CN109833890A - A kind of residual oil hydrocatalyst and its preparation - Google Patents
A kind of residual oil hydrocatalyst and its preparation Download PDFInfo
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- CN109833890A CN109833890A CN201711192852.5A CN201711192852A CN109833890A CN 109833890 A CN109833890 A CN 109833890A CN 201711192852 A CN201711192852 A CN 201711192852A CN 109833890 A CN109833890 A CN 109833890A
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- residual oil
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- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 239000003054 catalyst Substances 0.000 claims abstract description 57
- 229910052751 metal Inorganic materials 0.000 claims abstract description 52
- 239000002184 metal Substances 0.000 claims abstract description 51
- 238000000034 method Methods 0.000 claims abstract description 39
- 230000000694 effects Effects 0.000 claims abstract description 20
- -1 polypropylene Polymers 0.000 claims abstract description 12
- 239000004094 surface-active agent Substances 0.000 claims abstract description 10
- 239000004743 Polypropylene Substances 0.000 claims abstract description 9
- 229920001155 polypropylene Polymers 0.000 claims abstract description 9
- 239000002253 acid Substances 0.000 claims abstract description 8
- 238000005470 impregnation Methods 0.000 claims abstract description 6
- 239000003960 organic solvent Substances 0.000 claims abstract description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 32
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical group [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 19
- 238000001035 drying Methods 0.000 claims description 13
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 claims description 13
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 claims description 13
- NWGKJDSIEKMTRX-AAZCQSIUSA-N Sorbitan monooleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O NWGKJDSIEKMTRX-AAZCQSIUSA-N 0.000 claims description 12
- 235000019441 ethanol Nutrition 0.000 claims description 12
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 7
- 229910000480 nickel oxide Inorganic materials 0.000 claims description 7
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims description 7
- 229910052698 phosphorus Inorganic materials 0.000 claims description 7
- 239000011574 phosphorus Substances 0.000 claims description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 229910000476 molybdenum oxide Inorganic materials 0.000 claims description 5
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 claims description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 4
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 4
- 229920002125 Sokalan® Polymers 0.000 claims description 4
- 229910052750 molybdenum Inorganic materials 0.000 claims description 4
- 239000011733 molybdenum Substances 0.000 claims description 4
- 239000004584 polyacrylic acid Substances 0.000 claims description 4
- CKQGJVKHBSPKST-UHFFFAOYSA-N [Ni].P#[Mo] Chemical compound [Ni].P#[Mo] CKQGJVKHBSPKST-UHFFFAOYSA-N 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- IYFATESGLOUGBX-YVNJGZBMSA-N Sorbitan monopalmitate Chemical compound CCCCCCCCCCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O IYFATESGLOUGBX-YVNJGZBMSA-N 0.000 claims description 2
- HVUMOYIDDBPOLL-XWVZOOPGSA-N Sorbitan monostearate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O HVUMOYIDDBPOLL-XWVZOOPGSA-N 0.000 claims description 2
- 239000006185 dispersion Substances 0.000 abstract description 9
- 239000007921 spray Substances 0.000 abstract description 4
- 239000000243 solution Substances 0.000 description 33
- 239000003921 oil Substances 0.000 description 26
- 238000007598 dipping method Methods 0.000 description 20
- 238000005984 hydrogenation reaction Methods 0.000 description 12
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 6
- 239000002738 chelating agent Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 238000002803 maceration Methods 0.000 description 6
- 102000002322 Egg Proteins Human genes 0.000 description 4
- 108010000912 Egg Proteins Proteins 0.000 description 4
- 238000004517 catalytic hydrocracking Methods 0.000 description 4
- 210000003278 egg shell Anatomy 0.000 description 4
- 229910001453 nickel ion Inorganic materials 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 3
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 3
- 229940010552 ammonium molybdate Drugs 0.000 description 3
- 235000018660 ammonium molybdate Nutrition 0.000 description 3
- 239000011609 ammonium molybdate Substances 0.000 description 3
- 150000001768 cations Chemical class 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 241000519996 Teucrium chamaedrys Species 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000013522 chelant Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000002386 leaching Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000010814 metallic waste Substances 0.000 description 2
- DHRLEVQXOMLTIM-UHFFFAOYSA-N phosphoric acid;trioxomolybdenum Chemical compound O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.OP(O)(O)=O DHRLEVQXOMLTIM-UHFFFAOYSA-N 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 1
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- FCKYPQBAHLOOJQ-UHFFFAOYSA-N Cyclohexane-1,2-diaminetetraacetic acid Chemical compound OC(=O)CN(CC(O)=O)C1CCCCC1N(CC(O)=O)CC(O)=O FCKYPQBAHLOOJQ-UHFFFAOYSA-N 0.000 description 1
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- MNZHBXZOPHQGMD-UHFFFAOYSA-N acetic acid;azane Chemical compound N.CC(O)=O.CC(O)=O.CC(O)=O MNZHBXZOPHQGMD-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical group [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 235000012538 ammonium bicarbonate Nutrition 0.000 description 1
- 239000001099 ammonium carbonate Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical class OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000012050 conventional carrier Substances 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 229960001484 edetic acid Drugs 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000012854 evaluation process Methods 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000001802 infusion Methods 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000003863 metallic catalyst Substances 0.000 description 1
- 150000001455 metallic ions Chemical class 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 238000009828 non-uniform distribution Methods 0.000 description 1
- 238000009527 percussion Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Abstract
The present invention discloses a kind of residual oil hydrocatalyst and its preparation, then the preparation is dried the following steps are included: (1) sprays residuum hydrogenating and metal-eliminating catalyst carrier with the organic solvent of the surfactant containing Span；(2) catalyst is made in the carrier with the active metal solution impregnation steps (1) containing polypropylene acid group after dry, then dry, roasting.The residual oil hydrocatalyst of this method preparation has many advantages, such as high activity metal utilization rate, high metal dispersion degree, high activity.
Description
Technical field
The present invention relates to a kind of residual oil hydrocatalyst and its preparation, a kind of high metal dispersion degree, height are related in particular to
Active residual oil hydrocatalyst and its preparation.
Background technique
With domestic and international crude oil heaviness, in poor quality increasingly, residual hydrocracking technology has obtained increasingly extensive application.
Currently, it is to carry that the catalyst for hydrotreatment of residual oil industrially applied, which is usually the aluminium oxide with aluminium oxide or containing a small amount of auxiliary agent,
Body, using VIII race and VI B race metallic element as active component.In the preparation process of residual oil hydrocatalyst, generally by load
Then the aqueous solution of the one or many impregnating metal compounds of body is made, this catalyst system by dry and roasting process
Preparation Method is described in such as EP0469675.
In catalyst dipping process, the hole of carrier surface is contacted with active metal solution, due to the work of surface tension
With and generate capillary pressure, penetrate into active metal solution inside capillary, active component occur in hole diffusion and
Carrier surface absorption.During residual hydrogenation, into the active metal in aperture since component large-sized in residual oil can not
Into so that active metal is unable to get utilization, and causing the waste of active metal；Active metal carrier surface adsorb when,
Due to the interaction of active metal and carrier, so that in catalyst surface a degree of aggregation occurs for active metal, reduce
The dispersion degree of active metal, and the dispersion degree of the activity and selectivity of catalyst and active metal is closely related.How to improve
The utilization rate of active metal and dispersion degree are problems to be solved in current residual oil hydrocatalyst preparation process in catalyst.
Patent EP0181035A2 is disclosed in Hydrobon catalyst preparation using chelating agent, and chelating agent can be with leaching
Active metal in stain liquid forms metallo-chelate, can weaken the strong interaction between active component and carrier, improves and lives
Property metal dispersity.So far, there are more and more chelating agents such as ethylenediamine tetra-acetic acid, 1,2-diaminocyclohexane tetraacetic acid, ammonia
Triacetic acid, ethylenediamine, citric acid, triethylene glycol, ethylene glycol etc. are applied in the preparation process of Hydrobon catalyst.Patent CN
101330972B discloses a kind of method for preparing Hydrobon catalyst.This method is using infusion process preparation hydrofinishing catalysis
Agent, and chelating agent is added in maceration extract, the additive amount of chelating agent is generally 0.2~3 times of catalytic metal moles total number, leaching
Carrier drying temperature is to 200 DEG C high after stain, and temperature is made to be lower than the temperature that chelate largely decomposes, and obtains after dry without roasting
Obtained the dry catalyst of desired activities.Chelating agent is added in dipping solution, the dispersion degree of active metal can be improved, still
As residual oil be different from Hydrobon catalyst handled by feedstock oil, so the preparation process in residual oil hydrocatalyst also needs
Consider diffusion of the active metal in aperture.
Ammonium hydrogen carbonate is added in body phase hydrogenation catalyst disclosed in CN102049265A during coprecipitated,
Carbon dioxide is added in body phase hydrogenation catalyst disclosed in CN102451703A during coprecipitated, generates carbonate or bicarbonate
Salt, the above method is that a certain amount of gas is released in roasting process using it, under the percussion of gas, increases catalysis
The Kong Rong of agent, specific surface area make more metal active positions be exposed to the surface of catalyst, but such method can make cell channels
Collapse, pore size distribution disperse, mechanical strength reduces.
CN102861598A discloses hydrogenation catalyst of containing fluorin and its preparation of a kind of active metal component non-uniform Distribution
Method.The catalyst contains molding fluorine-containing hydration alumina support, at least one of load on this carrier is selected from VIII group
Non-noble metal metal salt and at least one metal salt selected from group vib metal, wherein along catalyst radial section be distributed,
The ratio between outer surface concentration and centre concentration of Section VIII race metal component are 0.1-0.9；The group vib metal group
The ratio between outer surface concentration and centre concentration for dividing are 0.1-0.8.Not only there is catalyst provided by the invention excellent hydrocarbon ils to add
Hydrogen refines performance, while preparation method is simple, production cost is low.Its disadvantage cannot also accomplish different acid materials well
Effective cooperation of material and metal active.
Patent CN102451722A discloses a kind of preparation method of eggshell hydrogenation catalyst.This method is used containing increasing
The active metal dipping solution of thick dose and active metal dispersing agent impregnates conventional carrier, and soaks under conditions of being passed through air and being bubbled
Stain, then through dry and roasting, obtain eggshell hydrogenation catalyst.Its process is more, comparatively laborious, and noble metal waste is tight
Weight.
Patent CN102451722B introduces a kind of preparation method of egg-shell catalyst, is by aluminium oxide precursor and double
Sub- surfactant, adhesive are uniformly mixed, and catalyst carrier is made in kneading, are then impregnated with the dipping solution containing thickener
Carrier, and impregnated under conditions of being passed through air and being bubbled, then through dry and roasting, obtain eggshell hydrogenation catalyst.Its process
It is more, it is comparatively laborious, and noble metal waste is serious.
CN201110133725.4 discloses a kind of special-shaped hydrocracking catalyst and its preparation method and application, catalyst
The method that preparation method uses post-treatment solution, makes metal uniform deposition on carrier, and do not migrate in subsequent drying process,
It is uniform to reach metal dispersion.Metal dispersion can be made uniform, and make carrier and metal that there is good cooperation, make catalytic performance
It improves.The invention hydrocracking catalyst optimum is used for middle oil type hydrocracking process.The method is primarily to make activity
Metal reaches evenly dispersed, but evenly dispersed active metal cannot reach the higher accumulation number of plies, with adding for formation high activity
There is bigger difference at hydrogen activity center.
Summary of the invention
In view of the deficiencies of the prior art, the present invention provides a kind of residual oil hydrocatalyst and preparation method thereof.Party's legal system
The advantages that active metal utilization of standby residual oil hydrocatalyst is high, metal dispersity is high and activity is high.
A kind of preparation of residual oil hydrocatalyst, comprising the following steps:
(1) residuum hydrogenating and metal-eliminating catalyst carrier is sprayed with the organic solvent of the surfactant containing Span, then dried；
(2) carrier with the active metal solution impregnation steps (1) containing polypropylene acid group after dry, then dry, roasting system
Obtain catalyst.
In the above method, residuum hydrogenating and metal-eliminating catalyst carrier as described in step (1) is alumina support, the oxygen
Commercial goods can be used by changing alumina supporter, can also be prepared according to the prior art.
In the above method, Span surfactant as described in step (1) is Span -40, Span -60, in Span-80
At least one, preferably Span-80.The organic solvent is at least one of ethyl alcohol, ether, methanol, preferred alcohol.It is organic
The concentration of Span surfactant is 0.01-40.0g/100ml, preferably 0.01-20.0g/100ml in solution.Drying condition
It is dried in vacuo 2-24 hours under the conditions of being 40-100 DEG C.It, can be with using the organic solution sprayed carrier of the surfactant containing Span
The polarity and free energy for making carrier surface reduce, and weaken the capillary pressure in dipping process, reduce the work entered in aperture hole
Property metal, improve the utilization rate of active metal, and the polyacrylic acid for being conducive to dipping is uniformly distributed.
In the above method, in the active metal solution described in step (2) containing polypropylene acid group polypropylene root origin in
Polyacrylic acid or Sodium Polyacrylate, the concentration of polypropylene acid group are 0.1-10.0g/100ml, preferably 0.1-5.0 g/100ml.
In the above method, active metal solution is molybdenum nickel phosphorus solution in step (2).The drying condition is in air
80-150 DEG C 2-15 hours dry, and roasting condition roasts 3-5 hours under the conditions of being 350-650 DEG C.
A kind of residual oil hydrocatalyst prepared using the above method, is formed as follows: on the basis of the quality of catalyst, oxygen
The content for changing molybdenum is 2.0%-20.0%, and preferably 4.0%-16.0%, the content of nickel oxide is 0.5%-10.0%, preferably 0.5%-
6.0%, the content of phosphorus is 0.01%-6.00%, preferably 0.10%-3.00%.
Result of study shows that presence is stronger near macromolecular chain due to the effect of carboxylate radical anion on macromolecular chain
Electrostatic force so that the electrostatic attraction between carboxylate radical and cation on macromolecular chain is much larger than corresponding monomeric carboxylic acids root
With the electrostatic attraction between identical cation, carboxylate radical increases the constraint effect of cation with polymer dissociation degree, is positive
Ion valence mumber increases, ionic radius reduces and increases.Therefore, polyacrylic acid and its sodium salt act on the constraint of bivalent metal ion
It is strong to compare monovalent metallic ion.After Sodium Polyacrylate is added in active metal maceration extract, high score that Sodium Polyacrylate dissociates
After daughter ion is in conjunction with the nickel ion of divalent, play the role of fixed nickel ion, in combination with the macroion of nickel ion
Still with the mutual electrostatic repulsion of phosphomolybdic acid root in negative electrical charge, with maceration extract, play the role of dispersed active metal molybdenum.
The method of the present invention sprays residuum hydrogenating and metal-eliminating catalyst carrier using the organic solvent of the surfactant containing Span,
The polarity and free energy of carrier surface are reduced, the capillary pressure in dipping process is weakened, reduces the activity entered in aperture hole
Metal, the Sodium Polyacrylate in maceration extract plays fixed effect to nickel ion, while effectively having dispersed phosphomolybdic acid root, makes
Obtaining active metal nickel and molybdenum in catalyst dipping process can effectively disperse, and prevent from assembling, improve catalyst surface active
The dispersion degree of metal.
Specific embodiment
The effect and effect of the method for the present invention are further illustrated below with reference to embodiment, but are not limited to following embodiment.
Embodiment 1
(1) the industrial residuum hydrogenating and metal-eliminating catalyst alumina catalyst support of 100g is weighed, is with 100ml Span-80 concentration
The ethanol solution of 0.5g/100ml sprays, and is then dried in vacuo 5 hours under the conditions of 60 DEG C；
(2) it prepares dipping solution: ammonium molybdate, nickel nitrate and phosphoric acid being added to the water dissolution, Sodium Polyacrylate is then added, obtains
Dipping solution, wherein the content of molybdenum oxide is 25.7 g/100ml, and the content of nickel oxide is 5.8g/100ml, and the content of phosphorus is
2.1g/100ml, the content of Sodium Polyacrylate are 0.5 g/100ml.After impregnating above-mentioned drying using prepared dipping solution
It is 5 hours dry under the conditions of 120 DEG C after catalyst carrier 2 hours, roast 4 hours under the conditions of 500 DEG C then to get residual oil
Hydrogenation catalyst A.
Embodiment 2
With embodiment 1, only when being sprayed with the ethanol solution containing Span-80, the Span-80 concentration used is 1.0g/100ml
Ethanol solution, 5 hours are dried in vacuo under the conditions of 60 DEG C, then with the load after the dipping solution impregnation drying in embodiment 1
Body obtains residual oil hydrocatalyst B.
Embodiment 3
With embodiment 1, only the content of Sodium Polyacrylate is 1.0g/100ml, dip time 3 in the dipping solution of preparation
Hour, it is then 5 hours dry under the conditions of 120 DEG C, 4 hours are roasted under the conditions of 500 DEG C to get residual oil hydrocatalyst C.
Embodiment 4
With embodiment 1, only when being sprayed with the ethanol solution containing Span-80, the Span-80 concentration used is 5.0g/100ml
Ethanol solution, be dried in vacuo 6 hours under the conditions of 50 DEG C, using Sodium Polyacrylate content be 1.0g/100ml activity gold
Carrier after belonging to dipping solution impregnation drying, dip time are 3 hours, then 5 hours dry under the conditions of 120 DEG C, at 500 DEG C
Under the conditions of roast 4 hours to get residual oil hydrocatalyst D.
Embodiment 5
With embodiment 1, only when being sprayed with the ethanol solution containing Span-80, the Span-80 concentration used is 5.0g/100ml
Ethanol solution, be dried in vacuo 6 hours under the conditions of 70 DEG C, using Sodium Polyacrylate content be 5.0g/100ml activity gold
Carrier after belonging to dipping solution impregnation drying, dip time are 3 hours, then 5 hours dry under the conditions of 120 DEG C, at 500 DEG C
Under the conditions of roast 4 hours to get residual oil hydrocatalyst E.
Comparative example 1
With embodiment 1, the process of the ethanol solution containing Span-80 is sprayed without step (1).Detailed process is as follows: by ammonium molybdate,
Nickel nitrate and phosphoric acid are added to the water dissolution, and Sodium Polyacrylate is then added, and obtain dipping solution, and wherein the content of molybdenum oxide is
25.7 g/100ml, the content of nickel oxide are 5.8g/100ml, and the content of phosphorus is 2.1g/100ml, and the content of Sodium Polyacrylate is
0.5 g/100ml.After impregnating the catalyst carrier after above-mentioned drying 2 hours using prepared dipping solution, in 120 DEG C of conditions
Then lower drying 5 hours roasts 4 hours under the conditions of 500 DEG C to get residual oil hydrocatalyst F.
Comparative example 2
With embodiment 1, only there is no Sodium Polyacrylate in step (2) maceration extract.It is de- to weigh the industrial residual hydrogenation of 100g
Metallic catalyst carrier aluminium oxide, Span-80 concentration is that the ethanol solution of 0.5g/100ml sprays, then true under the conditions of 60 DEG C
Sky is 5 hours dry；Ammonium molybdate, nickel nitrate and phosphoric acid are added to the water to obtain dipping solution, wherein the content of molybdenum oxide is 25.7
G/100ml, the content of nickel oxide are 5.8g/100ml, and the content of phosphorus is 2.1g/100ml.It is soaked using prepared dipping solution
It is 5 hours dry under the conditions of 120 DEG C behind catalyst carrier 2 hours after the above-mentioned drying of stain, then 4 are roasted under the conditions of 500 DEG C
Hour is to get residual oil hydrocatalyst G.
Comparative example 3
The industrial residuum hydrogenating and metal-eliminating catalyst carrier of 100g is weighed, is impregnated using conventional molybdenum nickel phosphorus solution,
The content of molybdenum oxide is 25.7 g/100ml in maceration extract, and the content of nickel oxide is 5.8g/100ml, and the content of phosphorus is 2.1g/
100ml.Dipping is 5 hours dry under the conditions of 120 DEG C after 3 hours, roasts 4 hours under the conditions of 500 DEG C to get residual hydrogenation
Catalyst H.
The catalyst property that above-described embodiment and comparative example are prepared is shown in Table 1.To obtained by above-described embodiment and comparative example
Catalyst carry out activity rating on 200ml residual hydrogenation midget plant.The residual oil raw material property that activity rating uses is shown in Table
2；Process conditions are shown in Table 3；Evaluating catalyst the results are shown in Table 4.
1 embodiment of table prepares the property of catalyst
Note: IMo/IAl、INi/IAlRespectively represent the active metal atom of catalyst surface and the number ratio of aluminium atom.
Activity is carried out on 200ml residual hydrogenation midget plant to catalyst obtained by above-described embodiment and comparative example to comment
Valence.Residual oil raw material property used and evaluation process conditions are shown in Table 2 and table 3, and evaluating catalyst the results are shown in Table 4.
2 residual oil raw material oil nature of table
3 process conditions of table
4 evaluating catalyst result of table
In table 4, HDS is hydrodesulfurization rate, and HDCCR is removal of ccr by hydrotreating rate, and HDM is hydrodemetallization rate.
Claims (10)
1. a kind of preparation of residual oil hydrocatalyst, it is characterised in that: the following steps are included:
(1) residuum hydrogenating and metal-eliminating catalyst carrier is sprayed with the organic solvent of the surfactant containing Span, then dried；
(2) carrier with the active metal solution impregnation steps (1) containing polypropylene acid group after dry, then dry, roasting system
Obtain catalyst.
2. according to the method described in claim 1, it is characterized by: residuum hydrogenating and metal-eliminating catalyst as described in step (1)
Carrier is aluminium oxide.
3. according to the method described in claim 1, it is characterized by: Span surfactant as described in step (1) is Span-
40, Span -60, at least one of Span-80.
4. according to the method described in claim 1, it is characterized by: organic solvent as described in step (1) be ethyl alcohol, ether,
At least one of methanol, the concentration of Span surfactant is 0.01-40.0g/100ml in organic solution.
5. according to the method described in claim 1, it is characterized by: drying condition is true under the conditions of being 40-100 DEG C in step (1)
Sky is 2-24 hours dry.
6. according to the method described in claim 1, it is characterized by: the activity described in step (2) containing polypropylene acid group is golden
Belonging to polypropylene root origin in solution, in polyacrylic acid or Sodium Polyacrylate, the concentration of polypropylene acid group is 0.1-10.0g/100ml.
7. according to the method described in claim 1, it is characterized by: active metal solution is molybdenum nickel phosphorus solution in step (2).
8. according to the method described in claim 1, it is characterized by: drying condition described in step (2) is 80- in air
150 DEG C 2-15 hours dry, and roasting condition roasts 3-5 hours under the conditions of being 350-650 DEG C.
9. a kind of residual oil hydrocatalyst prepared using claim 1 to 8 either method, it is characterised in that: composition is as follows: with
On the basis of the quality of catalyst, the content of molybdenum oxide is 2.0%-20.0%, and the content of nickel oxide is 0.5%-10.0%, the content of phosphorus
For 0.01%-6.00%.
10. catalyst according to claim 9, it is characterised in that: composition is as follows: on the basis of the quality of catalyst, oxygen
The content for changing molybdenum is 4.0%-16.0%, and the content of nickel oxide is 0.5%-6.0%, and the content of phosphorus is 0.10%-3.00%.
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| CN112742424A (en) * | 2019-10-29 | 2021-05-04 | 中国石油化工股份有限公司 | Preparation method of heavy oil hydrotreating catalyst |
| CN112742429A (en) * | 2019-10-29 | 2021-05-04 | 中国石油化工股份有限公司 | Preparation method of hydrotreating catalyst |
| CN112973716A (en) * | 2019-12-16 | 2021-06-18 | 北京中能炜业科技发展有限公司 | Hydrofining catalyst and preparation method thereof |
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| WO2006112890A1 (en) * | 2005-04-12 | 2006-10-26 | Headwaters Technology Innovation Llc | Nanocatalyst anchored onto acid functionalized solid support and methods of making and using same |
| CN101330972A (en) * | 2005-12-14 | 2008-12-24 | 先进炼制技术有限公司 | Method of making hydroprocessing catalyst |
| CN101433848A (en) * | 2007-11-15 | 2009-05-20 | 中国石油化工股份有限公司 | Heavy oil hydrogenating treatment catalyst and preparation method thereof |
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| WO2006112890A1 (en) * | 2005-04-12 | 2006-10-26 | Headwaters Technology Innovation Llc | Nanocatalyst anchored onto acid functionalized solid support and methods of making and using same |
| CN101330972A (en) * | 2005-12-14 | 2008-12-24 | 先进炼制技术有限公司 | Method of making hydroprocessing catalyst |
| CN101433848A (en) * | 2007-11-15 | 2009-05-20 | 中国石油化工股份有限公司 | Heavy oil hydrogenating treatment catalyst and preparation method thereof |
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| CN112742424A (en) * | 2019-10-29 | 2021-05-04 | 中国石油化工股份有限公司 | Preparation method of heavy oil hydrotreating catalyst |
| CN112742429A (en) * | 2019-10-29 | 2021-05-04 | 中国石油化工股份有限公司 | Preparation method of hydrotreating catalyst |
| CN112973716A (en) * | 2019-12-16 | 2021-06-18 | 北京中能炜业科技发展有限公司 | Hydrofining catalyst and preparation method thereof |
| CN112973716B (en) * | 2019-12-16 | 2023-08-18 | 山西腾茂科技股份有限公司 | Hydrofining catalyst and preparation method thereof |
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