CN1718684A - Preparation method of hydrogenated process catalyst - Google Patents
Preparation method of hydrogenated process catalyst Download PDFInfo
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- CN1718684A CN1718684A CN 200410020927 CN200410020927A CN1718684A CN 1718684 A CN1718684 A CN 1718684A CN 200410020927 CN200410020927 CN 200410020927 CN 200410020927 A CN200410020927 A CN 200410020927A CN 1718684 A CN1718684 A CN 1718684A
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- catalyst
- body catalyst
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- fluorine
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- 239000003054 catalyst Substances 0.000 title claims abstract description 97
- 238000000034 method Methods 0.000 title claims description 54
- 238000002360 preparation method Methods 0.000 title claims description 33
- 239000000843 powder Substances 0.000 claims abstract description 39
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000011737 fluorine Substances 0.000 claims abstract description 26
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 26
- 239000000243 solution Substances 0.000 claims abstract description 14
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 13
- 238000001035 drying Methods 0.000 claims abstract description 10
- 239000003929 acidic solution Substances 0.000 claims abstract description 8
- 238000010298 pulverizing process Methods 0.000 claims abstract description 4
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 24
- 239000011230 binding agent Substances 0.000 claims description 16
- -1 ammonium salt compound Chemical class 0.000 claims description 13
- 239000002253 acid Substances 0.000 claims description 12
- 238000000975 co-precipitation Methods 0.000 claims description 9
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 8
- 150000003863 ammonium salts Chemical class 0.000 claims description 8
- 229910017604 nitric acid Inorganic materials 0.000 claims description 8
- LDDQLRUQCUTJBB-UHFFFAOYSA-N ammonium fluoride Chemical group [NH4+].[F-] LDDQLRUQCUTJBB-UHFFFAOYSA-N 0.000 claims description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 6
- 150000002736 metal compounds Chemical class 0.000 claims description 6
- 238000001556 precipitation Methods 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- 230000018044 dehydration Effects 0.000 claims description 4
- 238000006297 dehydration reaction Methods 0.000 claims description 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 4
- 229940070337 ammonium silicofluoride Drugs 0.000 claims description 3
- 239000003637 basic solution Substances 0.000 claims description 3
- 229910052750 molybdenum Inorganic materials 0.000 claims description 3
- 238000001179 sorption measurement Methods 0.000 claims description 3
- 229910052721 tungsten Inorganic materials 0.000 claims description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 235000019260 propionic acid Nutrition 0.000 claims description 2
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims description 2
- 239000012266 salt solution Substances 0.000 claims 1
- 239000011148 porous material Substances 0.000 abstract description 14
- 230000002378 acidificating effect Effects 0.000 abstract description 3
- 150000001875 compounds Chemical class 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 abstract 2
- 239000000853 adhesive Substances 0.000 abstract 1
- 230000001070 adhesive effect Effects 0.000 abstract 1
- 150000003868 ammonium compounds Chemical class 0.000 abstract 1
- 238000001354 calcination Methods 0.000 abstract 1
- 238000007493 shaping process Methods 0.000 abstract 1
- 230000000694 effects Effects 0.000 description 25
- 229910052751 metal Inorganic materials 0.000 description 21
- 239000002184 metal Substances 0.000 description 21
- 238000002156 mixing Methods 0.000 description 16
- 238000000465 moulding Methods 0.000 description 12
- 239000000203 mixture Substances 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 239000012752 auxiliary agent Substances 0.000 description 7
- 239000012018 catalyst precursor Substances 0.000 description 7
- 239000003921 oil Substances 0.000 description 7
- 239000000463 material Substances 0.000 description 6
- 238000005984 hydrogenation reaction Methods 0.000 description 5
- 239000012535 impurity Substances 0.000 description 5
- 238000001935 peptisation Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 101150009760 CATB gene Proteins 0.000 description 4
- 101100453510 Streptomyces coelicolor (strain ATCC BAA-471 / A3(2) / M145) katG gene Proteins 0.000 description 4
- 101150071300 catC gene Proteins 0.000 description 4
- 101150111658 katE gene Proteins 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 101100273316 Acinetobacter baylyi (strain ATCC 33305 / BD413 / ADP1) catF gene Proteins 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 3
- 101100296558 Pseudomonas knackmussii (strain DSM 6978 / LMG 23759 / B13) pcaF gene Proteins 0.000 description 3
- 101100494806 Pseudomonas syringae pv. syringae katB gene Proteins 0.000 description 3
- 239000010953 base metal Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 description 2
- 206010013786 Dry skin Diseases 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 2
- 239000005864 Sulphur Substances 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000010779 crude oil Substances 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 235000021050 feed intake Nutrition 0.000 description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 239000002808 molecular sieve Substances 0.000 description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 2
- IRPGOXJVTQTAAN-UHFFFAOYSA-N 2,2,3,3,3-pentafluoropropanal Chemical compound FC(F)(F)C(F)(F)C=O IRPGOXJVTQTAAN-UHFFFAOYSA-N 0.000 description 1
- KLZUFWVZNOTSEM-UHFFFAOYSA-K Aluminum fluoride Inorganic materials F[Al](F)F KLZUFWVZNOTSEM-UHFFFAOYSA-K 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 241000219793 Trifolium Species 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- QGAVSDVURUSLQK-UHFFFAOYSA-N ammonium heptamolybdate Chemical compound N.N.N.N.N.N.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.[Mo].[Mo].[Mo].[Mo].[Mo].[Mo].[Mo] QGAVSDVURUSLQK-UHFFFAOYSA-N 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 229910021417 amorphous silicon Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000000796 flavoring agent Substances 0.000 description 1
- 235000019634 flavors Nutrition 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000007669 thermal treatment Methods 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
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- Catalysts (AREA)
Abstract
A process for preparing the hydrocatalyst with high pore volume and specific surface area includes such steps as codepositing of the solution of metallic compounds, dewatering, pulverizing to obtain the main body of catalyst, sufficiently contacting with the ammonium compound of fluorine to make the fluorine to be combined with said main body of catalyst and adsorb the released ammonia by the millipores of catalyst powder, adding acidic solution or acidic adhesive, shaping, drying and calcining.
Description
Technical field
The present invention relates to a kind of preparation method of hydrotreatment catalyst, particularly contain the preparation method of hydrotreatment catalyst of auxiliary agent fluorine.
Background technology
Contain sulphur, nitrogen, oxygen and metal impurities in crude oil and the distillate that from crude oil, obtains.The existence of these impurity not only influences the stability of oil product, and in use also can discharge SO
x, NO
xDeng the obnoxious flavour contaminate environment.In the secondary processing process of oil product, the existence of sulphur, nitrogen, oxygen and metal impurities can make poisoning of catalyst.Distillate hydrogenation is handled and is meant that under certain temperature and pressure stock oil contacts with catalyzer with hydrogen, removes impurity, and the saturated process of aromatic hydrocarbons.
The hydrotreating catalyst of excellent property must have good hydrogenation activity and certain cracking activity, in addition, and from considering that economically Preparation of catalysts technology should be tried one's best simply.Oxide compound or sulfide that typical hydrotreating catalyst is VIII family and vib metal are supported on the carrier.In general, these catalyzer are the aqueous solution by carrier one or many impregnating metal compound, utilize one or more dryings and roasting process then and make.Also can be with solid support material and VIII family and vib metal composition prepared by co-precipitation hydrotreating catalyst.In order to improve metal and carrier interactions, improve the acidity of catalyzer, the adding auxiliary agent of still needing sometimes.Fluorine is one of hydrotreating catalyst auxiliary agent commonly used.Add the auxiliary agent fluorine in the hydrotreating catalyst and can improve metal and carrier interactions, improve the acidity of catalyzer, improve the ability that the anti-organic basic nitride of catalyzer is poisoned.Chinese patent CN85104438, CN98114342, U.S. Pat 3,434,964, US4,285,836 and US4,220,557 have described the preparation method of hydrotreatment catalyst that contains the auxiliary agent fluorine respectively.
Because carrier itself is not or have a very low activity, the above-mentioned activity of such catalysts that contains carrier is not high.EP0379433 has narrated a kind of carrier (generally being called body catalyst) Preparation of catalysts method that do not have, wherein with a kind of VIII family's base metal composition and the co-precipitation of a kind of vib metal composition.US4596785 and US4820677 have narrated another kind of method for preparing catalyst, promptly make in the co-precipitation in the presence of the sulfide with the water-soluble cpds of a kind of VIII family's base metal composition and two kinds of VIB.CN1342102A has narrated another kind of Preparation of catalysts method, the vib metal composition of a kind of VIII family base metal composition of solubilised state and at least two kinds of solubilised state is mixed in reactor and react, obtain a kind of stable throw out, then this throw out is vulcanized.This method can prepare active very high body catalyst, particularly adds the mixed metal catalyst that obtains after the binding agent moulding and has quite high hydrodenitrogenationactivity activity.
Above described coprecipitation method prepare the method for catalyzer, though can prepare active very high catalyzer, but, the pore volume and the specific surface area of the catalyzer of this method preparation are very low, in addition, the precipitated metal thing that aforesaid method obtains can not directly apply to existing full scale plant, and they must make pellet type catalyst through forming step and could use at full scale plant, and their pore volume and specific surface area can further reduce in moulding process.Can prepare pore volume and the higher catalyzer of specific surface area though adopt extreme condition, but, at this moment need low or do not have a metal (for example chromium) of hydrogenation activity with hydrogenation activity, this will cause active metallic content to reduce and molybdenum (or tungsten) nickle atom does not match than seriously, reduced activity of such catalysts, a large amount of metals are not well utilized.Catalyzer pore volume and specific surface area reduce reaction contact area, and the reactive metal utilization ratio descends, and the ability of holding impurity of catalyzer reduces, and particularly is that it is poorer that the stability of catalyzer will become at processing heavy oil.In moulding process, add pore volume and the specific surface area that solid support material can improve catalyzer, still, because the basic non-activity of carrier loses catalyst activity inevitably so add solid support material.
Summary of the invention
At the deficiencies in the prior art, the invention provides a kind of preparation method of fluorine-containing mixed metal catalyst, the pore volume of the catalyzer of this method preparation is compared with the mixed metal catalyst of prior art for preparing with specific surface area and is significantly improved, and give full play to the effect of auxiliary agent fluorine, improve prepared activity of such catalysts.
Method for preparing catalyst of the present invention may further comprise the steps: the metal compound solution precipitation, and the powdery body catalyst is made in throw out dehydration, pulverizing; The powdery body catalyst is fully contacted with the ammonium salt compound of fluorine, and fluorion combines with body catalyst, and the ammonia that discharges is by the micro-porous adsorption of body catalyst; Then this body catalyst powder is added acidic solution or acid binding agent aftershaping, drying and roasting is made catalyzer.
After the present invention adds the ammonium salt compound of fluorine at the body catalyst powder; fluorion combines with body catalyst; improve the latent activity of catalyst activity metal; the ammonia that discharges is formed the ammonium salt microcrystallite by body catalyst powder absorption back and acid effect; these particulates be dispersed in the original duct of body catalyst and bulk catalyst particles in; in moulding process, protected original duct; thereafter these ammonium salt microcrystallite decompose volatilization in the roasting process; guarantee that promptly original duct reduces the loss; formed new micropore again; thereby improved the pore volume and the specific surface area of catalyzer, and then improved the use properties of catalyzer.
Embodiment
Preparation of catalysts method of the present invention is that the powdery body catalyst of coprecipitation method preparation fully contacts with the ammonium salt compound of fluorine, and fluorion combines with body catalyst, and the ammonia that discharges is by the micro-porous adsorption of body catalyst; Then this body catalyst powder is added acidic solution or acid binding agent aftershaping, drying and roasting is made catalyzer.Particularly, the present invention can may further comprise the steps:
(1) metal compound solution co-precipitation;
(2) throw out that step (1) is obtained removes all or part of water, pulverizing, makes the body catalyst powder;
(3) the body catalyst powder that step (2) is obtained fully contacts with the ammonium salt compound of fluorine;
(4) the body catalyst powder of adsorb ammonia that step (3) is obtained or ammonium and acidic solution or acid binding agent mixing aftershaping;
(5) the catalyst precursor thing drying and roasting that step (4) is obtained is made catalyzer.
The described coprecipitation method of step (1) prepares body catalyst and can adopt ordinary method of the prior art, adds the precipitation agent precipitation as the saline solution with required metal.Metallic salt is generally group vib and VIII family metallic salt, as one or more of the saline solution of metals such as Mo, W, Co, Ni, precipitation agent can select the material of white and above-mentioned salt generation precipitin reaction, as obtaining with basic solution that contains Mo and/or W and the methods such as acidic solution co-precipitation that contain Co and/or Ni.Concrete grammar and condition are well known to those skilled in the art, as preparing by the described process of CN1342102A.
The described body catalyst dehydration of step (2) is according to the method for this area routine, it is the process that volatile matter removes in the catalyst precursor thing, the general operation temperature is 100 ℃～600 ℃, be preferably 200 ℃～500 ℃, be preferably 250 ℃～450 ℃, time was generally 1～30 hour, was preferably 2～10 hours.
In the abundant contact process of ammonium salt compound of described body catalyst powder of step (3) and fluorine, the ammonium salt compound of fluorine can be Neutral ammonium fluoride, ammonium silicofluoride etc.The body catalyst powder fully contacts with the ammonium salt compound of fluorine, when using solid chemical compound, fluorion is fully combined with body catalyst.The ammonia that discharges should make the body catalyst powder fully adsorb.When using the ammonium salt compound solution of fluorine, should make the body catalyst powder keep pulverulence, solution usage is generally 0.01～1ml/g pressed powder.The body catalyst powder with can mix with the common carrier raw material powder before the ammonium salt compound of fluorine contacts.Fluorine content is 0.2wt%～7.0wt% in the catalyzer, is preferably 0.5wt%～5.0wt%.Mixing process is preferably in the encloses container carries out.
The body catalyst powder of described adsorb ammonia of step (4) or ammonium and acidic solution or acid binding agent mixing process, the consumption of acid can be determined according to the factors such as peptization of material, is generally 0.02～0.2mol/100g pressed powder.Acid can be mineral acid or organic acid, and suitable sour kind and consumption are that those skilled in the art are known, as nitric acid, hydrochloric acid, acetate, propionic acid, citric acid etc.The adding binding agent can improve the pore volume and the specific surface area of catalyzer, and the intensity of catalyzer, in addition, because the active low or basic non-activity of binding agent reduces activity of such catalysts so add binding agent.
Moulding process can be moulding processes such as extrusion, compressing tablet or a ball, and the shape of catalyzer can be sphere, sheet, cylinder bar or special-shaped bars such as trifolium bar, Herba Galii Bungei bar.
In catalyst preparation process, can also add additive modification as required, as Si, P, Ti, Zr etc.
In catalyst preparation process, can also add carrier components as required, as aluminum oxide etc.
In catalyst preparation process, can also add acidic components as required, as molecular sieve, amorphous silicon aluminium etc.Also can add their mixture as required.
Auxiliary agent, carrier component and acidic components can add in bulk catalyst preparation process, also can add in the ammonium salt compound of thereafter mixed fluorine and moulding process, and adding kind, quantity and method all is that persons skilled in the art are known.
Described drying of step (5) and roasting condition can be adopted the condition of capable territory routine, and drying was generally descended dry 1～10 hour at 90～200 ℃, and roasting is generally 300～550 ℃ of following roastings 1～10 hour.
In catalyst preparation process, can also add ammonia or other ammonium salt simultaneously, with the pore volume and the specific surface area of further increase catalyzer.
The feature that the invention is further illustrated by the following examples, but these embodiment can not limit the present invention.
Embodiment 1
Prepare the body catalyst powder by the described method of CN1342102A.
(1) Ammonium Heptamolybdate and ammonium metawolframate are dissolved in fully and mix at first reactor, and temperature is risen to 90 ℃.
(2) in first reactor, add ammoniacal liquor to form a kind of basic solution.
(3) nickelous nitrate is dissolved in second reactor and be heated to 90 ℃.
(4) solution with step (3) gained under agitation drops in first reactor, with formed suspension restir 30 minutes, with sedimentation and filtration and washing, throw out is following dry 5 hours at 120 ℃ in air, 385 ℃ of following thermal treatment is 1 hour in air, pulverize then and sieve, obtain the body catalyst powder with 180 mesh sieves.
Various materials feed intake and comprise 38.9w%NiO, 22.2w%MoO by body catalyst in the said process
3And 38.9w%WO
3Ratio feed intake.
Embodiment 2
The inventive method prepares catalyzer.
(1) with 0.06mol nitric acid and 120ml water and 15g (butt) SB-aluminum oxide powder (Germany produces) thorough mixing peptization, makes binding agent.
(2) body catalyst 85g (butt) powder of 8g Neutral ammonium fluoride and embodiment 1 preparation is joined fully contact mixing in the airtight mixing tank.
(3) after the body catalyst powder of the adsorb ammonia that step 2 is obtained and binding agent that step 1 obtains mixed, extruded moulding was made the catalyst precursor thing.
(4) step 3 is obtained catalyst precursor thing 120 ℃ of dryings 2 hours in air.
(5) handled 1 hour under 350 ℃ of catalyzer to the catalyzer dried strip that step 4 obtains.The catalyzer note of preparation is catA.
Embodiment 3
The inventive method prepares catalyzer.
(1) the body catalyst 85g (butt) that gets embodiment 1 preparation pulverizes back and 15g (butt) SB-aluminum oxide powder (Germany produces) thorough mixing.
(2) the 8g Neutral ammonium fluoride is added fully dissolving in the 20ml deionized water.
(3) body catalyst 85g (butt) powder that step 2 is obtained ammonium fluoride solution and embodiment 1 preparation joins and fully contacts mixing in the airtight mixing tank.
(4) powder mix thorough mixing, the extruded moulding of the adsorb ammonia that 0.06mol nitric acid and 100ml water nitric acid and water and step 3 are obtained are made the catalyst precursor thing.
(5) with embodiment 2 steps 4.
(6) with embodiment 2 steps 5.
The catalyzer note of preparation is catB.
Embodiment 4
The inventive method prepares catalyzer.
Replace Neutral ammonium fluoride with the 6g ammonium silicofluoride, all the other are with embodiment 3.
The catalyzer note of preparation is catC.
Embodiment 5
The inventive method prepares catalyzer.
(1) with 0.04mol nitric acid and 100ml water and 15g (butt) SB-aluminum oxide powder (Germany produces) thorough mixing peptization, makes binding agent.
(2) the 8g Neutral ammonium fluoride is added fully dissolving in the 20ml deionized water.
(3) body catalyst 80g (butt) powder that step 2 is obtained ammonium fluoride solution and embodiment 1 preparation joins and fully contacts mixing in the airtight mixing tank.
(4) the body catalyst powder of the adsorb ammonia that step 3 is obtained and 0.02mol phosphoric acid and 5gUSY molecular sieve (Fushun Petrochemical Research Institute's production) mix.Other is with embodiment 2 steps 3.
(5) with embodiment 2 steps 4.
(6) with embodiment 2 steps 5.
The catalyzer note of preparation is catD
Comparative example 1
(1) with 0.04mol nitric acid and 120ml water and 15g (butt) SB-aluminum oxide powder (Germany produces) thorough mixing peptization, makes binding agent.
(2) after the body catalyst 85g (butt) that gets embodiment 1 preparation pulverized binding agent that back and step 1 obtain and mixes, extruded moulding was made the catalyst precursor thing.
(3) with embodiment 2 steps 4.
(4) with embodiment 2 steps 5.
The catalyzer note of preparation is catE.
Comparative example 2
(1) with 0.04mol nitric acid and 120ml water and 15g (butt) SB-aluminum oxide powder (Germany produces) thorough mixing peptization, makes binding agent.
(2) the body catalyst 85g (butt) that gets embodiment 1 preparation pulverize and 5.9g aluminum fluoride thorough mixing after after the binding agent that obtains with step 1 mixes, extruded moulding is made the catalyst precursor thing.
(3) with embodiment 2 steps 4.
(4) with embodiment 2 steps 5.
The catalyzer note of preparation is catF.
The main physico-chemical property of catalyzer sees Table 1.
As can be seen from Table 1, adopt the pore volume and the specific surface area of the mixed metal catalyst of the inventive method preparation to significantly improve, overcome body catalyst or the mixed metal catalyst pore volume and the low deficiency of specific surface area of prior art for preparing.
Embodiment 6
Present embodiment is the activity rating of catalyst test.
The catalyst activity evaluation test is carried out on the 40ml small hydrogenation device, before the activity rating catalyzer is carried out prevulcanized.The evaluating catalyst condition is hydrogen dividing potential drop 14.7MPa, and temperature of reaction is 380 ℃, volume space velocity 1.0h
-1, hydrogen to oil volume ratio 1000: 1.Active evaluation test sees Table 2 with stock oil character, and active evaluation test the results are shown in Table 3.
From the data of table 3 as can be seen, adopt identical stock oil, under identical processing condition, adopt catA, catB, the catC of the inventive method preparation, the denitrification activity of four kinds of catalyzer of catD obviously to be better than adopting the catalyzer of prior art for preparing.
As can be seen; after the present invention adds the ammonium salt compound of fluorine at the body catalyst powder; fluorion combines with body catalyst; the ammonia that discharges is formed the ammonium salt microcrystallite by body catalyst powder absorption back and acid effect; these particulates be dispersed in the original duct of body catalyst and bulk catalyst particles in; in moulding process, protected original duct; thereafter these ammonium salt microcrystallite decompose volatilization in the roasting process; guarantee that promptly original duct reduces the loss; formed new micropore again; thereby improved the pore volume and the specific surface area of catalyzer, improve the latent activity of catalyst activity metal.
Table 1 catalyzer physico-chemical property
| Physico-chemical property | catA | catB | catC | catD | catE | catF |
| Pore volume, ml/g specific surface area, m 2/ g crushing strength, N/mm | 0.231 133 10.1 | 0.243 137 10.5 | 0.213 125 11.0 | 0.245 151 11.4 | 0.136 107 11.9 | 0.132 104 11.5 |
Table 2 stock oil character
| Density (20 ℃), g/cm 3Boiling range, ℃ IBP EBP S, μ g/g N, μ g/g | 0.8244 197 350 1000 1226 |
Table 3 evaluating catalyst result
| Catalyzer | catA | catB | catC | catE | catF |
| Relative denitrification activity, % | 124 | 127 | 114 | 100 | 103 |
Claims (10)
1, a kind of preparation method of hydrotreatment catalyst may further comprise the steps: the metal compound solution precipitation, and the powdery body catalyst is made in throw out dehydration, pulverizing; The powdery body catalyst is fully contacted with the ammonium salt compound of fluorine, and fluorion combines with body catalyst, and the ammonia that discharges is by the micro-porous adsorption of body catalyst; Then this body catalyst powder is added acidic solution or acid binding agent aftershaping, drying and roasting is made catalyzer.
2, in accordance with the method for claim 1, it is characterized in that described metal compound solution is selected from one or more of Mo, W, Co, Ni metallic salt solution.
3, in accordance with the method for claim 1, it is characterized in that described metal compound solution precipitation obtains with basic solution that contains Mo and/or W and the acidic solution coprecipitation method that contains Co and/or Ni.
4, in accordance with the method for claim 1, it is characterized in that described body catalyst dehydration conditions is: service temperature is 100 ℃～600 ℃, and the time was generally 1～30 hour.
5, in accordance with the method for claim 1, it is characterized in that the ammonium salt compound of described fluorine is selected from Neutral ammonium fluoride, ammonium silicofluoride, the ammonium salt of fluorine is with pressed powder or solution form and body catalyst powder mixes.
6, in accordance with the method for claim 5, the ammonium salt that it is characterized in that fluorine makes the body catalyst powder keep pulverulence during with solution form and body catalyst powder mixes, and solution usage is generally 0.01～1ml/g pressed powder.
7, in accordance with the method for claim 1, the ammonium salt add-on that it is characterized in that described fluorine is that fluorine content is 0.2wt%～7.0wt% in the final catalyzer.
8, in accordance with the method for claim 1, the consumption that it is characterized in that described acid is 0.02～0.2mol/100g pressed powder.
9, in accordance with the method for claim 8, it is characterized in that described acid is selected from nitric acid, hydrochloric acid, acetate, propionic acid, citric acid.
10, in accordance with the method for claim 1, it is characterized in that described drying process is to descend dry 1～10 hour at 90～200 ℃, roasting process is 300～550 ℃ of following roastings 1～10 hour.
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