may include: temperature
Degree is 360-500 DEG C (preferably 360-450 DEG C), and the time is 1-10 hours (preferably 2-6 hours).
According to the present invention, above-mentioned preparation method can also include that other upper this fields of removal of ccr by hydrotreating catalyst load are normal
The adjuvant component of rule, such as Si.Such adjuvant component can introduce the removal of ccr by hydrotreating in the method for this field routine and urge
In agent, for example, can the introducing when preparing carrier, can the introducing when preparing modified hydrogen at-ing catalyst carrier, can load
It is introduced when active metal component, alternatively, before supported active metals component, it individually will be containing the compound for being provided with adjuvant component
Solution and modified hydrogen at-ing catalyst carrier carry out immersive contact, and mode (dipping, dry and roasting condition of drying and roasting
Can be carried out using the condition that above any one place records), to this present invention, there is no particular limitation.
The present invention also provides application of the above-mentioned removal of ccr by hydrotreating catalyst 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
Hydrogen, which takes off in the catalytic reactor of carbon residue catalyst, to carry out, for example, in the fixed bed reactors, moving-burden bed reactor or boiling
It rises in a reactor and carries out.
According to the conventional method in this field, the removal of ccr by hydrotreating catalyst before the use, usually can be in hydrogen
In the presence of, presulfurization is carried out with sulphur, hydrogen sulfide or containing sulfur feedstock at a temperature of 140-370 DEG C, this presulfurization can be outside device
Progress can also be In-situ sulphiding in device, and the active metal component that it is loaded is converted into metal sulfide component.
Catalyst provided by the invention can be used alone, and can also use with other catalyst combinations, and the present invention provides
Removal of ccr by hydrotreating catalyst can heavy-oil hydrogenation processing application in obtain higher metal removal rate and asphaltene removal
Rate, to provide qualified feedstock oil for subsequent technique (such as catalytic cracking process).
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 2000 grams of Chang Ling catalyst plants produce, (butt is 73 weight %, wherein boehmite content
For 68 weight %, hibbsite content is 5 weight %, and surplus is amorphous alumina), 60 grams of sesbania powder (Henan Lankao
Sesbania gum factory product), 60g hydroxymethyl cellulose and 15g carbon black and be uniformly mixed, 1800 milliliters of nitric acid containing 32g are added later
Aqueous solution is extruded into the butterfly wet bar that outer diameter is 1.4mm on plunger type bar extruder.Then by butterfly wet bar dry 4 at 120 DEG C
Hour, it is roasted 3 hours at 600 DEG C, obtains carrier Z.It is obtained using mercury injection method measurement, the Kong Rongwei 0.7mL/g of carrier Z,
Specific surface area is 231m2Bimodal shape distribution is presented in/g, pore structure, and wherein the hole 4nm-10nm accounts for 65%, 100nm- of total pore volume
The hole 200nm accounts for the 10% of total pore volume.
Embodiment 1
The present embodiment is for illustrating removal of ccr by hydrotreating catalyst and preparation method thereof of the invention.
(1) 200 grams of carrier Z prepared by preparation example 1 are taken, first by carrier in 70 DEG C hydro-thermal process 24 hours, then will be through water
Carrier after heat treatment 165 milliliters of temperature are 50 DEG C and contain 15 grams per liter H3BO3Aqueous solution (pH value 6) saturation dipping it is 1 small
When, it is 3 hours dry in 100 DEG C later, obtain the carrier that load has B component；
(2) will load obtained in step (1) to have the carrier of B component in 140 milliliters of temperature be 50 DEG C containing 15 grams per liters
NH4Dipping 1 hour in the aqueous solution (pH value 11) of F, it is then 3 hours dry in 120 DEG C, it roasts 3 hours, obtains then at 400 DEG C
To modified hydrogen at-ing catalyst carrier S 1.
(3) 200 grams of carrier Ss 1 are taken, with 160 milliliters of molybdenum oxides and basic cobaltous carbonate mixed solution (wherein, with MoO3Meter
The concentration of Mo element is 136 grams per liters, and the concentration of the Co element in terms of CoO is 49 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 catalyst CS1.Molybdenum oxide in catalyst CS1
Table 3 is listed in the content of cobalt oxide.
Embodiment 2
The present embodiment is for illustrating removal of ccr by hydrotreating catalyst and preparation method thereof of the invention.
(1) 200 grams of carrier Z prepared by preparation example 1 are taken, first by carrier in 150 DEG C hydro-thermal process 10 hours, then will be through water
Carrier after heat treatment 155 milliliters of temperature are 80 DEG C and contain 6 grams per liter H3BO3Aqueous solution (pH value 2) saturation dipping it is 1 small
When, it is 6 hours dry in 120 DEG C later, obtain the carrier that load has B component；
(2) will load obtained in step (1) to have the carrier of B component in 135 milliliters of temperature be 80 DEG C containing 8 grams per liters
H3PO4Aqueous solution (pH value 2) in dipping 1 hour, 8 hours dry in 180 DEG C later, obtaining load has B component and P component
Carrier；
(3) it in 125 milliliters of temperature is 80 DEG C containing 10 that the load for obtaining step (2), which has the carrier of B component and P component,
Grams per liter NH4Dipping 1 hour in the aqueous solution (pH value 10) of F, it is then 3 hours dry in 120 DEG C, it is small then at 400 DEG C of roastings 3
When, obtain modified hydrogen at-ing catalyst carrier S 2.
(4) 200 grams of carrier Ss 2 are taken, with 160 milliliters of molybdenum oxides and basic nickel carbonate mixed solution (wherein, with MoO3Meter
The concentration of 136 grams per liter of concentration of Mo element, the Ni element in terms of NiO is 49 grams per liters, and solvent is water) under room temperature (about 25 DEG C)
Dipping 1 hour is dried 2 hours in 120 DEG C, and 420 DEG C roast 3 hours, obtain catalyst CS2.Molybdenum oxide in catalyst CS2 and
The content of nickel oxide is listed in table 3.
Embodiment 3
The present embodiment is for illustrating removal of ccr by hydrotreating catalyst and preparation method thereof of the invention.
(1) 200 grams of carrier Z prepared by preparation example 1 are taken, first by carrier in 100 DEG C hydro-thermal process 24 hours, then will be through water
Carrier after heat treatment 135 milliliters of temperature are 70 DEG C and contain 10 grams per liter H3PO4Aqueous solution (pH value 4) saturation dipping it is 1 small
When, it is 8 hours dry in 120 DEG C later, obtain the carrier that load has P component；
(2) will load obtained in step (1) to have the carrier of P component in 155 milliliters of temperature be 70 DEG C containing 10 grams per liters
H3BO3Aqueous solution (pH value 8) in dipping 1 hour, it is then 3 hours dry in 120 DEG C, roast 3 hours, obtain then at 400 DEG C
Modified hydrogen at-ing catalyst carrier S 3.
(3) 200 grams of carrier Ss 3 are taken, with 160 milliliters of molybdenum oxides and basic nickel carbonate mixed solution (wherein, with MoO3Meter
The concentration of Mo element is 186 grams per liters, and the concentration of the Ni element in terms of NiO is 57 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 catalyst CS3.Molybdenum oxide in catalyst CS3
Table 3 is listed in the content of nickel oxide.
Embodiment 4
The present embodiment is for illustrating removal of ccr by hydrotreating catalyst and preparation method thereof of the invention.
According to the method for (1)-(3) the step of embodiment 2, the difference is that, contain H3BO3Aqueous solution, contain H3PO4It is water-soluble
Liquid and contain NH4The pH of the aqueous solution of F is 7, obtains modified hydrogen at-ing catalyst carrier S 4.
(4) 200 grams of carrier Ss 4 are taken, with 160 milliliters of molybdenum oxides and basic cobaltous carbonate mixed solution (wherein, with MoO3Meter
The concentration of Mo element is 186 grams per liters, and the concentration of the Co element in terms of CoO is 57 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 catalyst CS4.Molybdenum oxide in catalyst CS4
Table 3 is listed in the content of cobalt oxide.
Embodiment 5
The present embodiment is for illustrating removal of ccr by hydrotreating catalyst and preparation method thereof of the invention.
According to (1) the step of embodiment 1 and (2), modified hydrogen at-ing catalyst carrier S 1 is made.
(3) 200 grams of carrier Ss 1 are taken, with 160 milliliters of molybdenum oxides and basic nickel carbonate mixed solution (wherein, with MoO3Meter
The concentration of Mo element is 280 grams per liters, and the concentration of the Ni element in terms of NiO is 80 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 catalyst CS5.Molybdenum oxide in catalyst CS5
Table 3 is listed in the content of nickel oxide.
Comparative example 1
(1) 200 grams of carrier Z prepared by preparation example 1 are taken, are 40 DEG C containing 28 grams per liter H with 160 milliliters of temperature3BO3Water
Solution (pH 7) 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 D1.
(2) according to the method for (3) the step of embodiment 1, the difference is that, carrier S 1 is substituted using carrier D1, to obtain
Catalyst CD1.The content of molybdenum oxide and cobalt oxide in catalyst CD1 is listed in table 3.
Comparative example 2
(1) 200 grams of carrier Z prepared by preparation example 1 are taken, at a temperature of 90 °C contain 25 grams per liter NH with 155 milliliters4F's is molten
Liquid (pH 7) 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 is urged
Agent carrier D2.
(2) according to the method for (3) the step of embodiment 2, the difference is that, carrier S 2 is substituted using carrier D2, to obtain
Catalyst CD2.The content of molybdenum oxide and nickel oxide in catalyst CD2 is listed in table 3.
Comparative example 3
Catalyst carrier is prepared according to the method for (1)-(3) the step of embodiment 2, unlike, the method for the comparative example
Do not include the steps that by carrier Z 150 DEG C hydro-thermal process 10 hours, to obtain reference modified hydrogen at-ing catalyst carrier D3.
(4) according to the method for (3) the step of embodiment 3, the difference is that, carrier S 3 is substituted using carrier D3, to obtain
Catalyst CD3.The content of molybdenum oxide and nickel oxide in catalyst CD3 is listed in table 3.
Comparative example 4
Catalyst carrier is prepared according to the method for (1)-(3) the step of embodiment 2, unlike, after step (2) dipping
It is 6 hours dry at 130 DEG C, that is, the dry temperature temperature drier than after adjacent preceding single-steeping is high after rear single-steeping
10 DEG C, the dry time is equal with the time dry after adjacent preceding single-steeping after rear single-steeping, obtains that reference is modified to be added
Hydrogen catalyst carrier D4.
(4) according to the method for (4) the step of embodiment 4, the difference is that carrier S 4 is substituted using carrier D4, thus
To catalyst CD4.The content of molybdenum oxide and cobalt oxide in catalyst CD4 is listed in table 3.
Comparative example 5
Prepare modified hydrogen at-ing catalyst carrier according to the method for embodiment 1, unlike, step (1) dipping after without
Operation that is dry and directly carrying out step (2), obtains reference modified hydrogen at-ing catalyst carrier D5.
(3) according to the method for (3) the step of embodiment 5, the difference is that carrier S 5 is substituted using carrier D5, thus
To catalyst CD5.The content of molybdenum oxide and nickel oxide in catalyst CD5 is listed in table 3.
Test case 1
Using SEM-EDX (Scanning Electron Microscope-Energy Dispersive
Spectrometry) method analyzes the Elemental redistribution in modified hydrogen at-ing catalyst carrier granular.It is tied since SEM-EDX is characterized
Numerical value in fruit along carrier radial direction every bit constituent content is corresponded to each other with the point element content, although the size of the numerical value may
The real content of the point element is not represented, but is able to reflect the point element content height.Therefore, in order to indicate acid additive edge
The regularity of distribution of carrier radial direction introduces distribution factor σ.With σ indicate acid additive on a certain position of particle with concentration at center it
Than (R is particle radius, using at modified hydrogen at-ing catalyst carrier granular center as starting point).The acid additive is on a certain position
Concentration refers to the average value of the position (position deviation≤20nm) 20 numerical points numeration nearby in SEM-EDX characterization result；Institute
State the average value of acid additive (position deviation≤20nm) 20 numerical point counting rates near point centered on the concentration at center.If
σ > 1 then shows that this acid additive constituent content is higher than at modified hydrogen at-ing catalyst carrier granular center；If σ=1 shows
This acid additive constituent content is identical as at modified hydrogen at-ing catalyst carrier granular center；If σ < 1, show that the point acidity helps
Agent constituent content is less than at modified hydrogen at-ing catalyst carrier granular center.Table 1 is the relevant parameter of modified hydrogen at-ing catalyst carrier,
Wherein, the content (calculating based on the element) of acid additive is calculated according to inventory.Table 2 be modified hydrogen at-ing catalyst carrier on not
With the distribution factor of acid additive at different locations.
Table 1
Table 2
| Number | S1 | S2 | S3 | S4 | D1 | D2 | D3 | D4 | D5 |
| σB(R) | 2.67 | 2.58 | 1.89 | 1.12 | 1.05 | - | 1.35 | 2.79 | 2.71 |
| σB(2/3R) | 2.00 | 1.97 | 1.76 | 1.35 | 0.98 | - | 0.97 | 2.01 | 1.91 |
| σB(1/3R) | 1.05 | 1.34 | 1.36 | 0.98 | 1.01 | - | 0.93 | 1.54 | 1.61 |
| σP(R) | - | 1.54 | 2.87 | 1.36 | - | - | 1.21 | 1.67 | - |
| σP(2/3R) | - | 2.36 | 2.15 | 1.45 | - | - | 1.09 | 2.69 | - |
| σP(1/3R) | - | 1.56 | 1.86 | 1.21 | - | - | 0.96 | 1.36 | - |
| σF(R) | 0.18 | 0.19 | - | 1.39 | - | 0.98 | 0.97 | 2.36 | 2.59 |
| σF(2/3R) | 0.32 | 0.42 | - | 0.96 | - | 0.96 | 1.45 | 1.78 | 1.81 |
| σF(1/3R) | 0.78 | 0.81 | - | 1.56 | - | 0.95 | 1.24 | 1.13 | 1.54 |
Table 3
Test case 2
Above-mentioned catalyst breakage is packed into heavy-oil hydrogenation fixed bed reactors at 2-3 millimeters of diameter of particle respectively.Reaction
Condition are as follows: 380 DEG C of reaction temperature, hydrogen partial pressure 14MPa measure the carbon residue of reaction front and back oil product using micro carbon residue method.Using
Nitrogen content in the oil product of chemiluminescence determination reaction front and back, reacts the S in the oil product of front and back using x-ray fluorescence spectrometry
Content measures the content of oily studies on asphaltene using Research Institute of Petro-Chemical Engineering from construction method.Pitch is calculated according to the following formula
Matter, carbon residue and sulphur, nitrogen removal efficiency:
Feedstock oil be nitrogen element content be 0.3 weight %, sulfur content is 4.7 weight %, asphalt content is 6.8 weights
Measure %, the normal slag of Kuwait that carbon residue is 15.8 weight %.Nitrogen element content, sulfur content, drip in feedstock oil after adding hydrogen
The denitrification percent of green matter content and carbon residue and each catalyst, desulfurization degree, asphaltene removal and carbon residue removal efficiency are shown in Table 4.
Table 4
From the results shown in Table 4, providing removal of ccr by hydrotreating catalyst by the present invention has preferable denitrogenation, sulphur activity
With carbon residue removal activity, special pitch removal activity, wherein denitrification percent can reach 50% or more, preferably can reach 51% with
On；Desulfurization degree can reach 89% or more, preferably can reach 91% or more；Carbon residue removal efficiency can reach 63% or more, preferably reachable
To 65% or more, asphaltene removal can reach 84% or more, preferably can reach 86% or more.To provided by the invention plus hydrogen
The de- great prospects for commercial application of carbon residue catalyst.
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 removal of ccr by hydrotreating catalyst, which contains active metal component and modified hydrogen at-ing catalyst carrier, special
Sign is that the modified hydrogen at-ing catalyst carrier is made by following methods, this method comprises: by the carrier Jing Guo hydro-thermal process
It is repeatedly successively impregnated and is dried, and the desciccate obtained for the last time is roasted, wherein each dipping process
Used in maceration extract containing being provided with identical or different acid additive compound, duplicate frequency n >=2, and as n >=3, from
During 2nd time is impregnated into (n-1)th dipping, dry temperature is drier than after adjacent preceding single-steeping after impregnating each time
Temperature it is 20-150 DEG C high, after impregnating each time the dry time it is drier than after adjacent preceding single-steeping time it is 1-10 long small
When；And
The active metal component contains at least one group VIII metal component and at least one vib metals component, with
Metal oxide meter and on the basis of the total weight of the catalyst, the content of the group VIII metal component are 3-15 weight
% is measured, the content of the vib metals component is 13-30 weight %.
2. removal of ccr by hydrotreating catalyst according to claim 1, wherein in terms of metal oxide and with the catalyst
On the basis of total weight, the content of the group VIII metal component is 3.1-10 weight %, and the vib metals component contains
Amount is 13.1-28 weight %.
3. removal of ccr by hydrotreating catalyst according to claim 2, wherein the group VIII metal component be selected from Co and/
Or Ni, vib metals group are selected from Mo and/or W.
4. removal of ccr by hydrotreating catalyst described in any one of -3 according to claim 1, wherein in the modified hydrogenation catalyst
In the preparation method of agent carrier, as n >=3, during from (n-1)th dipping is impregnated into the 2nd time, done after impregnating each time
The dry temperature temperature drier than after adjacent preceding single-steeping is 30-120 DEG C high, and the dry time is than adjacent after impregnating each time
Preceding single-steeping after the dry time it is 1-9 hours long.
5. removal of ccr by hydrotreating catalyst according to claim 4, wherein as n >=3, be impregnated into (n-1)th from the 2nd time
During secondary dipping, the dry temperature temperature drier than after adjacent preceding single-steeping is 30-80 DEG C high after impregnating each time,
The dry time is 2-5 hours longer than the time of drying after adjacent preceding single-steeping after impregnating each time.
6. removal of ccr by hydrotreating catalyst according to claim 5, wherein dry condition includes: temperature after impregnating for the first time
Degree is 30-300 DEG C, and the time is 1-20 hours；It is 30-300 DEG C that last time condition dry after impregnating, which includes: temperature, the time
It is 1-20 hours.
7. removal of ccr by hydrotreating catalyst according to claim 5 or 6, wherein the condition of roasting includes: that temperature is 300-
900 DEG C, the time is 1-10 hours.
8. removal of ccr by hydrotreating catalyst described in any one of -3 and 5-6 according to claim 1, wherein add in the modification
In the preparation method of hydrogen catalyst carrier, it is in acidity that first n-1 times, which impregnates used maceration extract,；Leaching used by n-th dipping
Stain liquid is in alkalinity.
9. removal of ccr by hydrotreating catalyst according to claim 8, wherein in the preparation of the modified hydrogen at-ing catalyst carrier
In method, first n-1 times the pH value for impregnating used maceration extract is 2-6；The pH value of maceration extract used by n-th impregnates is 8-
11。
10. removal of ccr by hydrotreating catalyst according to claim 8, wherein in the system of the modified hydrogen at-ing catalyst carrier
In Preparation Method, the number of the dipping is 2-3 times.
11. according to claim 1-3, removal of ccr by hydrotreating catalyst described in any one of 5-6 and 9-10, wherein described
In the preparation method of modified hydrogen at-ing catalyst carrier, the carrier is aluminium oxide or aluminium oxide and silica, titanium oxide and oxygen
Change the mixture of at least one of zirconium；The aluminium oxide is gama-alumina, η-aluminium oxide, θ-aluminium oxide, δ-aluminium oxide and χ-oxygen
Change at least one of aluminium.
12. according to claim 1-3, removal of ccr by hydrotreating catalyst described in any one of 5-6 and 9-10, wherein described
In the preparation method of modified hydrogen at-ing catalyst carrier, the acid additive is selected from least one of F, P and B component.
13. removal of ccr by hydrotreating catalyst according to claim 12, wherein maceration extract used in each dipping process contains
The compound of different acid additives is provided.
14. removal of ccr by hydrotreating catalyst according to claim 12, wherein in the modified hydrogen at-ing catalyst carrier, with
On the basis of the total weight of the modified hydrogen at-ing catalyst carrier, the content of the acid additive in terms of tri- kinds of elements of F, P and B is
0.1-15 weight %.
15. the preparation method of removal of ccr by hydrotreating catalyst described in a kind of any one of claim 1-14, this method comprises:
The modified hydrogen at-ing catalyst carrier is impregnated in the solution containing the compound for being provided with the active metal component, so
After be dried and roast.
16. according to the method for claim 15, wherein in the preparation method of removal of ccr by hydrotreating catalyst, the dipping
Condition include: temperature be 15-40 DEG C, the time be 1-6 hours.
17. according to the method for claim 16, wherein in the preparation method of removal of ccr by hydrotreating catalyst, the drying
Condition include: temperature be 100-250 DEG C, the time be 1-10 hours.
18. according to the method for claim 16, wherein in the preparation method of removal of ccr by hydrotreating catalyst, the item of roasting
Part includes: that temperature is 360-500 DEG C, and the time is 1-10 hours.
19. the answering in heavy-oil hydrogenation processing of removal of ccr by hydrotreating catalyst described in any one of -14 according to claim 1
With.
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