CN1091136C - Hydrogenating catalyst for demetalation and its preparing process and application method - Google Patents
Hydrogenating catalyst for demetalation and its preparing process and application method Download PDFInfo
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- CN1091136C CN1091136C CN99113272A CN99113272A CN1091136C CN 1091136 C CN1091136 C CN 1091136C CN 99113272 A CN99113272 A CN 99113272A CN 99113272 A CN99113272 A CN 99113272A CN 1091136 C CN1091136 C CN 1091136C
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- catalyzer
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- acid
- pore volume
- demetalation
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- 239000003054 catalyst Substances 0.000 title claims abstract description 51
- 238000000034 method Methods 0.000 title claims abstract description 38
- 238000007324 demetalation reaction Methods 0.000 title claims abstract description 17
- 230000008569 process Effects 0.000 title claims description 15
- 239000011148 porous material Substances 0.000 claims abstract description 37
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000002253 acid Substances 0.000 claims abstract description 20
- 238000002360 preparation method Methods 0.000 claims abstract description 20
- 239000007921 spray Substances 0.000 claims abstract description 18
- 229910052751 metal Inorganic materials 0.000 claims abstract description 16
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 10
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 19
- 239000002184 metal Substances 0.000 claims description 15
- 239000003921 oil Substances 0.000 claims description 15
- 150000007524 organic acids Chemical class 0.000 claims description 11
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 10
- 238000001125 extrusion Methods 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 10
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 9
- 150000003863 ammonium salts Chemical class 0.000 claims description 9
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 9
- 150000004682 monohydrates Chemical class 0.000 claims description 9
- 229910052710 silicon Inorganic materials 0.000 claims description 9
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 8
- 229910052796 boron Inorganic materials 0.000 claims description 8
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 8
- 229910052698 phosphorus Inorganic materials 0.000 claims description 8
- 239000011574 phosphorus Substances 0.000 claims description 8
- 239000010703 silicon Substances 0.000 claims description 8
- 150000003839 salts Chemical class 0.000 claims description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 6
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 6
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 6
- 229910000765 intermetallic Inorganic materials 0.000 claims description 6
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 5
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims description 4
- 229940010552 ammonium molybdate Drugs 0.000 claims description 4
- 235000018660 ammonium molybdate Nutrition 0.000 claims description 4
- 239000011609 ammonium molybdate Substances 0.000 claims description 4
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 3
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 claims description 3
- 239000005695 Ammonium acetate Substances 0.000 claims description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
- 235000019257 ammonium acetate Nutrition 0.000 claims description 3
- 229940043376 ammonium acetate Drugs 0.000 claims description 3
- CUBCNYWQJHBXIY-UHFFFAOYSA-N benzoic acid;2-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=CC=C1.OC(=O)C1=CC=CC=C1O CUBCNYWQJHBXIY-UHFFFAOYSA-N 0.000 claims description 3
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 3
- 239000004327 boric acid Substances 0.000 claims description 3
- 235000019253 formic acid Nutrition 0.000 claims description 3
- 239000000295 fuel oil Substances 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 238000001935 peptisation Methods 0.000 claims description 3
- 235000019260 propionic acid Nutrition 0.000 claims description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 3
- 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 3
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 3
- 235000012239 silicon dioxide Nutrition 0.000 claims description 3
- 229940095064 tartrate Drugs 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 235000011054 acetic acid Nutrition 0.000 claims description 2
- 239000003513 alkali Substances 0.000 claims description 2
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 2
- 235000015165 citric acid Nutrition 0.000 claims description 2
- MPMSMUBQXQALQI-UHFFFAOYSA-N cobalt phthalocyanine Chemical compound [Co+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 MPMSMUBQXQALQI-UHFFFAOYSA-N 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 238000005984 hydrogenation reaction Methods 0.000 claims description 2
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 claims description 2
- ZULUUIKRFGGGTL-UHFFFAOYSA-L nickel(ii) carbonate Chemical compound [Ni+2].[O-]C([O-])=O ZULUUIKRFGGGTL-UHFFFAOYSA-L 0.000 claims description 2
- 238000002791 soaking Methods 0.000 claims description 2
- 235000002639 sodium chloride Nutrition 0.000 claims description 2
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims 1
- 235000005985 organic acids Nutrition 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 10
- 230000002411 adverse Effects 0.000 abstract 1
- 239000012670 alkaline solution Substances 0.000 abstract 1
- 239000012752 auxiliary agent Substances 0.000 abstract 1
- 238000001192 hot extrusion Methods 0.000 abstract 1
- 238000007654 immersion Methods 0.000 abstract 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 15
- 238000001035 drying Methods 0.000 description 9
- 206010013786 Dry skin Diseases 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 238000006477 desulfuration reaction Methods 0.000 description 7
- 230000023556 desulfurization Effects 0.000 description 7
- 238000009826 distribution Methods 0.000 description 6
- 239000012535 impurity Substances 0.000 description 6
- 238000004898 kneading Methods 0.000 description 6
- 229910052759 nickel Inorganic materials 0.000 description 6
- 229910052720 vanadium Inorganic materials 0.000 description 6
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 6
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 5
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 4
- 239000003637 basic solution Substances 0.000 description 4
- 238000004939 coking Methods 0.000 description 4
- 239000003292 glue Substances 0.000 description 4
- 239000004033 plastic Substances 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000010792 warming Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 241000772415 Neovison vison Species 0.000 description 3
- 229960000583 acetic acid Drugs 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000005096 rolling process Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- FEWJPZIEWOKRBE-JCYAYHJZSA-L L-tartrate(2-) Chemical compound [O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O FEWJPZIEWOKRBE-JCYAYHJZSA-L 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 239000000571 coke Substances 0.000 description 2
- 238000005336 cracking Methods 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
- 238000002474 experimental method Methods 0.000 description 2
- 239000012362 glacial acetic acid Substances 0.000 description 2
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 229910052755 nonmetal Inorganic materials 0.000 description 2
- 150000002902 organometallic compounds Chemical class 0.000 description 2
- 239000004576 sand Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000004438 BET method Methods 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- 229910017313 Mo—Co Inorganic materials 0.000 description 1
- 229910017318 Mo—Ni Inorganic materials 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 238000009530 blood pressure measurement Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 235000011089 carbon dioxide Nutrition 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 229960004106 citric acid Drugs 0.000 description 1
- 239000002826 coolant Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 229940013688 formic acid Drugs 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 229910052945 inorganic sulfide Inorganic materials 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 150000002894 organic compounds Chemical group 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229940095574 propionic acid Drugs 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
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- Catalysts (AREA)
Abstract
The present invention discloses a hydrotreating catalyst for demetalation, and a preparation method and application method thereof. In the catalyst, theta phase alumina containing an auxiliary agent is used as a carrier, and carries metallic elements of group VIB and group VIII. The catalyst is in a pore structure with a single peak value, the pore diameter is from 15 nm to 20 nm, the volume of pores with the pore diameter of 10 nm to 20 nm is at least 80%, wherein the volume of pores with the pore diameter of 14 nm to 20 nm is at least 70%. The catalyst has high demetallization activity and stability, and is prepared by using alkaline solution as a peptizing agent and adopting techniques of hot extrusion forming and unsaturated spray and immersion, which prevents acid from adversely influencing the pore structure, enhances the strength of the catalyst and simplifies the preparation process.
Description
The present invention relates to Hydrodemetalation catalyst and preparation thereof and adopt this catalyzer to carry out the method for residuum hydrogenating and metal-eliminating.
As everyone knows, in the middle of the heavy oils (particularly residual oil), contain the organosulfur and the organometallic compound of higher concentration.In order to obtain the clean fuel of environmentally safe, adopt hydrodesulfurization usually.Heavy oil is being carried out in the process of hydrogenating desulfurization, contained organometallic compound can be deposited on the surfaces externally and internally of Hydrobon catalyst in the middle of the raw material, causes catalytic activity to descend rapidly, even blocking catalyst duct and whole beds.
The effective ways that address the above problem at present are; before Hydrobon catalyst, use the special catalyst for demetalation of one or more different in kinds; make stock oil before the contact desulfuriation catalyzer; utilize the efficient demetalization performance of catalyst for demetalation; remove and be contained in most of metallic impurity contained in the stock oil in the catalyst for demetalation; protect Hydrobon catalyst thus, the activity that it is maintained a long-term stability.
Chinese patent 89108358.8 discloses a kind of hydrodemetallation (HDM)/Hydrobon catalyst, contains the macropore of the diameter of 5～11% pore volumes greater than 100nm in this catalyzer.This catalyzer has high metals capacity and well imagines.Yet,, more metallic impurity are flow on the desulfurization catalyst because the active surface area of this catalyzer unit volume is low, therefore lower to the demetalization reactive activity.One to catalyzer effective innovative approach is: this catalyzer not only will have the ability of higher appearance metallic impurity, holds amount of metal to improve it; But also to have higher metal removal activity, to reduce the load of downstream desulfurization catalyst; Also to possess demetalization selectivity preferably simultaneously, reduce the generation of coking reaction.
Studies show that according to people (Ind.Eng.Chen.Res.1987,26,2245～2250) such as Satoru Kobayashi for the mink cell focus Hydrodemetalation catalyst, when bore dia was 10～15nm, nickel removal and vanadium removal activity had maximum value.
Consider catalyst for demetalation in use, along with the deposition of metallic impurity, aperture this fact that will constantly narrow down, in order to keep secular demetalization stability, bore dia should be at 10～20nm preferably, and best bore dia should be 14～20nm.
Acidity is another important factor that influences the catalyst for demetalation performance.Yet strong excessively acidity not only can be accelerated the demetalization reaction, and can also promote the generation of cracking reaction and coking reaction, and this will seriously reduce the selectivity and the stability of catalyst for demetalation.Therefore, catalyst for demetalation should not have too much strong acid, to reduce cracking reaction and coking reaction takes place.According to above basic concept, we develop the residuum hydrogenating and metal-eliminating catalyst of a kind of ZL89108358.8 of being different from.
The purpose of this invention is to provide a kind of mink cell focus hydrodemetallation (HDM) process that is used for, either have or high stability, simultaneously but have more high reactivity and catalyzer optionally.Another object of the present invention provides a kind of preparation method and the using method of catalyst for demetalation of the present invention.
The feature of catalyst for demetalation of the present invention is: (1) is carrier with the θ phase alumina that contains 0.15～0.85m% silicon and/or boron and/or phosphorus; (2) catalyzer contains the group vib of 3.0～7.0m% and/or the VIII family metal element of 0.5～3.0m%, preferably the VIII family metal element of the group vib of 4.0～6.0m% and/or 1.0～2.0m%; (3) total acid content of catalyzer is 0.250～0.300mmol pyridine/g, wherein accounts for 5～15% of total acid content greater than 450 ℃ strong acid, preferably 8～12%.
Catalyzer of the present invention in addition is being characterized as aspect pore volume and the pore distribution: (1) catalyzer is unimodal value pore structure, and the most probable bore dia is between 15～20nm; (2) pore volume of catalyst pores diameter between 10～20nm is 80～86%, and particularly the pore volume between 14～20nm is 70～80%, is preferably 75～80%; Pore volume less than 10nm is less than 3%; All the other are the hole greater than 20nm, and the bore dia that wherein is lower than 5% pore volume is greater than 100nm; (3) pore volume of catalyzer is 0.65～0.95ml/g; (4) the specific surface area 140～200m of catalyzer
2/ g.
The preparation main points of catalyst for demetalation of the present invention are:
(1) with a kind of alkaline peptizing agent alumina monohydrate is carried out peptization.Contain at least a organic acid and ammoniacal liquor in this alkalescence peptizing agent, contain at least a volatile ammonium salt fully and the soluble compound that contains silicon and/or boron and/or phosphorus simultaneously, wherein the alkali equivalents of contained ammoniacal liquor is 1.2～1.8 times of organic acid equivalents, and ammonium salt weight is 0.2～2.2m% of butt alumina weight.
(2) do not add under the condition of any cooling provision at banded extruder that material heats up naturally in extrusion, the extrusion machine barrel.
(3) product to step (2) carries out roasting, obtains stable θ phase Al
2O
3And remove most of strong acid.
(4) adopt the unsaturated method that sprays, the salts solution that will contain reactive metal sprays on the carrier.
(5) directly to send into temperature be in 300～400 ℃ the stoving oven to the catalyzer bar after will soaking, after the roasting finished catalyst.
The concrete preparation process of catalyst for demetalation of the present invention is:
(1) with carborization or Tai-Ace S 150 method or aluminium chloride process, or the alumina monohydrate dry glue powder that other method is produced is a raw material, mix in brute force and to pinch under the condition, add a kind of alkaline peptizing agent, contain ammoniacal liquor, at least a organic acid (better being formic acid, acetic acid, propionic acid, citric acid, tartrate, Whitfield's ointment) in this alkalescence peptizing agent, contain at least a volatile ammonium salt fully (better being volatile salt, bicarbonate of ammonia, ammonium acetate) simultaneously and contain the soluble compound (better being silicic acid, boric acid, phosphoric acid) of silicon and/or boron and/or phosphorus.Wherein the equivalents of ammoniacal liquor is 1.2～1.8 times of organic acid equivalents, better is 1.3～1.6 times, and volatile ammonium salt weight is 0.2～2.2m% of butt alumina weight fully, better is 0.5～1.5m%.Utilize the heat that produces in the kneading process, temperature of charge rises to 45～65 ℃ by room temperature, and powerful with this understanding mixing pinched 30～90 minutes, made material be plastic.
(2) a large amount of heats that utilize the extrusion process to produce carry out the extruded moulding operation under 65～95 ℃ of conditions.50～100 ℃ of dryings 1～7 hour, 105～140 ℃ of dryings 1～8 hour, then in the presence of air, be warming up to 930～1150 ℃ with 160～300 ℃/hour speed, preferably 950～1080 ℃, constant temperature calcining 1～6 hour promptly obtains containing the θ phase alumina carrier of silicon and/or boron and/or phosphorus.
(3) group vib metallic compound (better being ammonium molybdate, ammonium metawolframate) and/or group VIII metallic compound (better being nickelous nitrate, Xiao Suangu, basic nickel carbonate, cobaltous dihydroxycarbonate) are mixed with the ammonia solution or the aqueous solution that is respectively 5～21g/ml and 0.6～5.6g/ml (in corresponding metal oxide).Then,, evenly spray above-mentioned solution to carrier, spray and finish, leave standstill or be rotated further 0.1～5 hour with atomizing type according to 70～95% of carrier pore space.
(4) directly to be sent to temperature be in 300～400 ℃ the stoving oven to the catalyzer bar that will be sprayed with above-mentioned salts solution, rise to 450～550 ℃ with 150～200 ℃/hour speed then, preferably 480～520 ℃, constant temperature is 1～5 hour in dry air, preferably 2～4 hours, promptly obtain finished catalyst.
The shape of catalyzer of the present invention can be as required, changes by changing the banded extruder die head, comprises cylindrical, cloverleaf pattern, trilobed wheel shape, Herba Galii Bungei shape, four impeller shapes.For the residual oil of nickel+foreign matter of vanadium content, be best with cloverleaf pattern and Herba Galii Bungei shape greater than 50ppm.The diameter of catalyzer is 0.8～4.0mm, is preferably 1.1～1.8mm.
Catalyzer of the present invention must pass through prevulcanized before use.Can in the VGO oil plant, sneak into CS
2Or the mode of other organic or inorganic sulfide is carried out.
Catalyzer of the present invention is mainly used in the hydrodemetallation (HDM) process of long residuum and vacuum residuum.Heavy metal (Ni+V) content suitable in the residual oil raw material oil is 30～200ppm, and sulphur content is 1-4m%, and above impurity all exists with the organic compound form.
The method that catalyzer of the present invention is used for residuum hydrogenating and metal-eliminating is, under certain condition, stock oil contacts with catalyst for demetalation of the present invention with dirty or go up the stream mode fixed-bed reactor of flowing through.Preferred hydrodemetallation (HDM) condition comprises that temperature is 350～420 ℃, and pressure is 12～20MPa, is preferably 14～17MPa, and hydrogen to oil volume ratio is 600～1500, is preferably 600～1000, and volume space velocity was 0.5～2.5h when resid feed was flowed through the liquid of catalyst bed
-1
Compare with the mink cell focus Hydrodemetalation catalyst that has earlier, the advantage of catalyzer of the present invention and method for making thereof is:
(1) duct of catalyzer is concentrated and is distributed in the bore dia scope of 10～20nm, and particularly the hole between 14～20nm is 75～80%.This had both helped improving the metal removal activity of catalyzer, helped improving its stability again.
(2) be carrier with the θ phase alumina that contains minor amount of silicon and/or boron and/or phosphorus, not only can improve the metal removal activity of catalyzer, also can effectively prevent the catalyzer coking, improve its demetallated selectivity and stability.
(3) with contain organic acid, ammoniacal liquor, the basic solution formed of volatile ammonium salt and other related substances is a peptizing agent fully, when alumina monohydrate is carried out effective peptization, has avoided the detrimentally affect of acid to its pore structure.And, owing to select organic acid, eliminated and used strong inorganic acid (as nitric acid, hydrochloric acid, hydrofluoric acid etc.) in the prior art to the destruction of alumina monohydrate with to the corrosion of equipment as peptizing agent.
(4) the hot extrude bar moulding under the employing certain temperature, not only avoided to force the refrigerative shortcoming to banded extruder among the conventional preparation method, utilize the heat that produces in the process to strengthen the interaction of alkaline peptizing agent and alumina monohydrate again, improved the intensity of catalyzer thus, and made the pore distribution of catalyzer more concentrated.
(5) adopt the unsaturated technology that sprays, reduced subsequent step and removed the required big energy of moisture.
(6) adopt the technology that sprays the back direct roasting, simplified the drying process of catalyzer, thereby helped reducing the catalyzer cost.
Below further specify catalyst for demetalation of the present invention and preparation method thereof with embodiment.
Embodiment 1
Take by weighing 1428g and contain Al
2O
370m%, with in the carbonic acid gas and the alumina monohydrate dry glue powder of sodium metaaluminate method preparation, put into kneading machine.The limit is mixed and to be pinched the limit and add 1380ml and contain 4g Glacial acetic acid, 15g citric acid, 20g ammoniacal liquor and (contain NH
335%), 6g volatile salt and 35g silicic acid (contain SiO
2Basic solution 40m%).Because the kneading effect, temperature of charge rises to 60 ℃ gradually by room temperature, and after about 50 minutes, material has been plastic.Then, extrude the Herba Galii Bungei shape bar that circumscribed circle diameter is Φ 1.4～1.8mm with F-26 (III) type twin screw banded extruder and Herba Galii Bungei shape die head.In the extrusion process, temperature of charge rises to 72 ℃ naturally by about 60 ℃ in the tube.Extrudate is 65 ℃ of dryings 5 hours, 110 ℃ of dryings 6 hours.In the presence of air, rise to 980 ℃ then with 200 ℃/hour speed, constant temperature calcining 3 hours, obtaining total pore volume is the siliceous θ phase alumina carrier of 0.85ml/g.
Preparation 160ml contains 5.5gNiO, 19.7gMoO
3The Mo-Ni ammonia solution: measuring 100ml concentration is 18gNH
3The ammoniacal liquor of/100ml adds nickelous nitrate and the 24g that 22g contains NiO25m% respectively and contains MoO under agitation condition
3The ammonium molybdate of 82m%.After the dissolving, in solution, add deionized water to 160ml.The back set aside for use stirs.
Getting the 200g overall porosity is the siliceous θ phase alumina carrier of 170ml, places to spray and rolls pot.Under the rolling situation, evenly spray the 160mlMo-Ni ammonia solution of preparation with the carrier of atomizing type in rolling pot.Spray finish after, material left standstill in rolling pot 45 minutes, then the catalyzer bar directly was transferred in 350 ℃ the stoving oven, was warming up to 500 ℃ with 160 ℃/hour speed again, kept constant temperature 3 hours, promptly obtained catalyst A.
Embodiment 2
Take by weighing 1538g and contain Al
2O
365m%, with the alumina monohydrate dry glue powder of Tai-Ace S 150 and sodium metaaluminate neutralization method preparation, put into kneading machine.Adding 1218ml contains the 45g Glacial acetic acid, 45g ammoniacal liquor (contains NH
335%), the basic solution of 15g ammonium acetate and 28.6g boric acid, mix and pinch.In kneading process, material rises to 62 ℃ naturally by room temperature, and after about 35 minutes, material has become plastic.Use F-26 (III) type twin screw banded extruder and Herba Galii Bungei shape die head then, extruding circumscribed circle diameter is the Herba Galii Bungei shape bar of Φ 1.4～1.8mm, and temperature of charge rises to 75 ℃ naturally in the tube in the extrusion process.Extrude strip 80 ℃ of dryings 3 hours, 110 ℃ of dryings 8 hours in the presence of air, rise to 1080 ℃ with 260 ℃/hour speed then, constant temperature 2 hours, and obtaining pore volume is the boracic θ phase alumina carrier of 0.83ml/g.
Getting the 200g total pore space is the boracic θ phase alumina carrier of 166ml, put it into to spray and roll in the pot, under the rotation condition, evenly spray the 125mlW-Ni aqueous solution with atomizing type to carrier, contain 21g nickelous nitrate (NiO content is 25m%) and 17g ammonium metawolframate (WO in this solution
3Content is 82m%).Spray end, roll pot and be rotated further 20 minutes, then it is directly put into 300 ℃ stoving oven, rise to 480 ℃ with 150 ℃/hour speed, and kept constant temperature 4 hours, promptly obtain catalyst B.
Embodiment 3
Take by weighing 14Kg and contain Al
2O
371m%, with the alumina monohydrate dry glue powder of aluminum chloride and ammoniacal liquor neutralization method preparation, put into kneading machine.Adding 15L contains 50g formic acid, 50g propionic acid, 50g tartrate, 50g Whitfield's ointment, 210g ammoniacal liquor and (contains NH
335%), the basic solution of 113g phosphoric acid and 190g volatile salt, mix and pinch operation.In this operating process, material is warming up to 65 ℃ naturally, and after about 70 minutes, material is plastic.Use F-75 type twin screw banded extruder and Herba Galii Bungei shape die head then, extruding circumscribed circle diameter is the Herba Galii Bungei shape bar of φ 1.4～1.8mm, in the extrusion process, because the heat that extrusion friction produces makes an interior temperature of charge reach 88 ℃.The strip of extruding is 50 ℃ of dryings 7 hours, 120 ℃ of dryings 4 hours.In the presence of air, rise to 940 ℃ then, constant temperature 5 hours with 280 ℃/hour speed.Obtaining total pore volume is the phosphorous θ phase alumina carrier of 0.86ml/g.
Preparation 1500ml contains 138gMoO
3Mo-Co ammonia solution with 30gCoO: measuring 1200ml concentration is 15gNH
3The ammoniacal liquor of/100ml under agitation adds 168g and contains MoO
3The ammonium molybdate of 82m% and 120g contain the Xiao Suangu of CoO25m%, all after the dissolving, add deionized water to 1500ml.
Getting the 2Kg total pore space is the phosphorous θ phase alumina carrier of 1720ml, puts into to spray and rolls pot, under the rotation condition, evenly sprays the 1500mlMo-Co ammonia solution with atomizing type to carrier.Spray end, continue upset 20 minutes, then the catalyzer bar is directly put into temperature and be in 400 ℃ the stoving oven, with 200 ℃/hour speed temperature is risen to 520 ℃ again, constant temperature 2 hours promptly obtains catalyzer C.
Comparative example 1
Prepare catalyzer D according to embodiment 1 in the Chinese patent 89108358.8 and embodiment 2 described methods and condition.
Comparative example 2
Changed carrier roasting condition among the embodiment 1 into 920 ℃, constant temperature in 3 hours 1 hour by 980 ℃, constant temperature, other is constant, promptly obtains catalyzer E.
Comparative example 3
Change embodiment 1 mesosilicic acid add-on into 70g by 35g, other is constant, obtains catalyzer F.
Comparative example 4
Change organic acid among the embodiment 1 nitric acid of equivalent number into, other is constant, promptly obtains catalyzer G.
Comparative example 5
In the embodiment 1 extrusion process, original material is warming up to 72 ℃ naturally, reduces to 30 ℃ by logical water coolant in the cylindrical shell chuck, other is constant, obtains catalyzer H.
Comparative example 6
Change embodiment 1 mesosilicic acid add-on into 0g by 35g, other is constant, obtains catalyst I.
Embodiment 4
This example is physico-chemical property test and result's (seeing Table 1,2) thereof of embodiment of the invention catalyzer and comparative example catalyzer.
Embodiment 5
This example is activity, stability and the selectivity contrast experiment of embodiment of the invention catalyst A and comparative example catalyzer D, E, F, I, the results are shown in Table 3 and table 4.
This experiment has been carried out 3800 hours in 200ml fixed bed hydrogenation device continuously.Reaction conditions is:
Total pressure 15.7MPa
Volume space velocity during liquid (LHSV) 1.0h
-1
385 ℃ of temperature of reaction (0～1800 hour);
389 ℃ (1800～2800 hours);
393 ℃ (2800～3800 hours)
Hydrogen-oil ratio 758V/V
Stock oil: vacuum gas oil (24wt%) in vacuum residuum in the sand (76wt%)/sand
Density, (20 ℃) 985.6kg/m
3
S 4.56wt％
N 2780ppm
Ni 41.1ppm
V 136.7ppm
MCR 16.6wt% table 1. catalyst physico-chemical property analytical method test event method and instrument phase structure X-ray diffraction pore volume and pore size distribution mercury injection method specific area BET method metal form ICP nonmetal ratio of components color method total acid content and acid strength distribution vacuum pyridine adsorption and program
The infrared spectroscopy pressure measurement strength instrument 2. catalyzer physico-chemical property analytical results catalyst A B C D E F G H I carrier phase θ-Al that heat up
2O
3θ-Al
2O
3θ-Al
2O
36-Al
2O
36-Al
2O
3θ-Al
2O
3θ-Al
2O
3θ-Al
2O
3θ-Al
2O
3Kong Rong; Ml/g 0.74 0.70 0.72 0.80 0.75 0.74 0.66 0.76 0.74 pore size distribution; %＜10nm 1.8 2.3 2.5 3.9 6.7 2.8 1.0 3.0 1.010-14nm 5.7 6.4 8.5 116 20.0 14.7 5.9 7.3 4.614-20nm 77.2 79.0 75.1 52.3 66.8 72.2 60.7 68.4 73.420-100nm 11.5 9.0 10.4 24.4 6.5 6.5 23.8 15.2 16.3＞100nm 3.8 3.3 3.5 7.8 0 3.8 8.6 6.1 4.7 most probable bore dias; Nm 18.2 18.0 16.2 21.9 14.0 15.6 21.0 19.5 20.4 specific areas, m2/ g 167 171 188 131 219 189 130 158 147 metal content; Wt%Mo 5.8-4.2 7.5 5.8 5.8 5.8 5.8 5.8Ni 1.9 1.9-2.0 1.9 1.9 1.9 1.9 1.9W-5.0-------Co--1.1------nonmetal content; Wt% Si 0.57---0.57 1.14 0.57 0.57-B-0.42-------P--0.35 0 97-----total acid content; MM/g 0.286 0.268 0.253 0.316 0.307 0.345 0.289 0.295 0.235 acid strength distributes; 160～250 ℃ of 38.7 36.9 38.9 39.8 39.2 37.9 38.0 37.8 45.9250～350 ℃ of 29.7 36.5 32.4 31.1 32.6 23.7 27.5 28.4 33.6350～450 ℃ of 20.4 18.4 18.2 7.7 10.3 14.2 20.8 21.6 16.8＞450 ℃ of 11.2 8.2 10.5 21.4 17.5 24.2 13.7 12.2 3.7 bulk density of %; G/ml 0.60 0.64 0.62 0.55 0.59 0.60 0.68 0.58 0.60 side pressure strength, N/mm 25 26 24 12 19 22 20 16 20
Comparing result shows, has more concentrated (14～20nm) pore distribution, more weak acid and better crush strength by the catalyst for demetalation of the inventive method preparation.Table 3. catalyzer takes off impurity performance comparison catalyst A D E F I0～800 hours: desulfurization degree, % 49.8 48.2 53.3 54.0 42.5 nickel removal rates, % 58.6 53.1 54.7 58.2 50.2 vanadium removal rates, % 73.5 66.3 67.5 72.8 60.4800～1800 hours: desulfurization degree, % 45.3 43.5 48.6 47.2 39.9 nickel removal rates, % 56.2 50.1 50.8 53.1 47.6 vanadium removal rates, % 71.4 63.8 63.1 70.2 58.31800～2800 hours: desulfurization degree, % 50.2 48.0 54.1 52.7 39.3 nickel removal rates, % 59.7 52.6 51.4 56.2 48.1 vanadium removal rates, % 73.3 65.2 65.4 70.5 59.62800～3800 hours: desulfurization degree, % 50.6 47.2 53.4 50.9 39.8 nickel removal rates, % 58.9 52.1 50.2 53.0 46.5 vanadium removal rates, % 73.8 65.4 64.3 68.4 56.4
After running finishes, used catalyzer is carried out solvent (ethanol/benzene=1: 1) extracting handle, use the carbon deposit situation of hydrocarbon nitrogen ~ oxygen quick analytic instrument analysis of catalyst then, the results are shown in Table 4.Table 4. catalyzer coke content is catalyst A D E F I coke content relatively, and wt% 7.10 10.86 10.59 11.68 5.49
From table 3 and table 4 result as can be seen, the catalyzer according to the inventive method preparation is all having bigger improvement aspect the over-all propertieies such as metal removal activity, stability and selectivity.
Claims (10)
1, a kind of catalyst for heavy oil hydrogenation demetal, the feature of this catalyzer is: (1) is carrier with the θ phase alumina that contains 0.15～0.85m% silicon and/or boron and/or phosphorus; (2) catalyzer contains the group vib of 3.0～7.0m% and/or the VIII family metal element of 0.5～3.0m%; (3) total acid content of catalyzer is 0.250～0.300mmol pyridine/g, wherein accounts for 5～15% of total acid content greater than 450 ℃ strong acid.
2, according to the described catalyzer of claim 1, it is characterized in that: (1) catalyzer is unimodal value pore structure, and the most probable bore dia is between 15～20nm; (2) pore volume of catalyst pores diameter between 10～20nm is 80～86%, and the pore volume between 14～20nm is 70～80%; Pore volume less than 10nm is less than 3%; All the other are the hole greater than 20nm, and the bore dia that wherein is lower than 5% pore volume is greater than 100nm; (3) pore volume of catalyzer is 0.65～0.95ml/g; (4) the specific surface area 140～200m of catalyzer
2/ g.
3,, it is characterized in that the strong acid greater than 450 ℃ accounts for 8～12% of total acid content in the feature (3) according to the described catalyzer of claim 1.
4,, it is characterized in that described catalyzer contains the group vib of 4.0～6.0m% and/or the VIII family metal element of 1.0～2.0m% according to the described catalyzer of claim 1.
5,, it is characterized in that the pore volume between 14～20nm is 75～80% in the feature (2) according to the described catalyzer of claim 2.
6, a kind of claim 1 or 2 described Preparation of catalysts methods: it is characterized in that may further comprise the steps:
(1) with a kind of alkaline peptizing agent alumina monohydrate is carried out peptization, contain one or more organic acids and ammoniacal liquor in this alkalescence peptizing agent, contain one or more volatile ammonium salt and the soluble compound that contains silicon and/or boron and/or phosphorus fully simultaneously, wherein the alkali equivalents of contained ammoniacal liquor is 1.2～1.8 times of organic acid equivalents, and ammonium salt weight is 0.2～2.2m% of butt alumina weight;
(2) do not add under the condition of any cooling provision at banded extruder that material heats up naturally in extrusion, the extrusion machine barrel;
(3) product to step (2) carries out roasting, obtains stable θ phase Al
2O
3And remove most of strong acid;
(4) adopt the unsaturated method that sprays, the salts solution that will contain reactive metal sprays on the carrier;
(5) directly to send into temperature be in 300～400 ℃ the stoving oven to the catalyzer bar after will soaking, after the roasting finished catalyst.
7,, it is characterized in that said organic acid is formic acid, acetic acid, propionic acid, citric acid, tartrate, Whitfield's ointment according to the described preparation method of claim 6; Said ammonium salt is volatile salt, bicarbonate of ammonia, ammonium acetate; The said soluble compound that contains silicon and/or boron and/or phosphorus is silicic acid, boric acid, phosphoric acid; Wherein the equivalents of ammoniacal liquor is 1.3～1.6 times of organic acid equivalents, and ammonium salt weight is 0.5～1.5m% of butt alumina weight.
8, according to the described preparation method of claim 6, it is characterized in that the reactive metal described in the step (4) is group vib metallic compound and/or group VIII metallic compound, is respectively in its concentration of corresponding oxide compound: 5～21g/100ml and 0.6～5.6g/100ml.
9,, it is characterized in that described group vib metallic compound is ammonium molybdate, ammonium metawolframate according to the described preparation method of claim 8; VIII family metallic compound is nickelous nitrate, Xiao Suangu, basic nickel carbonate, cobaltous dihydroxycarbonate.
10, claim 1 or the application method of 2 described catalyzer in the hydrodemetallation (HDM) process: stock oil is with dirty or go up the stream mode fixed-bed reactor of flowing through, it is characterized in that stock oil contacts with catalyst for demetalation of the present invention, the hydrodemetallation (HDM) condition comprises that temperature is 350～420 ℃, pressure is 12～20MPa, hydrogen to oil volume ratio is 600～1500, and incoming flow volume space velocity when the liquid of catalyst bed is 0.5～2.5h
-1
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| CN100371077C (en) * | 2004-10-29 | 2008-02-27 | 中国石油化工股份有限公司 | A kind of macroporous alumina carrier and preparation method thereof |
| CN101314139B (en) * | 2007-05-31 | 2010-07-21 | 中国石油化工股份有限公司 | Boron containing composite alumina support and preparation thereof |
| CN102233271B (en) * | 2010-04-30 | 2013-03-06 | 中国石油化工股份有限公司 | Fischer-Tropsch synthesis catalyst taking aluminum oxide as carrier and application thereof |
| CN102641738A (en) * | 2011-02-17 | 2012-08-22 | 中国石油化工股份有限公司 | Catalyst for heavy oil hydrotreatment, preparation and application thereof |
| CN104226369B (en) * | 2013-06-21 | 2017-01-25 | 中国石油天然气股份有限公司 | Catalyst suitable for hydrogenation of heavy oil products and preparation and application thereof |
| CN104941654B (en) * | 2015-05-21 | 2017-07-21 | 中国石油大学(北京) | A kind of alumina base Hydrobon catalyst and preparation method and application |
| CN107837798B (en) * | 2016-09-21 | 2020-10-27 | 中国石油化工股份有限公司 | Alumina pellet carrier, preparation method thereof and catalytic reforming catalyst |
| CN111001424A (en) * | 2019-11-27 | 2020-04-14 | 浙江石油化工有限公司 | Phosphorus-containing residual oil hydrotreating catalyst and preparation method thereof |
| CN116159569B (en) * | 2023-01-03 | 2024-01-26 | 武汉科林化工集团有限公司 | Waste lubricating oil hydrodesilicification agent |
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| CN1024135C (en) * | 1988-10-04 | 1994-04-06 | 切夫尔昂研究公司 | Process for oxygen demetallization and hydrodesulfurization using a macroporous catalyst |
| CN1024145C (en) * | 1988-05-02 | 1994-04-06 | 莫托罗拉公司 | Semiconductor device metallization process |
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| CN1024145C (en) * | 1988-05-02 | 1994-04-06 | 莫托罗拉公司 | Semiconductor device metallization process |
| CN1024135C (en) * | 1988-10-04 | 1994-04-06 | 切夫尔昂研究公司 | Process for oxygen demetallization and hydrodesulfurization using a macroporous catalyst |
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