CN109718796A - A kind of hydrogenation catalyst and preparation method thereof - Google Patents
A kind of hydrogenation catalyst and preparation method thereof Download PDFInfo
- Publication number
- CN109718796A CN109718796A CN201711019737.8A CN201711019737A CN109718796A CN 109718796 A CN109718796 A CN 109718796A CN 201711019737 A CN201711019737 A CN 201711019737A CN 109718796 A CN109718796 A CN 109718796A
- Authority
- CN
- China
- Prior art keywords
- microreactor
- reaction
- hydrogenation catalyst
- active metal
- acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 102
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 79
- 238000002360 preparation method Methods 0.000 title claims abstract description 38
- 239000000463 material Substances 0.000 claims abstract description 110
- 238000006243 chemical reaction Methods 0.000 claims abstract description 92
- 229910052751 metal Inorganic materials 0.000 claims abstract description 84
- 239000002184 metal Substances 0.000 claims abstract description 84
- 239000002253 acid Substances 0.000 claims abstract description 68
- 239000000243 solution Substances 0.000 claims abstract description 62
- 238000000034 method Methods 0.000 claims abstract description 28
- 230000010355 oscillation Effects 0.000 claims abstract description 23
- 230000032683 aging Effects 0.000 claims abstract description 22
- 239000003513 alkali Substances 0.000 claims abstract description 20
- 239000000047 product Substances 0.000 claims abstract description 16
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 14
- 229910000329 aluminium sulfate Inorganic materials 0.000 claims abstract description 11
- 150000004645 aluminates Chemical class 0.000 claims abstract description 9
- 230000008569 process Effects 0.000 claims abstract description 9
- 159000000013 aluminium salts Chemical class 0.000 claims abstract description 6
- 239000012266 salt solution Substances 0.000 claims abstract description 3
- 238000009826 distribution Methods 0.000 claims description 26
- 238000010438 heat treatment Methods 0.000 claims description 24
- 239000013078 crystal Substances 0.000 claims description 17
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 15
- 230000000694 effects Effects 0.000 claims description 15
- 229910044991 metal oxide Inorganic materials 0.000 claims description 14
- 150000004706 metal oxides Chemical class 0.000 claims description 14
- 239000002245 particle Substances 0.000 claims description 14
- 239000011148 porous material Substances 0.000 claims description 14
- 239000007864 aqueous solution Substances 0.000 claims description 13
- 150000002739 metals Chemical class 0.000 claims description 11
- 239000007788 liquid Substances 0.000 claims description 9
- 238000001556 precipitation Methods 0.000 claims description 9
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical group Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 8
- 230000001276 controlling effect Effects 0.000 claims description 7
- 239000012530 fluid Substances 0.000 claims description 7
- 229910001388 sodium aluminate Inorganic materials 0.000 claims description 7
- 229910052593 corundum Inorganic materials 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 229910052750 molybdenum Inorganic materials 0.000 claims description 5
- 229910052759 nickel Inorganic materials 0.000 claims description 5
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 5
- 230000002378 acidificating effect Effects 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 229910052721 tungsten Inorganic materials 0.000 claims description 3
- 238000000889 atomisation Methods 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 230000007935 neutral effect Effects 0.000 claims description 2
- 150000004965 peroxy acids Chemical class 0.000 claims description 2
- 230000005855 radiation Effects 0.000 claims description 2
- 230000029219 regulation of pH Effects 0.000 claims description 2
- 230000001105 regulatory effect Effects 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims 4
- 239000004411 aluminium Substances 0.000 claims 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims 2
- 239000010931 gold Substances 0.000 claims 2
- 229910052737 gold Inorganic materials 0.000 claims 2
- 239000001301 oxygen Substances 0.000 claims 2
- 229910052760 oxygen Inorganic materials 0.000 claims 2
- 150000001875 compounds Chemical class 0.000 claims 1
- 230000003647 oxidation Effects 0.000 claims 1
- 238000007254 oxidation reaction Methods 0.000 claims 1
- 238000006386 neutralization reaction Methods 0.000 abstract 1
- 239000011541 reaction mixture Substances 0.000 description 21
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Inorganic materials O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 19
- 230000035939 shock Effects 0.000 description 13
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 9
- 238000001914 filtration Methods 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 238000012546 transfer Methods 0.000 description 6
- 238000000975 co-precipitation Methods 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 4
- 230000001965 increasing effect Effects 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 230000008901 benefit Effects 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 230000006911 nucleation Effects 0.000 description 3
- 238000010899 nucleation Methods 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- WURBVZBTWMNKQT-UHFFFAOYSA-N 1-(4-chlorophenoxy)-3,3-dimethyl-1-(1,2,4-triazol-1-yl)butan-2-one Chemical compound C1=NC=NN1C(C(=O)C(C)(C)C)OC1=CC=C(Cl)C=C1 WURBVZBTWMNKQT-UHFFFAOYSA-N 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 239000005864 Sulphur Substances 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 239000000908 ammonium hydroxide Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 238000001994 activation Methods 0.000 description 1
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 1
- 235000018660 ammonium molybdate Nutrition 0.000 description 1
- 239000011609 ammonium molybdate Substances 0.000 description 1
- 229940010552 ammonium molybdate Drugs 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 230000003698 anagen phase Effects 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 230000002844 continuous effect Effects 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000000295 emission spectrum Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 238000009616 inductively coupled plasma Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000005360 mashing Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000002159 nanocrystal Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 description 1
- ZULUUIKRFGGGTL-UHFFFAOYSA-L nickel(ii) carbonate Chemical compound [Ni+2].[O-]C([O-])=O ZULUUIKRFGGGTL-UHFFFAOYSA-L 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 1
- 238000009527 percussion Methods 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 238000005549 size reduction Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000004148 unit process Methods 0.000 description 1
Abstract
The invention discloses a kind of hydrogenation catalysts and preparation method thereof.The reaction system that the preparation of the hydrogenation catalyst uses includes concatenated N number of microreactor, first microreactor is impact flow reactor, acid and alkaline material enters the first microreactor and carries out neutralization reaction, product sequentially enters second to N-1 microreactor, and pH value is combined to swing, to when alkali side oscillation, reaction temperature is 20~30 DEG C lower than the first microreactor；To when sour side oscillation, reaction temperature is 20~30 DEG C higher than the first microreactor, and gained reaction product enters N microreactor and carries out aging reaction, and roasting obtains hydrogenation catalyst.Wherein acid material is acid aluminium salt solution and acid active metal solution, and alkaline material is alkali aluminate soln and basic activated metallic solution.The hydrogenation catalyst aperture of this method preparation and hole appearance are larger, and grain size is uniform, and catalyst table phase active metal density is big, eliminates enlarge-effect, is suitably applied hydrodesulfurization and the denitrification process of residual oil.
Description
Technical field
The present invention relates to a kind of hydrogenation catalysts and preparation method thereof, and in particular to one kind is for residuum hydrodesulfurization and takes off
Nitrogen catalyst and preparation method thereof.
Background technique
In recent years, microreactor causes numerous areas researcher greatly academic and commercial interest.This interest results from
The following characteristics of microtechnology, including size reduction, productivity improve, and amplification system scale to the production capacity arbitrarily needed is (i.e.
" dilatation "), heat transfer increases and mass transfer increases.Gavilidis etc. is in " Technology And Applications Of
Microengineered Reactors " Trans. IchemE is right in volume 80, part A, the 3-30 pages (in January, 2002)
The certain work for being related to microreactor are reviewed.Microreactor is the change that a kind of unit process interface width is micron dimension
Reaction system is learned, is the micro- Chemical Engineering Technology risen the nineties.Since deMello and its colleague reported microreactor in 2002
After the prediction and advantage for preparing nanoparticle, the microchannel of microreactor etc. is more and more general on preparing nanocrystal
Time.Microreactor has the advantage that flowing is laminar flow in (1) channel；(2) large specific surface area, heat-transfer capability is strong, and temperature control holds
Easily；(3) molecule diffusion length is short, and mass transfer is fast.
Conventional load type hydrogenation catalyst is limited by carrier pore structure, and active metal load capacity is usually no more than
30wt%, the activated centre quantity that loaded catalyst can be provided is limited, although can to activated centre number amount and type distribution
Adjustment is optimized, but since the limit bottleneck of activated centre quantity can not be broken through, the space for increasing substantially hydrogenation activity has
Limit.Body phase method prepares hydrogenation catalyst and is largely made of active metal component, can get rid of the limitation of tenor, can be any
The ratio of each active component in regulating catalyst, improves the Hydrogenation of catalyst.Coprecipitation prepares bulk phase catalyst technology,
It can be to catalyst pore structure, on channel surfaces in active metallic content and activity using different coprecipitation modes, Gelation Conditions etc.
Interaction relationship has very big shadow between heart density, the distribution of different hydrogenation active metals and difference hydrogenation active metals
It rings.But catalyst aperture, Kong Rong prepared by coprecipitation are smaller, are not suitable for preparing heavy resid hydrodesulfurization and denitrogenation
Catalyst.
CN1951558A, which is disclosed, is related to a kind of preparation method of carbon monoxide-olefin polymeric.Ni is generated using coprecipitationxWyOz
Composite oxides precursor, then with MoO3Mashing mixing, filtering, molding, activation are final catalyst.Wherein coprecipitation is raw
At NixWyOzThe method of composite oxides precursor are as follows: matched by catalytic component content and prepare Ni containing active metal, W component
Then plastic in the reactor tank equipped with water purification is added in saline mixed solution with alkaline precipitating agent cocurrent, the pH of slurries in reactor tank
Value is 7.0 ~ 9.0, and it is composite oxides Ni that gelatinous mixture, which is made,xWyOzPrecursor.Catalyst prepared by this method
Aperture, Kong Rong are smaller, are not suitable for preparing heavy resid hydrodesulfurization and denitrification catalyst.
Summary of the invention
In view of the deficiencies of the prior art, the present invention provides a kind of hydrogenation catalysts and preparation method thereof.The hydrogenation catalyst
Agent aperture, hole appearance are larger, and pore-size distribution is extremely concentrated, and particle size distribution is uniform, and catalyst table phase active metal density is bigger,
Hydrogenation active metals utilization rate is higher.The method and process for preparing hydrogenation catalyst is simple, and the reaction time is short, process continuous effect
Rate is high, eliminates enlarge-effect, is very suitable for industrialized production.
The present invention provides a kind of hydrogenation catalyst, which is bulk phase catalyst, including aluminium oxide and active metal
The particle size distribution of component, the hydrogenation catalyst is as follows :≤50 μm of crystal grain quantity account for the 1% of hydrogenation catalyst crystal grain sum
~5%, greater than 50 μm and less than 100 μm crystal grain quantity account for the 85%~90% of hydrogenation catalyst crystal grain sum, >=100 μm of number of die
Amount accounts for the 5%~10% of hydrogenation catalyst crystal grain sum.
The property of hydrogenation catalyst provided by the invention is as follows: specific surface area is 200~300m2/ g, Kong Rongwei 1.0~
1.2mL/g, pore-size distribution are as follows: 5%~10% of Kong Rongwei total pore volume shared by the hole bore dia < 15nm, 15~25nm of bore dia
Hole shared by Kong Rongwei total pore volume 85%~95%, > 25nm hole shared by Kong Rongwei total pore volume 5%~10%.
In hydrogenation catalyst of the invention, active metal component is group VIII metal and vib metals, group VIII
The content of metal oxide is 5wt%~15wt%, and the content of preferably 5wt%~10wt%, vib metals oxide are
30wt%~50wt%, preferably 30wt%~45wt%, the content of aluminium oxide are 35wt%~65wt%, preferably 45 wt%~
65wt%。
Hydrogenation catalyst of the invention, active metal component is in terms of oxide, active metal and the body phase of table phase VIII group
The weight content ratio of VIII group active metal is 5.0:1 ~ 11.0:1, preferably 8.0 ~ 11.0:1, table phase VIB active metal and body
The weight content ratio of phase VIB active metal is 10.0:1 ~ 25.0:1, preferably 14.0:1 ~ 21.0:1.
In hydrogenation catalyst of the invention, group VIII active metal is selected from one of Ni, Co or a variety of, and Section VI B is living
Property metal be selected from one of Mo, W or a variety of.
In hydrogenation catalyst of the invention, in terms of oxide, the weight content of table phase VIII group active metal is in table phase
The weight content of group VIII active metal, the weight content of body phase VIII group active metal component are group VIII in catalyst
The weight content of active metal；The weight content of table phase VIB active metal component is that the weight of Section VI B activity metal in table phase contains
Amount, the weight content of body phase VIB active metal are the weight content of Section VI B activity metal in catalyst.Catalyst table is mutually active
Tenor is measured using x-ray photoelectron spectroscopy (XPS), caltalyst phase active metallic content using inductive coupling etc. from
Daughter atom emission spectrum (ICP-AES) measurement.
The present invention provides a kind of preparation methods of hydrogenation catalyst, wherein used reaction system includes concatenated N
A microreactor, along logistics direction be respectively the first microreactor, the second microreactor ..., N microreactor, first is micro-
Reactor uses impact flow reactor, comprising the following steps:
(1) alkaline material and acid material are prepared respectively；
(2) alkaline material and acid material are introduced into the first microreactor respectively, carry out neutralization-precipitation reaction；
(3) the resulting reaction product mixed liquor of step (2) is sequentially entered to the second microreactor to N-1 microreactor, and is made
Reaction system passes through pH value swing repeatedly；
(4) the resulting reaction product mixed liquor of step (3) enters N microreactor, carries out aging reaction, the micro- anti-device of N
Effluent enters in product collecting tank, is filtered, washed, then through dry and roasting, obtains hydrogenation catalyst.
Wherein, step (1) neutral and alkali material is alkali aluminate soln and basic activated metallic solution, and acid material is acid
Property aluminate solution and acid active metal solution, the basic activated metallic solution is to contain group VIII and group VIB is living
Property metal alkaline aqueous solution, it is described acidity active metal solution be the acidity containing group VIII and group VIB active metal
Aqueous solution；
Wherein, in step (3), for reaction system to when alkali side oscillation, reaction temperature is 20~30 DEG C lower than the first microreactor；Make anti-
Answer system to when sour side oscillation, reaction temperature is 20~30 DEG C higher than the first microreactor.
In the method for the present invention, concatenated N number of microreactor, N is no less than 5 integer, preferably 5 ~ 11, further preferably
It is 5 ~ 7.
In the method for the present invention, when concatenated N number of microreactor, detailed process that step (3) pH value is swung are as follows:
The resulting reaction product mixed liquor of step (2) enters the second microreactor, while it is micro- anti-that sour material is introduced into second
It answers in device, makes reaction system to sour side oscillation；The resulting reaction product mixed liquor of second microreactor enters the micro- reaction of third
Device, while alkaline material being introduced into third microreactor, make reaction system later successively will be resulting to alkali side oscillation ...
Reaction product mixed liquor is sequentially entered to the 4th microreactor to N-1 microreactor, and makes reaction system repeatedly through peracid side
It swings and alkali side oscillation.
In the preparation method of hydrogenation catalyst of the present invention, alkaline material and acid material are prepared in step (1) respectively, wherein
Alkaline material is alkali aluminate soln and basic activated metallic solution, and the basic aluminate is selected from NaAlO2And KAlO2In
One or two, preferably NaAlO2, the concentration of basic aluminate aqueous solution is with Al2O3It is calculated as 20~200g/100mL；The alkali
Property active metal solution be the alkaline aqueous solution containing group VIII and group VIB active metal, the basic activated metal water
For the concentration of solution in terms of reactive metal oxides, the content of group VIII reactive metal oxides is 10 ~ 30g/100mL, Section VI B
The content of race's reactive metal oxides is 40 ~ 120g/100mL；Acid material is that acid aluminium salt solution and acid active metal are molten
Liquid, the acid aluminium salt are selected from AlCl3、Al2(SO4)3With Al (NO)3One or more of, preferably Al2(SO4)3Or
AlCl3, the concentration of acid aluminium salt aqueous solution is with Al2O3It is calculated as 20~200g/100mL；It is described acidity active metal solution be containing
The acidic aqueous solution of group VIII and group VIB active metal, the concentration of the acidity active metal aqueous solution is with active metal
The content of oxide meter, group VIII reactive metal oxides is 10 ~ 30g/100mL, and group VIB reactive metal oxides contain
Amount is 40 ~ 120g/100mL.
It is in step (2) that alkaline material and acid material introducing first is micro- in the preparation method of hydrogenation catalyst of the present invention
Reactor can be introduced by way of atomization, can also be introduced by liquid mode.
In the preparation method of hydrogenation catalyst of the present invention, the first microreactor, which uses, hits fluid micro-reactor, wherein it is preferred that
If there are two feed inlets to introduce alkaline material and acid material respectively, alkaline material and acid material enter the micro- reaction of percussion flow
It is connected to after device by jet port, alkaline material jet port is hit at an angle with acid material jet port, projected angle of impact 150
~180 °.
In the preparation method of hydrogenation catalyst of the present invention, head tank and the first microreactor use oil bath heating, remaining is micro-
Reactor is heated using microwave radiation.
In the preparation method of hydrogenation catalyst of the present invention, precipitation reaction described in step (2), reaction condition is as follows: anti-
Answering temperature is 50~150 DEG C, and preferably 50~120 DEG C, pH value is 8.0~9.0.The diameter of inner pipe of first microreactor be 10~
20mm, preferably 10~15mm, the residence time for controlling material is 1~5min, preferably 1~2min.
In step (2), the flow velocity of the alkaline material is 10~50mL/min, preferably 15~30mL/min.The acidity
The flow velocity of material can regulate and control according to the pH value that system requires.
In the preparation method of hydrogenation catalyst of the present invention, in step (3), make reaction system to when alkali side oscillation, control
Reaction condition is as follows: reaction temperature is 20~30 DEG C lower than the first microreactor, and pH value is 10.0~11.0.The microreactor it is interior
Pipe diameter is 5~10mm bigger than an adjacent upper microreactor, preferably 8~10mm.The stop of material is controlled in the microreactor
Time is 8~15min, preferably 10~15min.
In the preparation method of hydrogenation catalyst of the present invention, in step (3), make reaction system to when sour side oscillation, control
Reaction condition is as follows: reaction temperature is 20~30 DEG C higher than the first microreactor, and pH value is 3.0~5.0.The microreactor
Diameter of inner pipe is 1~10mm bigger than an adjacent upper microreactor, preferably 2~3mm.The stop of material is controlled in the microreactor
Time is 2~5min, preferably 3~5min.
In the preparation method of hydrogenation catalyst of the present invention, what (4) N microreactor of step carried out is ageing process, control
Aging condition it is as follows: aging temperature is 20~30 DEG C lower than the first microreactor, pH value be 8.0~9.0.The wherein regulation of pH value
Alkaline material can be prepared using step (1) or acid material carries out, and can also be carried out using other acidic or alkaline substances
Regulation.The caliber of N microreactor is 5~10mm bigger than N-1 microreactor, preferably 8~10mm.In N microreactor
Residence time is 8~15min, preferably 10~15min.
In the preparation method of hydrogenation catalyst of the present invention, in step (4), the drying condition are as follows: at 60~150 DEG C
It is 3~10 hours dry；Roasting condition are as follows: roasted 2 ~ 15 hours at 450 ~ 650 DEG C.
Compared with prior art, hydrogenation catalyst provided by the invention and preparation method thereof has the advantage that
1, hydrogenation catalyst aperture of the invention, hole appearance are larger, and pore-size distribution is extremely concentrated, and particle size distribution is uniform, especially
It is suitable as the material of processing macromolecular raw material or reactant, such as residuum hydrodesulfurization and denitrification catalyst.
2, the method that the present invention prepares hydrogenation catalyst, is to tend to reactant concentration in reaction process using microreactor
Constant, and pH value is combined to swing, i.e. the first microreactor uses impact flow reactor, can generate that crystal grain is small and partial size point first
The hydrogenation catalyst nucleus that cloth is concentrated, the condition then swung by control pH value, when making subsequent sour side oscillation using high temperature and
On the one hand amorphous hydroted alumina in hydrogenation catalyst is dissolved, more active metals is exposed to by fast reaction mode
Table phase, another aspect high temperature promote nucleation rate, and are formed and stablized, uniform nucleus, are conducive to the formation of monodisperse crystal, alkali
Side oscillation uses low temperature and slow reaction mode, it is suppressed that new nucleus occurs in growth phase, but straight on the nucleus of formation
Deliver a child it is long simultaneously sufficiently react, utmostly reduce the free energy of system, the crystal grain to be formed enable in stable condition to deposit with monodispersed
?.The sour side oscillation and alkali side oscillation of the method for the present invention in this way repeatedly, are conducive to ten diversity of hydrogenation catalyst pore-size distribution
In, the distribution of crystal grain is uniform and concentrates, and stability is good.In addition, the method for the present invention is conducive to hydrogenation catalyst crystal grain uniform and ordered
Ground accumulation, pore distribution concentration, specific surface area and Kong Rongjun higher can greatly improve containing for active metal in hydrogenation catalyst
Amount, and ensure that catalyst table active metal density mutually with higher, hydrogenation active metals utilization rate is higher.
3, the method that the present invention prepares hydrogenation catalyst, the second microreactor and subsequent microreactor are all made of microwave
Radiant heating avoids the ion Preferential Nucleation that may be brought later to microfluid close to tube wall of mass transfer heating moment, even
May due to the effect of tube wall occur heterogeneous nucleation and stick on tube wall, reduce the rate of mass transfer and due to the high surface of nucleus from
The problem of being reunited by energy, further influencing crystallinity, particle diameter distribution, dispersibility and the yield of crystal grain.
4, the method that the present invention prepares hydrogenation catalyst, compared with autoclave body phase synthesi, reaction process is realized continuously
Change, solve the problems, such as that production efficiency is low, and enlarge-effect is not present in this method, is very suitable for industrialized production.
Detailed description of the invention
Fig. 1 is the schematic flow diagram that the present invention prepares hydrogenation catalyst using 5 microreactors；
Wherein, the first microreactor of 1-, the second microreactor of 2-, 3- third microreactor, the 4th microreactor of 4-, 5- the 5th are micro-
Reactor.
Specific embodiment
Hydrogenation catalyst of the present invention and preparation method thereof is described in more detail below by specific embodiment.Implement
Example is not only to the specific embodiment of the method for the present invention for example, constitute the limitation of the scope of the present invention.This hair
In bright, wt% is mass fraction.
In the present invention, hydrogenation catalyst particle diameter distribution is measured by particles distribution instrument.The specific surface area of hydrogenation catalyst,
Kong Rong and pore-size distribution are measured using low temperature liquid nitrogen Adsorption-desorption processes.Catalyst table phase active metallic content uses X-
X-ray photoelectron spectroscopy X (XPS) measurement, caltalyst phase active metallic content use inductively coupled plasma body atomic emissions light
Compose (ICP-AES) measurement.
The method of the present invention is described in detail for using 5 microreactors below with reference to Fig. 1.The present invention adds hydrogen
Catalyst the preparation method is as follows: alkaline material and acid material are introduced into the first microreactor 1 respectively, it is heavy neutralize
It forms sediment and reacts, wherein the first microreactor 1 is using shock fluid micro-reactor；The resulting product mixture of first microreactor 1 enters
Second microreactor 2, while sour material being introduced into the second microreactor 2, make reaction system to sour side oscillation；Second is micro- anti-
It answers the resulting reaction product mixed liquor of device 2 to enter third microreactor 3, while alkaline material is introduced into third microreactor
In 3, make reaction system to alkali side oscillation；The resulting reaction product mixed liquor of third microreactor 3 enters the 4th microreactor
4, make reaction system to sour side oscillation；The resulting reaction product mixed liquor of 4th microreactor 4 enters the 5th microreactor 5
Aging reaction is carried out, and alkaline material is added and adjusts pH value, the product after aging enters in product collecting tank, filtered, washed
It washs, then through dry and roasting, obtains hydrogenation catalyst；Wherein alkaline material is that alkali aluminate soln and basic activated metal are molten
Liquid, acid material are bialuminate solution and acid active metal solution, and the basic activated metallic solution is to contain the
The alkaline aqueous solution of VIII group and group VIB active metal, the acidity active metal solution is to contain group VIII and Section VI B
The acidic aqueous solution of race's active metal.
In the embodiment of the present invention and comparative example, the diameter of inner pipe of each microreactor is as follows: the inner tube of the first microreactor is straight
Diameter is 12mm, and the diameter of inner pipe of the second microreactor is 14 mm, and the diameter of inner pipe of third microreactor is 23mm, and the 4th is micro- anti-
The diameter of inner pipe for answering device is 25mm, and the diameter of inner pipe of the 5th microreactor is 34mm.
In the present invention, NaAlO2Solution and Al2(SO4)3The concentration of solution is with Al2O3Meter.
Embodiment 1
The present embodiment introduces the preparation method of Mo, Ni original solution.The present embodiment respectively prepares Mo, Ni acid of a kind of concentration and ratio
Property active metal solution A 1 and basic activated metallic solution B1, can prepare the solution of other ratios and concentration according to the method.
The configuration of acid active metal solution A 1: taking 386g molybdenum oxide, and 123g basic nickel carbonate is put into more mouthfuls of flasks, adds
After entering a certain amount of deionized water, it is stirred until then vial matter is slowly added 86g phosphoric acid, waits startings anti-in pulpous state
It should be slowly heated again later, being kept for 90~110 DEG C of times of solution temperature is 1~3 hour, molten to gained while hot after stopping heating
Then liquid filtering is added phosphoric acid and adjusts the pH value of solution to 1.0~4.0 to get clear acid active metal solution A 1 is arrived.
Solution composition is MoO3: 69.27g/100mL；NiO:12.49g/100mL.
The configuration of basic activated metallic solution B1: taking 296g ammonium molybdate, and 105g nickel nitrate is put into more mouthfuls of flasks, is added one
After quantitative deionized water, it is stirred until then vial matter is slowly added 150g ammonium hydroxide, startings is waited to react in pulpous state
It is slowly heated again afterwards, being kept for 70~80 DEG C of times of solution temperature is 1~2 hour, after stopping heating, while hot to acquired solution mistake
Then filter is added ammonium hydroxide and adjusts the pH of solution to 10.0~12.0 to get basic activated metallic solution B1 is arrived.Solution composition is
MoO3: 58.2g/100mL；NiO:10.5g/100mL.
Embodiment 2
The NaAlO for being 50g/100mL by concentration2The alkaline material of solution and basic activated metallic solution B1 and concentration are 80g/
The Al of 100mL2(SO4)3Solution and the acid material of acid active metal solution A 1 are added in respective component tank, Jiang Geyuan
Batch can and first shock fluid micro-reactor, which are put into oil bath, is heated to 90 DEG C, opens the booster pump of two component tanks, simultaneously
Alkaline material and acid material are entered in first shock flow reactor by atomizer, the flow velocity for controlling alkaline material is
15mL/min adjusts the pH value 8.5 in impact flow reactor, carries out neutralization-precipitation reaction, reaction mixture is in first shock stream
It is entered in the second microreactor after stopping 1min in microreactor；Using microwave heating by the reaction temperature of the second microreactor
110 DEG C are raised to, the booster pump of the second microreactor is opened, acid material is injected into the second microreactor, controls pH value
3.0, reaction mixture enters in third microreactor after stopping 3min in the second microreactor；Using microwave heating by
The reaction temperature of three microreactors is increased to 60 DEG C, opens the booster pump of third microreactor, alkaline material is injected into third
In microreactor, pH value 10.0 is controlled, reaction mixture enters the 4th micro- reaction after stopping 10min in third microreactor
In device；The reaction temperature of the 4th microreactor is increased 110 DEG C using microwave heating, opens the booster pump of the 4th microreactor,
Acid material is injected into the 4th microreactor, and controls pH value 3.0, reaction mixture stops in the 4th microreactor
It is entered after 3min in the 5th microreactor；The reaction temperature of the 5th microreactor is raised to 60 DEG C using microwave heating, is opened
Alkaline material is injected into the 5th microreactor by the booster pump of the 5th microreactor, and it is anti-to control the progress aging of pH value 8.0
It answers, reaction mixture after aging 15min, enters in product collecting tank in the 5th microreactor, and product is through filtering, 120
Dry 3h, obtains hydrogenation catalyst A after roasting 3h at 600 DEG C, particle diameter distribution and pore structure are shown in Table 1 at DEG C.
Embodiment 3
The NaAlO for being 80g/100mL by concentration2Solution and basic activated metallic solution B2(MoO3: 50.2g/100mL；NiO:
The Al that alkaline material and concentration 10.1g/100mL) is 100g/100mL2(SO4)3Solution and 45g/100mL acidity active metal
Solution A 2(MoO3: 40.7g/100mL；NiO:11.5g/100mL acid material) is added in respective component tank, Jiang Geyuan
Batch can and first shock fluid micro-reactor, which are put into oil bath, is heated to 80 DEG C, opens the booster pump of two component tanks, simultaneously
Acid material and alkaline material are entered in first shock flow reactor by atomizer, the flow velocity for controlling alkaline material is
15mL/min adjusts the pH value 9.0 in impact flow reactor, carries out neutralization-precipitation reaction, reaction mixture is in first shock stream
It is entered in the second microreactor after stopping 1.5min in microreactor；Using microwave heating by the reaction temperature of the second microreactor
Degree is raised to 100 DEG C, opens the booster pump of the second microreactor, acid material is injected into the second microreactor, controls pH value
3.5, reaction mixture enters in third microreactor after stopping 5min in the second microreactor；Using microwave heating by
The reaction temperature of three microreactors is 60 DEG C, opens the booster pump of third microreactor, and it is micro- anti-that alkaline material is injected into third
It answers in device, controls pH value 10.5, reaction mixture enters the 4th microreactor after stopping 12min in third microreactor
In；The reaction temperature of the 4th microreactor is raised to 110 DEG C using microwave heating, opens the booster pump of the 4th microreactor, it will
Acid material is injected into the 4th microreactor, and controls pH value 3.5, and reaction mixture stops 4min in the 4th microreactor
After enter in the 5th microreactor；The reaction temperature of the 5th microreactor is raised to 55 DEG C using microwave heating, opens the 5th
Alkaline material is injected into the 5th microreactor by the booster pump of microreactor, and is controlled pH value 8.5 and carried out aging reaction, instead
It answers mixed liquor in the 5th microreactor after aging 15min, enters in product collecting tank, product is done at 120 DEG C through filtering
Dry 3h obtains hydrogenation catalyst B after roasting 3h at 600 DEG C, measures its particle diameter distribution and pore structure is shown in Table 1.
Embodiment 4
By the NaAlO of concentration 150g/100mL2Solution and basic activated metallic solution B3(MoO3: 49.8g/100mL；NiO:
The Al that alkaline material and concentration 12.1g/100mL) is 100g/100mL2(SO4)3Solution and acid active metal solution A 3
(MoO3: 56.7g/100mL；NiO:12.3g/100mL acid material) is added in respective component tank, by each head tank with
And first shock fluid micro-reactor is put into oil bath and is heated to 120 DEG C, opens the booster pump of two component tanks, while will be alkaline
Material and acid material are entered in first shock flow reactor by atomizer, and the flow velocity for controlling alkaline material is 15mL/
Min adjusts the pH value 8.5 in impact flow reactor, carries out neutralization-precipitation reaction, reaction mixture is in the micro- reaction of first shock stream
It is entered in the second microreactor after stopping 2min in device；The reaction temperature of the second microreactor is raised to using microwave heating
140 DEG C, the booster pump of the second microreactor is opened, acid material is injected into the second microreactor, controls pH value 4.0, instead
It is entered in third microreactor after answering mixed liquor to stop 5min in the second microreactor；It is using microwave heating that third is micro- anti-
It answers the reaction temperature of device to be raised to 100 DEG C, the booster pump of third microreactor is opened, by NaAlO2Solution is injected into the micro- reaction of third
In device, pH value 11.0 is controlled, reaction mixture enters in the 4th microreactor after stopping 10min in third microreactor；
The reaction temperature of the 4th microreactor is raised to 140 DEG C using microwave heating, opens the booster pump of the 4th microreactor, it will be acid
Material is injected into the 4th microreactor, and controls pH value 3.0, and it is laggard that reaction mixture stops 3min in the 4th microreactor
Enter into the 5th microreactor；The reaction temperature of the 5th microreactor is raised to 100 DEG C using microwave heating, it is micro- anti-to open the 5th
Alkaline material is injected into the 5th microreactor by the booster pump for answering device, and is controlled pH value 9.0 and carried out aging reaction, and reaction is mixed
It closes liquid after aging 15min, to enter in product collecting tank in the 5th microreactor, product is dry at 120 DEG C through filtering
3h obtains hydrogenation catalyst C after roasting 3h at 600 DEG C, measures its particle diameter distribution and pore structure is shown in Table 1.
Embodiment 5
The NaAlO for being 200g/100mL by concentration2Solution and basic activated metallic solution B4(MoO3: 60.2g/100mL；NiO:
The Al that alkaline material and concentration 13.1g/100mL) is 120g/100mL2(SO4)3Solution and acid active metal solution A 4
(MoO3: 57.6g/100mL；NiO:12.3g/100mL acid material) is added in respective component tank, by each head tank with
And first shock fluid micro-reactor is put into oil bath and is heated to 85 DEG C, opens the booster pump of two component tanks, while will be alkaline
Material and acid material are entered in first shock flow reactor by atomizer, control NaAlO2The flow velocity of solution is 20mL/
Min adjusts the pH value 9.0 in impact flow reactor, carries out neutralization-precipitation reaction, reaction mixture is in the micro- reaction of first shock stream
It is entered in the second microreactor after stopping 1min in device；The reaction temperature of the second microreactor is raised to using microwave heating
115 DEG C, the booster pump of the second microreactor is opened, acid material is injected into the second microreactor, controls pH value 3.7, instead
It is entered in third microreactor after answering mixed liquor to stop 3min in the second microreactor；It is using microwave heating that third is micro- anti-
It answers the reaction temperature of device to be raised to 55 DEG C, opens the booster pump of third microreactor, alkaline material is injected into third microreactor
In, pH value 10.7 is controlled, reaction mixture enters in the 4th microreactor after stopping 8min in third microreactor；Using
The reaction temperature of 4th microreactor is raised to 115 DEG C by microwave heating, the booster pump of the 4th microreactor is opened, by acid material
It is injected into the 4th microreactor, and controls pH value 3.8, reaction mixture enters after stopping 3min in the 4th microreactor
In 5th microreactor；The reaction temperature of the 5th microreactor is raised to 65 DEG C using microwave heating, opens the 5th microreactor
Booster pump, alkaline material is injected into the 5th microreactor, and control pH value 8.9 carry out aging reaction, reaction mixture
In the 5th microreactor after aging 13min, entering in product collecting tank, product is through filtering, the dry 3h at 120 DEG C,
Hydrogenation catalyst D is obtained after roasting 3h at 600 DEG C, its particle diameter distribution is measured and pore structure is shown in Table 1.
Comparative example 1
The comparative example is using conventional batch process preparation.
The temperature of reactor tank is heated to 120 DEG C, stirring rate is adjusted to 200rad/min, will with the flow velocity of 15mL/min
Concentration is the NaAlO of 100g/100mL2The alkaline material of solution and basic activated metallic solution B4 are added in reactor tank, simultaneously
The Al that concentration is 100g/100mL is added2(SO4)3The acid material of solution and acid active metal solution A 4, adjust pH value to
Between 8.5, after stablizing 10min, acid material is added and adjusts pH value to 3.0, after stablizing 10min, alkaline material is added, adjusts
PH value is to 11.0, and after stablizing 10min, the acid material that concentration is 40g/100mL is added, and adjusts pH value to 8.0, aging 2h it
Afterwards, through filtering, the dry 3h at 120 DEG C, hydrogenation catalyst E is obtained after roasting 3h at 600 DEG C, measures its particle diameter distribution and hole
Structure is shown in Table 1.
Comparative example 2
This comparative example uses five series connection microreactors same as Example 4, and detailed process is as follows: being 100g/ by concentration
The NaAlO of 100mL2The Al that the alkaline material of solution and basic activated metallic solution B4 and concentration are 100g/100mL2(SO4)3It is molten
Liquid and the acid material of acid active metal solution A 4 are added in respective component tank, by each head tank, the first microreactor
Using oil bath heating, other each reactors use microwave heating, open the booster pump of two component tanks, while by alkaline material
It is entered in the first microreactor with acid material, the flow velocity for controlling alkaline material is 20mL/min, is adjusted in microreactor
PH value 9.0, reaction temperature are 120 DEG C, neutralization-precipitation reaction are carried out, after reaction mixture stops 1min in the first microreactor
It enters in the second microreactor；The reaction temperature of second microreactor is 120 DEG C, opens the booster pump of the second microreactor,
Acid material is injected into the second microreactor, pH value 3.7 is controlled, reaction mixture stops 3min in the second microreactor
After enter in third microreactor；The reaction temperature of third microreactor is 120 DEG C, opens the pressurization of third microreactor
Pump, alkaline material is injected into third microreactor, controls pH value 10.7, and reaction mixture stops in third microreactor
It is entered after 8min in the 4th microreactor；The reaction temperature of 4th microreactor is 120 DEG C, opens the increasing of the 4th microreactor
Acid material is injected into the 4th microreactor by press pump, and controls pH value 3.8, and reaction mixture is in the 4th microreactor
It is entered in the 5th microreactor after stopping 3min；The reaction temperature of 5th microreactor is 120 DEG C, opens the 5th microreactor
Booster pump, alkaline material is injected into the 5th microreactor, and control pH value 8.9 carry out aging reaction, reaction mixture
In the 5th microreactor after aging 13min, entering in product collecting tank, product is through filtering, the dry 3h at 120 DEG C,
After roasting 3h at 600 DEG C, hydrogenation catalyst F is obtained, its particle diameter distribution is measured and pore structure is shown in Table 1.
The property of the hydrogenation catalyst of 1 Examples and Comparative Examples of table preparation
| Hydrogenation catalyst | A | B | C | D | E | F |
| Specific surface area, m2/g | 285 | 289 | 296 | 300 | 182 | 245 |
| Kong Rong, mL/g | 1.25 | 1.27 | 1.24 | 1.23 | 0.85 | 0.93 |
| Can several apertures, nm | 20.5 | 21.1 | 20.5 | 20.5 | 12.5 | 15.3 |
| MoO3, wt% | 42.9 | 37.5 | 45.0 | 35.9 | 43.9 | 32.9 |
| NiO, wt% | 6.9 | 7.9 | 9.7 | 8.9 | 6.8 | 7.6 |
| Particle diameter distribution, % | ||||||
| ≤50μm | 2.7 | 1.5 | 2.5 | 3.0 | 47.9 | 32.5 |
| Greater than 50 μm and less than 100 μm | 89.5 | 89.9 | 88.9 | 89.2 | 51.3 | 67.3 |
| ≥100μm | 7.8 | 8.6 | 8.6 | 7.8 | 0.8 | 0.2 |
| Pore-size distribution, % | ||||||
| < 15nm | 5.7 | 5.0 | 6.9 | 6.0 | 46.8 | 42.2 |
| 15~25nm | 87.9 | 88.6 | 85.2 | 86.2 | 48.6 | 54.3 |
| > 25nm | 6.4 | 6.4 | 7.9 | 7.8 | 4.7 | 3.5 |
In 2 catalyst of table the weight content of the weight content of table phase reactive metal oxides and body phase reactive metal oxides it
Than
| A | B | C | D | E | F | |
| Table phase IMo/ body phase IMo | 20.0 | 19.8 | 18.7 | 19.2 | 8.7 | 13.2 |
| Table phase INi/ body phase INi | 9.0 | 9.7 | 10.0 | 8.9 | 3.2 | 4.8 |
The hydrogenation catalyst prepared by the method for the present invention it can be seen from the data of Tables 1 and 2, partial size integrated distribution are being greater than
50 μm and less than 100 μm in the range of, by its resulting hydrogenation catalyst, specific surface area is high, and Kong Rong, aperture are larger, aperture collection
In be distributed in 15 ~ 25nm, and the dispersion of table phase active metal is higher in hydrogenation catalyst, is well suited for for residuum hydrodesulfurization and de-
The preparation of the mesoporous hydrogenation catalyst such as nitrogen.
Embodiment 6
Catalyst activity evaluation experimental carries out on 100mL reaction under high pressure kettle device, carries out pre- sulphur to catalyst before activity rating
Change.Catalyst is 380 DEG C, reaction time 2h in reaction stagnation pressure 15.5MPa, hydrogen to oil volume ratio 800:1, reaction temperature, is carried out
Activity rating, raw material oil nature and evaluation result are shown in Table 3 ~ table 4 respectively.
3 raw material oil nature of table.
| Feedstock oil | Maoming residual oil |
| Density (20 DEG C), g/cm3 | 0.998 |
| Carbon residue, wt% | 5.45 |
| S, wt% | 3.54 |
| N, μ g/g | 1498 |
4 catalyst activity evaluation result of table
| A | B | C | D | E | F | |
| It is relatively desulphurizing activated | 159 | 145 | 162 | 141 | 100 | 121 |
| Opposite denitrification activity | 145 | 138 | 151 | 131 | 100 | 119 |
The catalyst prepared by the method for the present invention it can be seen from the data of table 4 is with higher de- under the conditions of same process
Sulphur and denitrification activity.
Claims (16)
1. a kind of hydrogenation catalyst, which is bulk phase catalyst, including aluminium oxide and active metal component, and described adds hydrogen
The particle size distribution of catalyst is as follows :≤50 μm of crystal grain quantity account for the 1%~5% of hydrogenation catalyst crystal grain sum, are greater than 50 μm
And less than 100 μm crystal grain quantity account for the 85%~90% of hydrogenation catalyst crystal grain sum, >=100 μm of crystal grain quantity account for hydrogenation catalyst
The 5%~10% of crystal grain sum.
2. hydrogenation catalyst described in accordance with the claim 1, it is characterised in that: the property of the hydrogenation catalyst is as follows: ratio
Surface area is 200~300m21.0~1.2mL/g of/g, Kong Rongwei, pore-size distribution are as follows: Kong Rong shared by the hole bore dia < 15nm
It is the 5%~10% of total pore volume, Kong Rong shared by the hole of 15~25nm of bore dia accounts for the hole institute of 85%~95%, the > 25nm of total pore volume
The 5%~10% of the Kong Rongwei total pore volume accounted for.
3. hydrogenation catalyst described in accordance with the claim 1, it is characterised in that: the hydrogenation catalyst, active metal component
For group VIII metal and vib metals, in terms of oxide, the content of group VIII metal oxide is 5wt%~15wt%,
Preferably 5wt%~10wt%, the content of vib metals oxide are 30wt%~50wt%, preferably 30wt%~45wt%, oxygen
The content for changing aluminium is 35wt%~65wt%, preferably 45 wt%~65wt%；Group VIII active metal in Ni, Co one
Kind is a variety of, and Section VI B activity metal is selected from one of Mo, W or a variety of.
4. hydrogenation catalyst described in accordance with the claim 1, it is characterised in that: the hydrogenation catalyst, active metal component
In terms of oxide, the active metal of table phase VIII group is 5.0:1 ~ 11.0 with the weight content ratio of body phase VIII group active metal:
1, preferably 8.0 ~ 11.0:1, table phase VIB active metal and the weight content ratio of body phase VIB active metal are 10.0:1 ~ 25.0:
1, preferably 14.0:1 ~ 21.0:1.
5. a kind of preparation method of hydrogenation catalyst, it is characterised in that: used reaction system includes concatenated N number of micro- reaction
Device, along logistics direction be respectively the first microreactor, the second microreactor ..., N microreactor, the first microreactor adopts
With impact flow reactor, comprising the following steps:
(1) alkaline material and acid material are prepared respectively；
(2) alkaline material and acid material are introduced into the first microreactor respectively, carry out neutralization-precipitation reaction；
(3) the resulting reaction product mixed liquor of step (2) is sequentially entered to the second microreactor to N-1 microreactor, and is made
Reaction system passes through pH value swing repeatedly；
(4) the resulting reaction product mixed liquor of step (3) enters N microreactor, carries out aging reaction, the micro- anti-device of N
Effluent enters in product collecting tank, is filtered, washed, then through dry and roasting, obtains hydrogenation catalyst；
Wherein, step (1) neutral and alkali material is alkali aluminate soln and basic activated metallic solution, and acid material is acidic aluminum
Acid salt solution and acid active metal solution, the basic activated metallic solution are containing group VIII and group VIB activity gold
The alkaline aqueous solution of category, the acidity active metal solution are that the acidity containing group VIII and group VIB active metal is water-soluble
Liquid；
Wherein, in step (3), for reaction system to when alkali side oscillation, reaction temperature is 20~30 DEG C lower than the first microreactor；Make anti-
Answer system to when sour side oscillation, reaction temperature is 20~30 DEG C higher than the first microreactor.
6. preparation method according to claim 5, it is characterised in that: the hydrogenation catalyst, active metal component are
Group VIII metal and vib metals, in terms of oxide, the content of group VIII metal oxide is 5wt%~15wt%, excellent
It is selected as 5wt%~10wt%, the content of vib metals oxide is 30wt%~50wt%, preferably 30wt%~45wt%, oxidation
The content of aluminium is 35wt%~65wt%, preferably 45 wt%~65wt%；Group VIII active metal is selected from one of Ni, Co
Or it is a variety of, Section VI B activity metal is selected from one of Mo, W or a variety of.
7. preparation method according to claim 5, it is characterised in that: in alkaline material as described in step (1), alkaline aluminium
Hydrochlorate is selected from NaAlO2And KAlO2One or both of, preferably NaAlO2, the concentration of basic aluminate aqueous solution is with Al2O3Meter
For 20~200g/100mL；The concentration of the basic activated aqueous metal solution is in terms of reactive metal oxides, VIII group activity gold
The content for belonging to oxide is 10 ~ 30g/100mL, and the content of group vib reactive metal oxides is 40 ~ 120g/100mL；Described
In acid material, acid aluminium salt is selected from AlCl3、Al2(SO4)3With Al (NO)3One or more of, preferably Al2(SO4)3Or
AlCl3, the concentration of acid aluminium salt aqueous solution is with Al2O3It is calculated as 20~200g/100mL；The acidity active metal aqueous solution it is dense
For degree in terms of reactive metal oxides, the content of VIII group reactive metal oxides is 10 ~ 30g/100mL, group vib active metal oxygen
The content of compound is 40 ~ 120g/100mL.
8. preparation method according to claim 5, it is characterised in that: concatenated N number of microreactor, N be no less than 5 it is whole
Number, preferably 5 ~ 11, further preferably 5 ~ 7.
9. preparation method according to claim 5, it is characterised in that: the detailed process that step (3) pH value is swung are as follows:
The resulting reaction product mixed liquor of step (2) enters the second microreactor, while it is micro- anti-that sour material is introduced into second
It answers in device, makes reaction system to sour side oscillation；The resulting reaction product mixed liquor of second microreactor enters the micro- reaction of third
Device, while alkaline material being introduced into third microreactor, make reaction system to alkali side oscillation ... later by resulting reaction
Product mixture is sequentially entered to the 4th microreactor to N-1 microreactor, and makes reaction system repeatedly through peracid side oscillation
With alkali side oscillation.
10. preparation method according to claim 5, it is characterised in that: first microreactor is set there are two feed inlet
Alkaline material and acid material are introduced respectively, and alkaline material and acid material, which enter after hitting fluid micro-reactor, passes through jet port
Connection, alkaline material jet port are hit at an angle with acid material jet port, and projected angle of impact is 150~180 °.
11. preparation method according to claim 5, it is characterised in that: the first microreactor uses oil bath heating, remaining is micro-
Reactor is heated using microwave radiation.
12. preparation method according to claim 5, it is characterised in that: item is reacted in precipitation reaction described in step (2)
Part is as follows: reaction temperature is 50~150 DEG C, and preferably 50~120 DEG C, pH value is 8.0~9.0；The inner tube of first microreactor is straight
Diameter is 10~20mm, preferably 10~15mm, and the residence time for controlling material is 1~5min, preferably 1~2min.
13. according to preparation method described in claim 5 or 12, it is characterised in that: by alkaline material and acid in step (2)
Material introduces the first microreactor, is introduced by way of atomization or liquid；The flow velocity of the alkaline material is 10~50mL/min,
It is preferred that 15~30mL/min.
14. according to preparation method described in claim 5 or 12, it is characterised in that: in step (3), make reaction system to alkali side
When swing, the reaction condition of control is as follows: reaction temperature is 20~30 DEG C lower than the first microreactor, and pH value is 10.0~11.0；
The diameter of inner pipe of the microreactor is 5~10mm bigger than an adjacent upper microreactor, preferably 8~10mm；In the microreactor
The residence time for controlling material is 8~15min, preferably 10~15min；
In step (3), make reaction system to when sour side oscillation, the reaction condition of control is as follows: reaction temperature reaction more micro- than first
Device is 20~30 DEG C high, and pH value is 3.0~5.0；The diameter of inner pipe of the microreactor is bigger by 1 than an adjacent upper microreactor
~10mm, preferably 2~3mm；The residence time that material is controlled in the microreactor is 2~5min, preferably 3~5min.
15. according to preparation method described in claim 5 or 14, it is characterised in that: (4) N microreactor of step carry out be
The aging condition of ageing process, control is as follows: aging temperature is 20~30 DEG C lower than the first microreactor, and pH value is 8.0~9.0；
The alkaline material or acid material that wherein the regulation of pH value is prepared using step (1) carry out, or using other acid or alkalinity
Substance is regulated and controled；The caliber of N microreactor is 5~10mm bigger than N-1 microreactor, preferably 8~10mm；It is micro- anti-in N
Answering the residence time in device is 8~15min, preferably 10~15min.
16. preparation method according to claim 5, it is characterised in that: in step (4), the drying condition are as follows: 60
It is 3~10 hours dry at~150 DEG C；The roasting condition are as follows: roasted 2 ~ 15 hours at 450 ~ 650 DEG C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711019737.8A CN109718796B (en) | 2017-10-27 | 2017-10-27 | Hydrogenation catalyst and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711019737.8A CN109718796B (en) | 2017-10-27 | 2017-10-27 | Hydrogenation catalyst and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109718796A true CN109718796A (en) | 2019-05-07 |
| CN109718796B CN109718796B (en) | 2021-11-09 |
Family
ID=66291608
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201711019737.8A Active CN109718796B (en) | 2017-10-27 | 2017-10-27 | Hydrogenation catalyst and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109718796B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110404549A (en) * | 2019-08-26 | 2019-11-05 | 北京化工大学 | A kind of the fining preparation and evaluation method of cold poly- hydrogenation of petroleum resin catalyst |
| CN113996308A (en) * | 2020-07-27 | 2022-02-01 | 中国石油化工股份有限公司 | Preparation method of heavy oil hydrogenation catalyst |
| CN114073962A (en) * | 2020-08-17 | 2022-02-22 | 中国石油化工股份有限公司 | Preparation method of bulk phase hydrogenation catalyst |
| CN116060022A (en) * | 2021-10-29 | 2023-05-05 | 中国石油化工股份有限公司 | Hydrogenation catalyst and production method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4721696A (en) * | 1987-03-11 | 1988-01-26 | Phillips Petroleum Company | Silica-modified alumina and process for its preparation |
| US20100152033A1 (en) * | 2007-08-27 | 2010-06-17 | Ackerman Russell Craig | Amorphous silica-alumina composition and a method of making and using such composition |
| CN102309969A (en) * | 2010-07-07 | 2012-01-11 | 中国石油化工股份有限公司 | Preparation method for hydro-treating catalyst |
| CN104549527A (en) * | 2013-10-22 | 2015-04-29 | 中国石油化工股份有限公司 | Preparation method for alumina supporter |
-
2017
- 2017-10-27 CN CN201711019737.8A patent/CN109718796B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4721696A (en) * | 1987-03-11 | 1988-01-26 | Phillips Petroleum Company | Silica-modified alumina and process for its preparation |
| US20100152033A1 (en) * | 2007-08-27 | 2010-06-17 | Ackerman Russell Craig | Amorphous silica-alumina composition and a method of making and using such composition |
| CN102309969A (en) * | 2010-07-07 | 2012-01-11 | 中国石油化工股份有限公司 | Preparation method for hydro-treating catalyst |
| CN104549527A (en) * | 2013-10-22 | 2015-04-29 | 中国石油化工股份有限公司 | Preparation method for alumina supporter |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110404549A (en) * | 2019-08-26 | 2019-11-05 | 北京化工大学 | A kind of the fining preparation and evaluation method of cold poly- hydrogenation of petroleum resin catalyst |
| CN113996308A (en) * | 2020-07-27 | 2022-02-01 | 中国石油化工股份有限公司 | Preparation method of heavy oil hydrogenation catalyst |
| CN113996308B (en) * | 2020-07-27 | 2023-10-10 | 中国石油化工股份有限公司 | Preparation method of heavy oil hydrogenation catalyst |
| CN114073962A (en) * | 2020-08-17 | 2022-02-22 | 中国石油化工股份有限公司 | Preparation method of bulk phase hydrogenation catalyst |
| CN114073962B (en) * | 2020-08-17 | 2023-10-10 | 中国石油化工股份有限公司 | Preparation method of bulk phase hydrogenation catalyst |
| CN116060022A (en) * | 2021-10-29 | 2023-05-05 | 中国石油化工股份有限公司 | Hydrogenation catalyst and production method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109718796B (en) | 2021-11-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109718796A (en) | A kind of hydrogenation catalyst and preparation method thereof | |
| EP2260004B1 (en) | Method for producing a nanocrystalline bismuth-molybdenum mixed oxide | |
| CN106179461B (en) | A kind of preparation method of hydrocracking catalyst | |
| CN106179386B (en) | The preparation method of Hydrobon catalyst | |
| CN106179381B (en) | The preparation method of Hydrobon catalyst | |
| CN106179474B (en) | A kind of Hydrobon catalyst and its preparation method | |
| CN109718794A (en) | A kind of boiling bed hydrogenation catalyst and preparation method thereof | |
| CN109721088A (en) | A kind of aluminium hydroxide and preparation method thereof | |
| CN106179467B (en) | A kind of sulfurized hydrogenation Cracking catalyst and preparation method thereof | |
| CN106179385B (en) | A kind of preparation method of Hydrobon catalyst | |
| CN109721087B (en) | Pseudo-boehmite and preparation method thereof | |
| CN106179462B (en) | A kind of hydrocracking catalyst and preparation method thereof | |
| DE102009054229A1 (en) | Producing a molybdenum mixed oxide precursor, comprises producing first and second solution, which contains e.g. niobium- and antimony-containing starting compounds, introducing the solutions into micro-mixed reactor, recovering precursor | |
| CN109718795B (en) | Hydrogenation catalyst and preparation method thereof | |
| CN109721085A (en) | Aluminium hydroxide and preparation method thereof | |
| CN106179288B (en) | A kind of hydrocracking catalyst and its preparation method | |
| CN106179464B (en) | A kind of preparation method of hydrocracking catalyst | |
| CN106179466B (en) | The preparation method of hydrocracking catalyst | |
| CN105817232A (en) | Hydrogenation catalyst composition and preparation method thereof | |
| CN106179480B (en) | A kind of Hydrobon catalyst composition and preparation method thereof | |
| CN106179514B (en) | A kind of hydrocracking catalyst and preparation method thereof containing heteropoly acid | |
| CN106179465B (en) | The preparation method of hydrocracking catalyst | |
| CN106179463B (en) | Hydrocracking catalyst and its preparation method | |
| CN106179380B (en) | A kind of Hydrobon catalyst and preparation method thereof | |
| CN106179391B (en) | Hydrocracking catalyst and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20231013 Address after: 100728 No. 22 North Main Street, Chaoyang District, Beijing, Chaoyangmen Patentee after: CHINA PETROLEUM & CHEMICAL Corp. Patentee after: Sinopec (Dalian) Petrochemical Research Institute Co.,Ltd. Address before: 100728 No. 22 North Main Street, Chaoyang District, Beijing, Chaoyangmen Patentee before: CHINA PETROLEUM & CHEMICAL Corp. Patentee before: DALIAN RESEARCH INSTITUTE OF PETROLEUM AND PETROCHEMICALS, SINOPEC Corp. |