CN116196949A - 一种含硫加氢活性保护催化剂的制备方法 - Google Patents
一种含硫加氢活性保护催化剂的制备方法 Download PDFInfo
- Publication number
- CN116196949A CN116196949A CN202211731321.XA CN202211731321A CN116196949A CN 116196949 A CN116196949 A CN 116196949A CN 202211731321 A CN202211731321 A CN 202211731321A CN 116196949 A CN116196949 A CN 116196949A
- Authority
- CN
- China
- Prior art keywords
- sulfur
- hydrogenation activity
- catalyst
- containing hydrogenation
- preparing
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 68
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 61
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims abstract description 51
- 239000011593 sulfur Substances 0.000 title claims abstract description 51
- 229910052717 sulfur Inorganic materials 0.000 title claims abstract description 51
- 230000000694 effects Effects 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 238000001035 drying Methods 0.000 claims abstract description 39
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 28
- 229910052751 metal Inorganic materials 0.000 claims abstract description 27
- 239000002184 metal Substances 0.000 claims abstract description 27
- 238000000034 method Methods 0.000 claims abstract description 23
- 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 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000008367 deionised water Substances 0.000 claims abstract description 16
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 16
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 14
- 238000002156 mixing Methods 0.000 claims abstract description 13
- 238000009210 therapy by ultrasound Methods 0.000 claims abstract description 13
- 239000002243 precursor Substances 0.000 claims abstract description 12
- 239000002131 composite material Substances 0.000 claims abstract description 11
- 238000003756 stirring Methods 0.000 claims abstract description 10
- 229940120146 EDTMP Drugs 0.000 claims abstract description 9
- 150000001868 cobalt Chemical class 0.000 claims abstract description 9
- ZKKLPDLKUGTPME-UHFFFAOYSA-N diazanium;bis(sulfanylidene)molybdenum;sulfanide Chemical compound [NH4+].[NH4+].[SH-].[SH-].S=[Mo]=S ZKKLPDLKUGTPME-UHFFFAOYSA-N 0.000 claims abstract description 9
- NFDRPXJGHKJRLJ-UHFFFAOYSA-N edtmp Chemical compound OP(O)(=O)CN(CP(O)(O)=O)CCN(CP(O)(O)=O)CP(O)(O)=O NFDRPXJGHKJRLJ-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000010438 heat treatment Methods 0.000 claims abstract description 9
- 150000002815 nickel Chemical class 0.000 claims abstract description 9
- YNNGZCVDIREDDK-UHFFFAOYSA-N aminocarbamodithioic acid Chemical compound NNC(S)=S YNNGZCVDIREDDK-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000002791 soaking Methods 0.000 claims abstract description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims abstract description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 8
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000003921 oil Substances 0.000 claims description 8
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 6
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- CHWRSCGUEQEHOH-UHFFFAOYSA-N potassium oxide Chemical compound [O-2].[K+].[K+] CHWRSCGUEQEHOH-UHFFFAOYSA-N 0.000 claims description 4
- 229910001950 potassium oxide Inorganic materials 0.000 claims description 4
- 239000000377 silicon dioxide Substances 0.000 claims description 4
- 235000012239 silicon dioxide Nutrition 0.000 claims description 4
- 239000004408 titanium dioxide Substances 0.000 claims description 4
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 3
- 239000012028 Fenton's reagent Substances 0.000 claims description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 3
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 3
- 229910052810 boron oxide Inorganic materials 0.000 claims description 3
- 239000006229 carbon black Substances 0.000 claims description 3
- 239000004917 carbon fiber Substances 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 claims description 3
- YWEUIGNSBFLMFL-UHFFFAOYSA-N diphosphonate Chemical compound O=P(=O)OP(=O)=O YWEUIGNSBFLMFL-UHFFFAOYSA-N 0.000 claims description 3
- 229910002804 graphite Inorganic materials 0.000 claims description 3
- 239000010439 graphite Substances 0.000 claims description 3
- 239000000395 magnesium oxide Substances 0.000 claims description 3
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 3
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052750 molybdenum Inorganic materials 0.000 claims description 3
- 239000011733 molybdenum Substances 0.000 claims description 3
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 3
- DLYUQMMRRRQYAE-UHFFFAOYSA-N phosphorus pentoxide Inorganic materials O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 claims description 3
- 239000011787 zinc oxide Substances 0.000 claims description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 2
- 229910052721 tungsten Inorganic materials 0.000 claims description 2
- 239000010937 tungsten Substances 0.000 claims description 2
- MGZTXXNFBIUONY-UHFFFAOYSA-N hydrogen peroxide;iron(2+);sulfuric acid Chemical compound [Fe+2].OO.OS(O)(=O)=O MGZTXXNFBIUONY-UHFFFAOYSA-N 0.000 claims 1
- 239000011148 porous material Substances 0.000 abstract description 28
- 230000005855 radiation Effects 0.000 abstract description 14
- 150000002739 metals Chemical class 0.000 abstract description 5
- 230000003197 catalytic effect Effects 0.000 abstract description 3
- 239000006185 dispersion Substances 0.000 abstract description 3
- 239000003223 protective agent Substances 0.000 description 12
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 description 4
- DCYNAHFAQKMWDW-UHFFFAOYSA-N azane;carbamodithioic acid Chemical compound N.NC(S)=S DCYNAHFAQKMWDW-UHFFFAOYSA-N 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 4
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 3
- 239000011575 calcium Substances 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 229910052809 inorganic oxide Inorganic materials 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 229940078494 nickel acetate Drugs 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 2
- 239000008139 complexing agent Substances 0.000 description 2
- 239000010779 crude oil Substances 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 229910052720 vanadium Inorganic materials 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- -1 VIB metal oxide Chemical class 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 description 1
- ZULUUIKRFGGGTL-UHFFFAOYSA-L nickel(ii) carbonate Chemical compound [Ni+2].[O-]C([O-])=O ZULUUIKRFGGGTL-UHFFFAOYSA-L 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
- B01J21/04—Alumina
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/185—Phosphorus; Compounds thereof with iron group metals or platinum group metals
- B01J27/1853—Phosphorus; Compounds thereof with iron group metals or platinum group metals with iron, cobalt or nickel
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/58—Fabrics or filaments
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/635—0.5-1.0 ml/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
- B01J37/343—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of ultrasonic wave energy
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
- B01J37/344—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of electromagnetic wave energy
- B01J37/346—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of electromagnetic wave energy of microwave energy
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
- C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
- C10G45/06—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
- C10G2300/205—Metal content
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- General Chemical & Material Sciences (AREA)
- Optics & Photonics (AREA)
- Health & Medical Sciences (AREA)
- Plasma & Fusion (AREA)
- Toxicology (AREA)
- Electromagnetism (AREA)
- Catalysts (AREA)
Abstract
本发明公开了一种含硫加氢活性保护催化剂的制备方法。该方法包括：先将二硫代氨基甲酸铵、镍盐和/或钴盐、乙二胺四亚甲基膦酸和一定量的去离子水混合加热搅拌，然后加入四硫代钼酸铵和/或四硫代钨酸铵，将得到的含硫复合活性金属前驱体浸渍液于50℃～90℃温度下等体积浸渍在含微波敏化剂的改性氧化铝载体上，先用超声处理后，在氮气保护下，先用辐射频率为840MHz的微波干燥，再用辐射频率为2450MHz的微波干燥，得到含硫加氢活性保护催化剂。本发明方法具有高效简便、活性金属分散均匀、不同活性金属之间协同性好、活性金属有效利用率高的特点，制备得到催化剂催化活性好、孔容大、比表面积高、强度高和加氢脱金属能力强，可广泛应用于油品加氢处理过程。
Description
技术领域
本发明涉及一种含硫加氢活性保护催化剂的制备方法。
背景技术
随着原油质量变差，原油中胶质、沥青质和有机金属化合物等杂质含量增高，这些杂质的存在很容易造成催化剂活性的快速下降以致失活。解决这一问题的有效方法是在加氢催化剂床层上部装填具有加氢活性的保护剂。具有较大孔容和孔直径的加氢保护催化剂容金属和容炭能力强，能够起到保护下游加氢主剂的作用，延长主剂的使用寿命。
现有技术中关于加氢保护催化剂及其制备的例子如：
CN200610113493.5公开了一种加氢保护剂及其制备，该保护剂含有一种或几种多孔的耐热无机氧化物，其特征在于，所述保护剂总的孔容为0.3－1.5毫米/克，其中含有毫米级大孔，毫米级大孔孔直径为0.1～1.5微米，毫米级大孔孔容为0.05～0.7毫升/克。所述加氢保护剂的制备方法，包括将一种或几种多孔的耐热无机氧化物和/或多孔的耐热无机氧化物的前身物与至少一种有机物混合、成型、干燥并焙烧，其中，所述有机化合物为熔点介于30～200℃、粒径0.3～2.5毫米且不溶于水的固体颗粒。
CN201010220850.4公开了一种加氢处理保护剂的制备方法。该方法中氧化铝载体是采用两种不同的拟薄水铝石干胶粉混捏法制备的，然后负载活性金属；其中第一种拟薄水铝石结晶度相对较小，孔容大，可提供孔直径30nm～100nm的孔，第二种拟薄水铝石结晶度相对较高，可提供微米级的孔，又因其酸性指数高，干燥后呈现出极硬的块状，将其粉碎后100％通过50目，不但能增加微米级孔的数量，也能提高催化剂载体的强度。通过调整两者之间的混合比例，可以制出强度高、堆积密度大、孔容大和磨损率低的加氢处理保护剂。
CN98111379.6公开了加氢保护催化剂及其制备方法，该催化剂载体为超大孔径，孔径为0.1－30μm的双峰孔，催化剂孔容为0.1－0.8mL/g，比表面0.1－20m2/g，含VIB族金属元素6.65m％－20.0m和/或Ⅷ族金属元素8.71％，－26.13m％。制备方法是采用颗粒堆砌法制备氧化铝载体，然后采用含钼溶液和含镍溶液等量浸渍，浸渍后的催化剂在100－120℃干燥2－5h，在500－550℃焙烧2～5h。
CN00110019.X公开了一种加氢活性保护剂及其制备方法，保护剂所用载体中同时含有γ一氧化铝和δ－氧化铝；保护剂中含VIB族金属氧化物3-22m％和Ⅷ族金属氧化物0.5-5m％，含IA族金属氧化物0-2m％，含磷0-3m％，比表面100-250m2/g。孔容0.4-0.8mL/g。
CN200910206230.2公开了一种渣油加氢保护催化剂及其应用。该催化剂孔容大，孔径大，孔隙率高，孔分布合理，外表面孔口较大，孔道贯穿性好，1000nm以上孔道含有36％以上。尤其是用于渣油固定床加氢方法中，可以使脱出的金属均匀沉淀在整个催化剂床层，杂质钒和钙可以沉淀在孔道内部，提高了孔隙的利用率，保持长周期运转。
上述现有技术针对加氢保护催化剂使用中的问题，给出了各种不同的解决方案。不难看出，其中的载体孔性质(包括孔容，孔径，孔分布等性质)直接决定着此类催化剂的性能。
发明内容
本发明的目的就在于克服上述现有技术的不足之处，本发明方法通过引入多功能络合剂，结合热浸渍，含微波敏化剂的改性氧化铝载体，先用频率为20KHz的超声处理，再用频率为50KHz的超声处理后，在氮气保护下，先用辐射频率为840MHz的微波干燥，再用辐射频率为2450MHz的微波干燥处理，提供一种高效简便、活性金属分散均匀、不同活性金属之间协同性好、活性金属有效利用率高、催化活性好、孔容大、比表面积高、强度高和加氢脱金属能力强的含硫加氢活性保护催化剂的制备方法。
本发明一种含硫加氢活性保护催化剂的制备方法，所述制备方法包括：先将二硫代氨基甲酸铵、镍盐和/或钴盐、乙二胺四亚甲基膦酸和一定量的去离子水混合加热搅拌，然后加入四硫代钼酸铵和/或四硫代钨酸铵，将得到的含硫复合活性金属前驱体浸渍液于50℃～90℃温度下等体积浸渍在含微波敏化剂的改性氧化铝载体上，先用频率为20KHz的超声处理，再用频率为50KHz的超声处理后，在氮气保护下，先用辐射频率为840MHz的微波干燥，再用辐射频率为2450MHz的微波干燥，得到一种含硫加氢活性保护催化剂，得到一种含硫加氢活性保护催化剂；其中所述的二硫代氨基甲酸铵使用的摩尔量为镍盐和/或钴盐摩尔量的50％～300％，优选100％～150％；所述的微波干燥温度为100～120℃。
本发明上述含硫加氢活性保护催化剂的制备方法中，优选所述的镍盐和/或钴盐选自碱式碳酸盐、硝酸盐和醋酸盐等中的一种或多种，进一步优选碱式碳酸盐。
本发明上述含硫加氢活性保护催化剂的制备方法中，优选所述的微波敏化剂为芬顿试剂、活性炭、石墨、导电碳黑、半导电碳黑和碳纤维敏化剂等中的一种或多种。
本发明上述含硫加氢活性保护催化剂的制备方法中，优选所述的改性氧化铝载体至少含有五氧化二磷、二氧化硅、二氧化锆、氧化镁、氧化锌、氧化钾、氧化硼和二氧化钛等中的两种或两种以上化合物，含量为载体组分重量的1wt％～20wt％。
本发明上述含硫加氢活性保护催化剂的制备方法中，优选所述的超声时间为5～30分钟。
本发明上述含硫加氢活性保护催化剂的制备方法中，优选所述的微波干燥时间为30～120分钟。
本发明上述含硫加氢活性保护催化剂的制备方法中，优选所述的含硫加氢活性保护催化剂以最终催化剂的重量为基准，镍和/或钴以元素计的总含量为0.5wt％～5wt％，钼和/或钨以元素计的总含量为1wt％～15wt％。
本发明还进一步提供了一种上述制备方法制得的硫加氢活性保护催化剂。
本发明还进一步提供了一种所述的硫加氢活性保护催化剂在油品加氢处理过程中的应用，特别是在高硫高氮高金属含量的劣质油品加氢处理过程中的应用。
本发明方法通过引入多功能络合剂，结合热浸渍，含微波敏化剂的改性氧化铝载体，先用频率为20KHz的超声处理，再用频率为50KHz的超声处理后，在氮气保护下，先用辐射频率为840MHz的微波干燥，再用辐射频率为2450MHz的微波干燥处理，提供一种高效简便、活性金属分散均匀、不同活性金属之间协同性好、活性金属有效利用率高、催化活性好、孔容大、比表面积高、强度高和加氢脱金属能力强的含硫加氢活性保护催化剂的制备方法。与现有技术提供的加氢保护催化剂相比，本发明提供的加氢保护催化剂在具有常规保护剂功能的同时具有优异的加氢脱金属活性，可广泛应用于油品加氢处理过程中，特别适合于作为高硫高氮高金属含量的劣质油品的加氢保护催化剂，能有效地解决工业加氢装置催化剂床层结垢、堵塞、压降过大而被迫停工的问题，延长加氢催化剂的使用寿命。
具体实施方式
下面用具体实施例来详细说明本发明的技术特点，但实施例并不限制本发明的保护范围。
本发明的具体制备步骤如下：先将二硫代氨基甲酸铵、镍盐和/或钴盐、乙二胺四亚甲基膦酸和一定量的去离子水混合加热搅拌，然后加入四硫代钼酸铵和/或四硫代钨酸铵，将得到的含硫复合活性金属前驱体浸渍液用去离子水定容，于50℃～90℃温度下等体积浸渍在含微波敏化剂的改性氧化铝载体上，先用频率为20KHz的超声处理，再用频率为50KHz的超声处理后，在氮气保护下，先用辐射频率为840MHz的微波干燥，再用辐射频率为2450MHz的微波干燥，得到一种含硫加氢活性保护催化剂，得到一种含硫加氢活性保护催化剂。
实施例1：
将4克的二硫代氨基甲酸铵、2克的碱式碳酸镍、3克的乙二胺四亚甲基膦酸和40克的去离子水混合，于90℃加热搅拌，然后加入10克四硫代钼酸铵，将得到的含硫复合活性金属前驱体浸渍液用去离子水定容，于90℃温度下等体积浸渍在100克含1wt％活性炭和1wt％碳纤维敏化剂的改性氧化铝载体(含2wt％的五氧化二磷和3wt％的氧化镁)，先用频率为20KHz的超声处理3分钟，再用频率为50KHz的超声处理2分钟后，在氮气保护下，先用辐射频率为840MHz的微波干燥，微波干燥温度为120℃，干燥时间为10分钟，再用辐射频率为2450MHz的微波干燥，微波干燥温度为120℃，干燥时间为20分钟，得到含硫加氢活性保护催化剂1。
实施例2：
将1克的二硫代氨基甲酸铵、2克的硝酸镍、1克醋酸镍、1克的乙二胺四亚甲基膦酸和40克的去离子水混合，于80℃加热搅拌，然后加入10克四硫代钨酸铵，将得到的含硫复合活性金属前驱体浸渍液用去离子水定容，于80℃温度下等体积浸渍含2wt％芬顿试剂的改性氧化铝载体(含10wt％的二氧化硅和10wt％的氧化硼)，先用频率为20KHz的超声处理5分钟，再用频率为50KHz的超声处理5分钟后，在氮气保护下，先用辐射频率为840MHz的微波干燥，微波干燥温度为100℃，干燥时间为60分钟，再用辐射频率为2450MHz的微波干燥，微波干燥温度为100℃，干燥时间为60分钟，得到含硫加氢活性保护催化剂2。
实施例3：
将1.5克的二硫代氨基甲酸铵、1.5克的硝酸镍、1.3克醋酸镍、2克的乙二胺四亚甲基膦酸和40克的去离子水混合，于70℃加热搅拌，然后加入7克四硫代钼酸铵和3克四硫代钨酸铵，将得到的含硫复合活性金属前驱体浸渍液用去离子水定容，于70℃温度下等体积浸渍含3wt％石墨的改性氧化铝载体(含0.5wt％的二氧化锆和0.5wt％的氧化锌)，先用频率为20KHz的超声处理10分钟，再用频率为50KHz的超声处理8分钟后，在氮气保护下，先用辐射频率为840MHz的微波干燥，微波干燥温度为110℃，干燥时间为30分钟，再用辐射频率为2450MHz的微波干燥，微波干燥温度为110℃，干燥时间为20分钟，得到含硫加氢活性保护催化剂3。
实施例4：
将1.5克的二硫代氨基甲酸铵、2.8克的醋酸镍、1克的乙二胺四亚甲基膦酸和40克的去离子水混合，于60℃加热搅拌，然后加入3克四硫代钼酸铵和7克四硫代钨酸铵，将得到的含硫复合活性金属前驱体浸渍液用去离子水定容，于60℃温度下等体积浸渍含5wt％半导电碳黑的改性氧化铝载体(含8wt％的二氧化钛和5wt％的氧化钾)，先用频率为20KHz的超声处理15分钟，再用频率为50KHz的超声处理15分钟后，在氮气保护下，先用辐射频率为840MHz的微波干燥，微波干燥温度为120℃，干燥时间为20分钟，再用辐射频率为2450MHz的微波干燥，微波干燥温度为120℃，干燥时间为20分钟，得到含硫加氢活性保护催化剂4。
实施例5：
将2克的二硫代氨基甲酸铵、2克硝酸镍、1克硝酸钴、1.5克的乙二胺四亚甲基膦酸和40克的去离子水混合，于50℃加热搅拌，然后加入10克四硫代钼酸铵，将得到的含硫复合活性金属前驱体浸渍液用去离子水定容，于50℃温度下等体积浸渍含2wt％导电碳黑的改性氧化铝载体(含5wt％的二氧化硅、3wt％的氧化钾和2wt％的二氧化钛)，先用频率为20KHz的超声处理20分钟，再用频率为50KHz的超声处理10分钟后，在氮气保护下，先用辐射频率为840MHz的微波干燥，微波干燥温度为110℃，干燥时间为30分钟，再微波辐射频率为2450MHz，微波干燥温度为110℃，干燥时间为25分钟，得到含硫加氢活性保护催化剂5。
对比例1：
将2克硝酸镍、1克硝酸钴、1克柠檬酸和40克去离子水混合，于30℃下搅拌1小时，然后加入10克四硫代钼酸铵，将得到的含硫复合活性金属前驱体浸渍液于30℃温度下等体积浸渍100克氧化铝载体，静置养生6小时，然后在氮气保护下，于120℃下干燥5小时，得到加氢活性保护催化剂A。
本发明制备的含硫加氢活性保护催化剂1、2、3、4和5及对比例加氢保护催化剂A的物化性质见表1。
表1加氢保护催化剂的物化性质
| 催化剂编号 | 1 | 2 | 3 | 4 | 5 | A |
| 比表面积，m2/g | 212 | 225 | 236 | 227 | 232 | 167 |
| 孔容，mL/g | 0.52 | 0.48 | 0.53 | 0.55 | 0.49 | 0.31 |
| 压碎强度，N/cm | 192 | 183 | 185 | 186 | 193 | 137 |
将本发明制备的含硫加氢活性保护催化剂1、2、3、4和5及对比例加氢保护催化剂A分别装填到固定床加氢反应器中，所处理的原料(见表2)，试验条件如下：反应压力为12MPa、氢油体积比为1200:1、体积空速为1.5h-1、反应温度为380℃，连续运转5000小时，脱杂质性质见表3。
表2原料油主要性质
| 项目 | 数据 |
| 密度(20℃)，g/cm3 | 0.953 |
| Ni，μg/g | 28.5 |
| V，μg/g | 79.6 |
| Fe，μg/g | 6.5 |
| Ca，μg/g | 7.8 |
表3催化剂的评价结果
| 催化剂编号 | 1 | 2 | 3 | 4 | 5 | A |
| 脱Ni+V，wt％ | 60.2 | 61.3 | 58.5 | 57.8 | 61.8 | 30.5 |
| 脱Fe，wt％ | 80.6 | 82.6 | 79.3 | 77.9 | 84.2 | 47.8 |
| 脱Ca，wt％ | 71.5 | 73.8 | 70.2 | 69.7 | 77.3 | 38.9 |
从表3的结果可以看出，本发明方法制备的含硫加氢活性保护催化剂具有更好的Ni、V、Fe、Ca脱除率和良好的稳定性。
Claims (10)
1.一种含硫加氢活性保护催化剂的制备方法，其特征在于，所述制备方法包括：先将二硫代氨基甲酸铵、镍盐和/或钴盐、乙二胺四亚甲基膦酸和一定量的去离子水混合加热搅拌，然后加入四硫代钼酸铵和/或四硫代钨酸铵，将得到的含硫复合活性金属前驱体浸渍液于50℃～90℃温度下等体积浸渍在含微波敏化剂的改性氧化铝载体上，先用频率为20KHz的超声处理，再用频率为50KHz的超声处理后，在氮气保护下，先用辐射频率为840MHz的微波干燥，再用辐射频率为2450MHz的微波干燥，得到含硫加氢活性保护催化剂；其中所述的二硫代氨基甲酸铵使用的摩尔量为镍盐和/或钴盐摩尔量的50％～300％；所述的微波干燥温度为100～120℃。
2.根据权利要求1所述的一种含硫加氢活性保护催化剂的制备方法，其特征在于，所述的二硫代氨基甲酸铵使用的摩尔量为镍盐和/或钴盐摩尔量的100％～150％。
3.根据权利要求1所述的一种含硫加氢活性保护催化剂的制备方法，其特征在于，所述的镍盐和/或钴盐选自碱式碳酸盐、硝酸盐和醋酸盐中的一种或多种。
4.根据权利要求1所述的一种含硫加氢活性保护催化剂的制备方法，其特征在于，所述的微波敏化剂为芬顿试剂、活性炭、石墨、导电碳黑、半导电碳黑和碳纤维敏化剂中的一种或多种。
5.根据权利要求1所述的一种含硫加氢活性保护催化剂的制备方法，其特征在于，所述的改性氧化铝载体至少含有五氧化二磷、二氧化硅、二氧化锆、氧化镁、氧化锌、氧化钾、氧化硼和二氧化钛等中的两种或两种以上化合物，含量为载体组分重量的1wt％～20wt％。
6.根据权利要求1所述的一种含硫加氢活性保护催化剂的制备方法，其特征在于，所述的超声时间为5～30分钟。
7.根据权利要求1所述的一种含硫加氢活性保护催化剂的制备方法，其特征在于，所述的微波干燥时间为30～120分钟。
8.根据权利要求1所述的一种含硫加氢活性保护催化剂的制备方法，其特征在于，所述的含硫加氢活性保护催化剂以最终催化剂的重量为基准，镍和/或钴以元素计的总含量为0.5wt％～5wt％，钼和/或钨以元素计的总含量为1wt％～15wt％。
9.一种权利要求1～8任一所述的制备方法制得的硫加氢活性保护催化剂。
10.一种权利要求9所述的硫加氢活性保护催化剂在油品加氢处理过程中的应用。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211731321.XA CN116196949A (zh) | 2022-12-31 | 2022-12-31 | 一种含硫加氢活性保护催化剂的制备方法 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211731321.XA CN116196949A (zh) | 2022-12-31 | 2022-12-31 | 一种含硫加氢活性保护催化剂的制备方法 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN116196949A true CN116196949A (zh) | 2023-06-02 |
Family
ID=86506919
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211731321.XA Pending CN116196949A (zh) | 2022-12-31 | 2022-12-31 | 一种含硫加氢活性保护催化剂的制备方法 |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116196949A (zh) |
-
2022
- 2022-12-31 CN CN202211731321.XA patent/CN116196949A/zh active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CA2659797C (en) | A catalyst and process for the manufacture of ultra-low sulfur distillate product | |
| EP2411145B1 (en) | A high surface area composition for use in the catalytic hydroconversion of a heavy hydrocarbon feedstock, a method making such composition and its use | |
| EP2424663B1 (en) | Method for making a hydroconversion multi-metallic catalyst | |
| EP2841198B1 (en) | A hydroprocessing catalyst and process for treating heavy hydrocarbon feedstocks | |
| EP2771113B1 (en) | Method of making A LOW COST AND HIGH ACTIVITY HYDROPROCESSING CATALYST | |
| JPH0154096B2 (zh) | ||
| SK286134B6 (sk) | Sférická katalyzátorová zmes, spôsob hydrogenačného spracovania surovín obsahujúcich kovy a sférický nosič katalyzátora | |
| CA2081130C (en) | Hydroprocessing catalyst composition | |
| CA2853105C (en) | A self-activating hydroprocessing catalyst and process for treating heavy hydrocarbon feedstocks | |
| US10703991B2 (en) | Ebullated bed process for high conversion of heavy hydrocarbons with a low sediment yield | |
| JP2006341221A (ja) | 炭化水素油の水素化処理触媒およびその製造方法、ならびに炭化水素油の水素化処理方法 | |
| JP3545943B2 (ja) | 水素化精製触媒 | |
| CN116196949A (zh) | 一种含硫加氢活性保护催化剂的制备方法 | |
| EP2908945A1 (en) | A self-activating hydroprocessing catalyst and process for treating heavy hydrocarbon feedstocks | |
| CA2759044A1 (en) | Hydroconversion multi-metallic catalyst and method for making thereof | |
| CN116037137A (zh) | 一种加氢脱金属催化剂及其制备方法 | |
| CN116139895A (zh) | 一种硫化型加氢脱金属催化剂的制备方法 | |
| WO1999019061A1 (fr) | Catalyseur d'hydrotraitement pour huile lourde, support de catalyseur et procede de preparation de ce catalyseur | |
| JP4519379B2 (ja) | 重質炭化水素油の水素化処理触媒 | |
| JP4316192B2 (ja) | チタンを含有した担体、その製造方法及び炭化水素油の水素化処理触媒 | |
| US10220374B2 (en) | Activation of a self-activating hydroprocessing catalyst with steam | |
| CN114433053B (zh) | 一种加氢处理催化剂及其制备方法和应用 | |
| JP4621371B2 (ja) | 水素化処理触媒床及び該触媒床を用いた重質炭化水素油の水素化処理方法 | |
| CN115814826A (zh) | 一种加氢脱硫脱氮催化剂及其制备方法 | |
| CN114950459A (zh) | 加氢催化剂载体及其制备方法、加氢催化剂及其制备方法 |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |