CN1251797C - Prepn process of hydroprocessing catalyst - Google Patents
Prepn process of hydroprocessing catalyst Download PDFInfo
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- CN1251797C CN1251797C CN 200310104904 CN200310104904A CN1251797C CN 1251797 C CN1251797 C CN 1251797C CN 200310104904 CN200310104904 CN 200310104904 CN 200310104904 A CN200310104904 A CN 200310104904A CN 1251797 C CN1251797 C CN 1251797C
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- 239000003054 catalyst Substances 0.000 title claims abstract description 111
- 238000000034 method Methods 0.000 title claims abstract description 48
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 68
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 34
- 239000000843 powder Substances 0.000 claims abstract description 32
- 238000002360 preparation method Methods 0.000 claims abstract description 27
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims abstract description 22
- 239000000243 solution Substances 0.000 claims abstract description 18
- 239000011230 binding agent Substances 0.000 claims abstract description 17
- 238000000975 co-precipitation Methods 0.000 claims abstract description 15
- 238000001035 drying Methods 0.000 claims abstract description 10
- 229910052751 metal Inorganic materials 0.000 claims description 17
- 239000002184 metal Substances 0.000 claims description 17
- 239000002253 acid Substances 0.000 claims description 16
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 11
- 150000003863 ammonium salts Chemical group 0.000 claims description 10
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 9
- 229910017604 nitric acid Inorganic materials 0.000 claims description 9
- 239000013049 sediment Substances 0.000 claims description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 6
- 239000003153 chemical reaction reagent Substances 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
- 238000002156 mixing Methods 0.000 claims description 6
- 230000001376 precipitating effect Effects 0.000 claims description 6
- 239000012266 salt solution Substances 0.000 claims description 6
- 230000018044 dehydration Effects 0.000 claims description 5
- 238000006297 dehydration reaction Methods 0.000 claims description 5
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 4
- 238000010298 pulverizing process Methods 0.000 claims description 4
- 238000001179 sorption measurement Methods 0.000 claims description 4
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 claims description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 3
- 239000012670 alkaline solution Substances 0.000 claims description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
- 229910052750 molybdenum Inorganic materials 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
- 239000005695 Ammonium acetate Substances 0.000 claims description 2
- 235000019257 ammonium acetate Nutrition 0.000 claims description 2
- 229940043376 ammonium acetate Drugs 0.000 claims description 2
- 235000019270 ammonium chloride Nutrition 0.000 claims description 2
- VZTDIZULWFCMLS-UHFFFAOYSA-N ammonium formate Chemical compound [NH4+].[O-]C=O VZTDIZULWFCMLS-UHFFFAOYSA-N 0.000 claims description 2
- VBIXEXWLHSRNKB-UHFFFAOYSA-N ammonium oxalate Chemical compound [NH4+].[NH4+].[O-]C(=O)C([O-])=O VBIXEXWLHSRNKB-UHFFFAOYSA-N 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
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims 3
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 claims 1
- 235000015165 citric acid Nutrition 0.000 claims 1
- 235000006408 oxalic acid Nutrition 0.000 claims 1
- 239000011148 porous material Substances 0.000 abstract description 13
- 230000002378 acidificating effect Effects 0.000 abstract description 3
- 239000011159 matrix material Substances 0.000 abstract 4
- 239000003929 acidic solution Substances 0.000 abstract 1
- 238000001354 calcination Methods 0.000 abstract 1
- 229910000765 intermetallic Inorganic materials 0.000 abstract 1
- 238000009740 moulding (composite fabrication) Methods 0.000 abstract 1
- 230000000694 effects Effects 0.000 description 13
- 239000000203 mixture Substances 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 8
- 239000012018 catalyst precursor Substances 0.000 description 7
- 239000012535 impurity Substances 0.000 description 5
- 238000000465 moulding Methods 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
- 239000012876 carrier material Substances 0.000 description 4
- 238000005984 hydrogenation reaction Methods 0.000 description 4
- 239000010953 base metal Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 101100273316 Acinetobacter baylyi (strain ATCC 33305 / BD413 / ADP1) catF gene Proteins 0.000 description 2
- 101150009760 CATB gene Proteins 0.000 description 2
- 206010013786 Dry skin Diseases 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 2
- 101100296558 Pseudomonas knackmussii (strain DSM 6978 / LMG 23759 / B13) pcaF gene Proteins 0.000 description 2
- 101100494806 Pseudomonas syringae pv. syringae katB gene Proteins 0.000 description 2
- 101100453510 Streptomyces coelicolor (strain ATCC BAA-471 / A3(2) / M145) katG gene Proteins 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
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 101150071300 catC gene Proteins 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000010779 crude oil Substances 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 235000021050 feed intake Nutrition 0.000 description 2
- 101150111658 katE gene Proteins 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 239000011812 mixed powder Substances 0.000 description 2
- 239000002808 molecular sieve Substances 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000012545 processing Methods 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
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 240000005702 Galium aparine Species 0.000 description 1
- 235000014820 Galium aparine Nutrition 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 241000612118 Samolus valerandi Species 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
- 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
- DVARTQFDIMZBAA-UHFFFAOYSA-O ammonium nitrate Chemical class [NH4+].[O-][N+]([O-])=O DVARTQFDIMZBAA-UHFFFAOYSA-O 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
- 239000012752 auxiliary agent Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 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
- 239000000295 fuel oil Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000003863 metallic catalyst Substances 0.000 description 1
- 150000007522 mineralic acids Chemical class 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
- 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
- 150000007524 organic acids Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 230000000505 pernicious effect Effects 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
- 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
- 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
The present invention relates to a preparation method of a hydrotreating catalyst, which comprises: a metallic compound solution is made into a powdery matrix catalyst after being coprecipitated, dewatered and pulverized; the powdery matrix catalyst sufficiently contacts ammonia or ammonium so that the ammonia or the ammonium is adsorbed by micropores of the matrix catalyst; the catalyst is obtained through forming, drying and calcining after an acidic solution or an acidic binding agent is added into the matrix catalyst powder with the adsorbed ammonia or the adsorbed ammonium. A catalyst prepared with a coprecipitation method of the prior art has the disadvantages of small pore volume and small specific surface area. The method of the present invention can effectively enlarge the pore volume and the specific surface area of the catalyst prepared with the coprecipitation method to improve the service performance of the catalyst.
Description
Technical field
The present invention relates to a kind of preparation method of hydrotreatment catalyst.
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 pernicious gas contaminated environment.In the secondary processing process of oil product, the existence of sulphur, nitrogen, oxygen and metal impurities can make catalyst poisoning.Distillate hydrogenation is handled and is meant that under uniform temperature and pressure feedstock oil contacts with catalyst with hydrogen, removes impurity, and the saturated process of aromatic hydrocarbons.
The hydrotreating catalyst of function admirable 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 or sulfide that typical hydrotreating catalyst is VIII family and vib metal are supported on the carrier.In general, these catalyst 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 carrier material and VIII family and vib metal composition prepared by co-precipitation hydrotreating catalyst.
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 compound 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 sediment of oxidation stability, then this sediment 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 prepare the method for catalyst, though can prepare active very high catalyst, but, the pore volume and the specific area of the catalyst of this method preparation are very low, in addition, the precipitated metal thing that said method obtains can not directly apply to existing commercial plant, and they must make pellet type catalyst through forming step and could use at commercial plant, and their pore volume and specific area can further reduce in forming process.Can prepare pore volume and the higher catalyst of specific 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.Catalyst pore volume and specific area reduce reaction contact area, and the reactive metal utilization rate descends, and the ability of holding impurity of catalyst reduces, and particularly is that it is poorer that the stability of catalyst will become at processing heavy oil.In forming process, add pore volume and the specific area that carrier material can improve catalyst, still, because the basic non-activity of carrier loses catalyst activity inevitably so add carrier material.
Summary of the invention
At the deficiencies in the prior art, the purpose of this invention is to provide the method that a kind of coprecipitation prepares mixed metal catalyst, the pore volume of the catalyst of this method preparation is compared with the mixed metal catalyst of prior art for preparing with specific area and is significantly improved.
Method for preparing catalyst of the present invention can may further comprise the steps: metal compound solution adds the precipitating reagent co-precipitation, and the powdery body catalyst is made in sediment dehydration, pulverizing; Grained catalyst is fully contacted with ammonia or ammonium, make the micro-porous adsorption ammonia or the ammonium of body catalyst; The body catalyst powder adding acid solution of adsorb ammonia or ammonium or acid binding agent aftershaping, drying and roasting are made catalyst.
The present invention forms the ammonium salt micromeritics with the acid effect behind body catalyst powder adsorb ammonia; or directly add ammonium salt solution; in catalyst preparation process, form the ammonium salt micromeritics; these particulates be dispersed in the original duct of body catalyst and bulk catalyst particles in; in forming process, protected original duct; thereafter these ammonium salt micromeritics decompose volatilization in the roasting process; guarantee that promptly original duct reduces the loss; form new micropore again, thereby improved the pore volume and the specific area of catalyst.
The specific embodiment
Preparation of catalysts method of the present invention is that the powdery body catalyst of coprecipitation preparation fully contacts with ammonia, makes the micro-porous adsorption ammonia or the ammonium of catalyst; Catalyst is made in the body catalyst powder adding acid solution of adsorb ammonia or ammonium or acid binding agent aftershaping, drying, roasting.Particularly, the present invention can may further comprise the steps:
(1) metal compound solution adds the precipitating reagent co-precipitation;
(2) sediment 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 ammonia or ammonium, makes the micro-porous adsorption ammonia or the ammonium of catalyst;
(4) the body catalyst powder of adsorb ammonia that step (3) is obtained or ammonium and acid solution or acid binding agent mixing aftershaping;
(5) the catalyst precursor thing drying and roasting that step (4) is obtained is made catalyst.
The described coprecipitation of step (1) prepares body catalyst and can adopt conventional method of the prior art, adds the precipitating reagent 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, precipitating reagent can be selected from the material with above-mentioned salt generation precipitation reaction, as obtaining with alkaline solution that contains Mo and/or W and the methods such as acid 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 described body catalyst powder of step (3) and ammonia or the abundant contact process of ammonium, the ammonia source can be ammonia, ammoniacal liquor, and ammonium can be selected from ammonium salt solution.Ammoniacal liquor preferred weight content is 2～40% ammoniacal liquor, and ammonium salt preferred weight concentration is 5% solution to saturated ammonium nitrate, ammonium chloride, ammonium formate, ammonium acetate, ammonium oxalate etc.The body catalyst powder fully contacts with ammonia or ammonium, when using ammonia, the body catalyst powder is fully adsorbed.When using ammoniacal liquor, ammonium salt solution, 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 material powder before ammonia or ammonium contact.
The body catalyst powder of described adsorb ammonia of step (4) or ammonium and acid solution or acid binding agent mixed 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 inorganic acid or organic acid, and suitable sour kind and consumption are that those skilled in the art are known, as nitric acid, hydrochloric acid, phosphoric acid, acetate, propionic acid, citric acid etc.The adding binding agent can improve the pore volume and the specific area of catalyst, and the intensity of catalyst, in addition, because the active low or basic non-activity of binding agent reduces activity of such catalysts so add binding agent.
Forming process can be forming processes such as extrusion, compressing tablet or a ball, and the shape of catalyst can be sphere, sheet, cylinder bar or special-shaped bars such as clover bar, bunge bedstraw herb 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 aluminium 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 thereafter mixed ammonia or ammonium and forming 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.
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 metatungstate 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 alkaline solution.
(3) nickel nitrate is dissolved in second reactor and be heated to 90 ℃.
(4) solution with step (3) gained under agitation drops in first reactor, formed suspension was stirred 30 minutes again, with sedimentation and filtration and washing, sediment is following dry 5 hours at 120 ℃ in air, 385 ℃ of following heat 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 catalyst.
(1) 0.06mol nitric acid and 120ml water are fully mixed peptization with 15g (butt) SB-alumina powder (Germany produces), make binding agent.
(2) body catalyst 85g (butt) powder of getting embodiment 1 preparation fully contacts mixing with ammonia.
(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 catalyst to the catalyst dried strip that step 4 obtains.
The catalyst note of preparation is catA.
Embodiment 3
The inventive method prepares catalyst.
(1) fully mix with 15g (butt) SB-alumina powder (Germany produces) body catalyst 85g (butt) the pulverizing back of getting embodiment 1 preparation.
(2) get step 1 mixed powder and fully contact mixing with ammonia.
(3) mixed powder of the adsorb ammonia that 0.06mol nitric acid and 120ml water nitric acid and water and step 2 are obtained fully mixes, extruded moulding makes the catalyst precursor thing.
(4) with embodiment 2 steps 4.
(5) with embodiment 2 steps 5.
The catalyst note of preparation is catB.
Embodiment 4
The inventive method prepares catalyst.
(1) 0.06mol nitric acid and 100ml water nitric acid and water are fully mixed peptization with 15g (butt) SB-alumina powder (Germany produces), make binding agent.
(2) the body catalyst 85g (butt) that gets embodiment 1 preparation pulverizes the back and fully contacts mixing with the ammoniacal liquor 20mL of weight content 25%.
(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) with embodiment 2 steps 4.
(5) with embodiment 2 steps 5.
The catalyst note of preparation is catC.
Embodiment 5
According to the method for embodiment 4, use the saturated ammonium acetate solution of 15mL to replace ammoniacal liquor wherein, other are identical with this example.Obtain the catalyst note and be catD.
Embodiment 6
The inventive method prepares catalyst.
(1) 0.04mol nitric acid and 120ml water are fully mixed peptization with 15g (butt) SB-alumina powder (Germany produces), make binding agent.
(2) body catalyst 80g (butt) powder of getting embodiment 1 preparation fully contacts mixing with ammonia.
(3) the body catalyst powder of the adsorb ammonia that step 2 is obtained and 0.02mol phosphoric acid and 5gUSY molecular sieve (Fushun Petrochemical Research Institute's production) mix.
(4) with embodiment 2 steps 3.
(5) with embodiment 2 steps 4.
(6) with embodiment 2 steps 5.
The catalyst note of preparation is catE
Comparative example 1
(1) 0.04mol nitric acid and 120ml water are fully mixed peptization with 15g (butt) SB-alumina powder (Germany produces), make 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 catalyst note of preparation is catF.
The main physico-chemical property of catalyst sees Table 1.
As can be seen from Table 1, adopt the pore volume and the specific area of the mixed metallic 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 area of prior art for preparing.
Table 1 catalyst physico-chemical property
| Physico-chemical property | catA | catB | catC | catD | catE | catF |
| Pore volume, ml/g specific area, m 2/ g crushing strength, N/mm | 0.248 135 12.1 | 0.233 131 11.5 | 0.237 139 11.0 | 0.234 133 11.3 | 0.261 161 12.6 | 0.136 107 11.9 |
Claims (8)
1, a kind of preparation method of hydrotreatment catalyst, metal compound solution is added the precipitating reagent co-precipitation, the powdery body catalyst is made in sediment dehydration, pulverizing, it is characterized in that the powdery body catalyst is fully contacted with ammonia or ammonium, make the micro-porous adsorption ammonia or the ammonium of body catalyst, the body catalyst powder adding acid solution of adsorb ammonia or ammonium or acid binding agent aftershaping, drying and roasting are made catalyst; Wherein the temperature of sediment dehydration is 100～600 ℃, and the time is 1～30 hour; Described drying is to descend dry 1～10 hour at 90～200 ℃, and roasting is 300～550 ℃ of following roastings 1～10 hour.
2, in accordance with the method for claim 1, it is characterized in that described metal compound solution is one or more of saline solution that contain Mo, W, Co, Ni metal.
3, in accordance with the method for claim 1, it is characterized in that it is with alkaline solution that contains Mo and/or W and the acid solution mixing co-precipitation that contains Co and/or Ni that described metal compound solution adds the precipitating reagent coprecipitation method.
4, in accordance with the method for claim 1, it is characterized in that described dehydration temperaturre is 200～500 ℃, the time is 2～10 hours.
5, in accordance with the method for claim 1, it is characterized in that described ammonia source is selected from ammonia, ammoniacal liquor, described ammonium is selected from ammonium salt solution.
6, in accordance with the method for claim 5, it is characterized in that described ammoniacal liquor is that weight content is 2～40% ammoniacal liquor, described ammonium salt solution is selected from the solution of ammonium nitrate, ammonium chloride, ammonium formate, ammonium acetate, ammonium oxalate.
7, in accordance with the method for claim 5, when it is characterized in that the ammonia source is ammoniacal liquor or ammonium salt solution, should make the body catalyst powder keep pulverulence, consumption is 0.01～1ml/g pressed powder.
8, in accordance with the method for claim 1, it is characterized in that described acid is selected from nitric acid, hydrochloric acid, phosphoric acid, acetate, oxalic acid, propionic acid, citric acid, consumption is 0.02～0.2mol/100g pressed powder.
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| CN1251797C true CN1251797C (en) | 2006-04-19 |
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| CN103801318B (en) * | 2012-11-08 | 2016-02-03 | 中国石油化工股份有限公司 | The preparation method of hydrotreating catalyst |
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