CN107138180B - A kind of porous zeolite class catalyst carrier and preparation method thereof and catalyst - Google Patents
A kind of porous zeolite class catalyst carrier and preparation method thereof and catalyst Download PDFInfo
- Publication number
- CN107138180B CN107138180B CN201710152348.6A CN201710152348A CN107138180B CN 107138180 B CN107138180 B CN 107138180B CN 201710152348 A CN201710152348 A CN 201710152348A CN 107138180 B CN107138180 B CN 107138180B
- Authority
- CN
- China
- Prior art keywords
- powder
- agate ball
- parts
- ball
- sio
- 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.)
- Active
Links
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical class O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 title claims abstract description 90
- 239000003054 catalyst Substances 0.000 title claims abstract description 83
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 139
- 229910052681 coesite Inorganic materials 0.000 claims abstract description 50
- 229910052906 cristobalite Inorganic materials 0.000 claims abstract description 50
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 50
- 229910052682 stishovite Inorganic materials 0.000 claims abstract description 50
- 229910052905 tridymite Inorganic materials 0.000 claims abstract description 50
- 239000011812 mixed powder Substances 0.000 claims abstract description 43
- 229910000323 aluminium silicate Inorganic materials 0.000 claims abstract description 40
- 239000002994 raw material Substances 0.000 claims abstract description 39
- 239000002808 molecular sieve Substances 0.000 claims abstract description 37
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 37
- 229920002261 Corn starch Polymers 0.000 claims abstract description 36
- 239000008120 corn starch Substances 0.000 claims abstract description 36
- 229940099112 cornstarch Drugs 0.000 claims abstract description 36
- 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 35
- 229910052593 corundum Inorganic materials 0.000 claims abstract description 35
- 229910001845 yogo sapphire Inorganic materials 0.000 claims abstract description 35
- 239000000843 powder Substances 0.000 claims abstract description 34
- 229920000049 Carbon (fiber) Polymers 0.000 claims abstract description 21
- 239000004917 carbon fiber Substances 0.000 claims abstract description 21
- 239000000463 material Substances 0.000 claims abstract description 21
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000002270 dispersing agent Substances 0.000 claims abstract description 20
- 238000009826 distribution Methods 0.000 claims abstract description 17
- 238000005245 sintering Methods 0.000 claims abstract description 15
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum oxide Inorganic materials [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000004519 manufacturing process Methods 0.000 claims abstract description 6
- 238000000498 ball milling Methods 0.000 claims description 18
- 238000010438 heat treatment Methods 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 239000007864 aqueous solution Substances 0.000 claims description 12
- 238000012545 processing Methods 0.000 claims description 12
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 12
- 239000002245 particle Substances 0.000 claims description 11
- 238000000227 grinding Methods 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 239000012530 fluid Substances 0.000 claims description 9
- 239000000314 lubricant Substances 0.000 claims description 9
- 229910052751 metal Inorganic materials 0.000 claims description 9
- 239000002184 metal Substances 0.000 claims description 9
- 238000001238 wet grinding Methods 0.000 claims description 9
- 239000000654 additive Substances 0.000 claims description 8
- 230000000996 additive effect Effects 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- 150000002739 metals Chemical class 0.000 claims description 8
- 239000012153 distilled water Substances 0.000 claims description 7
- 238000004321 preservation Methods 0.000 claims description 7
- 239000000243 solution Substances 0.000 claims description 7
- 229920002125 Sokalan® Polymers 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 235000019441 ethanol Nutrition 0.000 claims description 6
- 239000012065 filter cake Substances 0.000 claims description 6
- 238000010907 mechanical stirring Methods 0.000 claims description 6
- 239000004584 polyacrylic acid Substances 0.000 claims description 6
- 238000002791 soaking Methods 0.000 claims description 6
- 238000003828 vacuum filtration Methods 0.000 claims description 6
- 238000005303 weighing Methods 0.000 claims description 6
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 claims description 3
- 229920000058 polyacrylate Polymers 0.000 claims description 3
- 229910052700 potassium Inorganic materials 0.000 claims description 3
- 239000011591 potassium Substances 0.000 claims description 3
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 claims description 3
- 239000000969 carrier Substances 0.000 claims description 2
- 239000006185 dispersion Substances 0.000 claims 1
- 239000011148 porous material Substances 0.000 abstract description 11
- 239000000203 mixture Substances 0.000 abstract description 5
- 238000012795 verification Methods 0.000 abstract description 4
- 238000009766 low-temperature sintering Methods 0.000 abstract description 2
- 229910002339 La(NO3)3 Inorganic materials 0.000 abstract 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 10
- 229910002651 NO3 Inorganic materials 0.000 description 8
- 229910021536 Zeolite Inorganic materials 0.000 description 7
- 239000010457 zeolite Substances 0.000 description 7
- 230000003197 catalytic effect Effects 0.000 description 6
- 235000013339 cereals Nutrition 0.000 description 6
- 239000000919 ceramic Substances 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000003208 petroleum Substances 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000005336 cracking Methods 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 229940078494 nickel acetate Drugs 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- MYAQZIAVOLKEGW-UHFFFAOYSA-N DMDBT Natural products S1C2=C(C)C=CC=C2C2=C1C(C)=CC=C2 MYAQZIAVOLKEGW-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- 208000035126 Facies Diseases 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 239000005864 Sulphur Substances 0.000 description 2
- 238000013459 approach Methods 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- DGUACJDPTAAFMP-UHFFFAOYSA-N 1,9-dimethyldibenzo[2,1-b:1',2'-d]thiophene Natural products S1C2=CC=CC(C)=C2C2=C1C=CC=C2C DGUACJDPTAAFMP-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 150000000703 Cerium Chemical class 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 229910020442 SiO2—TiO2 Inorganic materials 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 235000013877 carbamide Nutrition 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 239000002817 coal dust Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910052878 cordierite Inorganic materials 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical compound [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 150000002696 manganese Chemical class 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 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
- 239000003921 oil Substances 0.000 description 1
- KTUFCUMIWABKDW-UHFFFAOYSA-N oxo(oxolanthaniooxy)lanthanum Chemical compound O=[La]O[La]=O KTUFCUMIWABKDW-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 229940100486 rice starch Drugs 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000011435 rock Substances 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 1
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 150000003608 titanium Chemical class 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
Classifications
-
- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/7049—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
-
- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
- B01J29/76—Iron group metals or copper
-
- 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
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
-
- 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
- B01J35/64—Pore diameter
- B01J35/651—50-500 nm
-
- 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
- B01J35/64—Pore diameter
- B01J35/653—500-1000 nm
-
- 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
- B01J35/64—Pore diameter
- B01J35/657—Pore diameter larger than 1000 nm
-
- 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
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
-
- 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
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0027—Powdering
- B01J37/0036—Grinding
-
- 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
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
-
- 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
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/088—Decomposition of a metal salt
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Crystallography & Structural Chemistry (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Catalysts (AREA)
Abstract
The present invention relates to a kind of porous zeolite class catalyst carrier and preparation method thereof and catalyst, are made of the raw material of following mass fraction: Al2O340~100 parts of powder, SiO28~20 parts of powder, La (NO3)35~10 parts, 10~20 parts of carbon fiber, 2~5 parts of dispersing agent and 10~20 parts of cornstarch；La(NO3)3Load to Al2O3Powder, SiO2Powder, cornstarch, dispersing agent and carbon fiber sintering production porous aluminosilicate molecular sieve surface, formed La2O3Modified porous aluminosilicate molecular sieve.The invention has the following advantages: the composition and proportion of porous zeolite class catalyst carrier are optimized by verification experimental verification, using grain size distribution principle, in Al2O3Powder and SiO2Prepared by mixed-powder is added cornstarch as pore creating material in the raw material of aluminosilicate molecular sieves, low-temperature sintering may be implemented；Meanwhile the addition of carbon fiber has greatly taken into account the intensity and toughness for the aluminosilicate molecular sieves being prepared, and extends the service life of aluminosilicate molecular sieves.
Description
Technical field
The present invention relates to catalyst technical fields more particularly to a kind of porous zeolite class catalyst carrier and preparation method thereof
And catalyst.
Background technique
With the sharp-decay of petroleum and other chemical resources, energy crisis is that 21 century whole world every country all must face
Pair one of serious problem.In order to guarantee that the sustainability of resource efficiently utilizes, many approach of scientists study, wherein more
Phase catalytic is to defer to Green Chemistry, advocates an approach of sustainable development path.Current 90% or more chemical synthesis
Technique is all of close concern to each other with multi-phase catalysis action.Used the natural clay of pickling as catalyst of cracking petroleum from 1936
Start, until in the 1960s, people just have found to use the catalyst of cracking petroleum based on zeolite that can significantly improve
Cracking efficiency.
Catalyst based on zeolite is known as molecular sieve catalyst.Molecular sieve is a kind of aluminosilicate of crystal type.Its
There is regular and uniform duct in crystal structure, aperture is the order of magnitude of molecular size, point that it only allows diameter than hole diameter small
Son enters, and the big molecule of diameter than hole diameter " is completely kept outside of the door ", therefore it can add by size the molecule in mixture
With screening, therefore named molecular sieve.Molecular sieve has natural zeolite and two kinds of artificial zeolite.Natural zeolite it is most of by volcanic tuff and
Tufaceous sedimentary rock is formed in marine facies or lacustrine facies environment, but its resource is limited after all, and due to place of production difference, natural to boil
The composition and property of stone change frequent occurrence, it is difficult to become ideal catalyst.Therefore, chemist just tries to utilize strict control
The method of purity, composition and property copies the structure of natural zeolite to carry out artificial synthesized, and having for being synthesized so is efficiently urged
The substance for changing performance is known as synthesis zeolite, and it is a kind of porous mass that it, which is a kind of hydrated aluminum silicate of crystal type, brilliant
There is uniform pore structure in body.Molecular sieve catalyst in addition to for being also used to be hydrocracked other than petroleum catalytic cracking, alkane it is different
Structure, xylene isomerization, ethylbenzene synthesis and methanol synthesized gasoline etc..
Recently as the heaviness of crude oil, the impurity contents such as sulphur therein, nitrogen are continuously increased, as environmental requirement is more next
It is higher, stringent limitation is required to the impurity contents such as sulphur, nitrogen in oil product.Generalling use hydrogen addition technology can be very good desulfurization removing nitric.
A kind of SCR denitration and preparation method thereof is disclosed in Chinese patent application CN101185886A, by the Al of preparation2O3-
SiO2-TiO2After complex sol ageing, then cordierite honeycomb ceramic is immersed in colloidal sol, after drying, roasting, then loads work
Denitrating catalyst made from property component.One kind is disclosed in Chinese patent application CN103894185A with TiO2The compound load of-ZnO
The preparation method of the SCR denitration of body is that titanium salt, zinc salt, manganese salt and cerium salt are added separately in distilled water, mixing,
With dioxygen water sedimentation, sediment catalyst obtained after centrifugation, washing, drying, roasting, the catalyst low-temperature activity is higher,
And cost is relatively low.
Researcher is usually fired by pore creating materials such as addition coal dust, graphite, starch, urea, sodium carboxymethylcelluloses
At porous ceramics can also be used as catalyst carrier and use, but by catalyst support material size and pore creating material particle
The stomata of the influence of size and shape, preparation gained porous ceramics is mostly to hold one's breath hole, and aperture is usually 5 μm of -1mm, while gas
The uniformity of pore size distribution is also poor, limits the application range of the type catalyst carrier.Existing porous ceramics class catalyst
The technical problems such as that there is also preparation difficulty is larger simultaneously for carrier, production efficiency is low.
Summary of the invention
In order to solve the above-mentioned technical problems, the present invention provides a kind of porous zeolite class catalyst carriers and preparation method thereof
And catalyst.Porous zeolite class catalyst carrier of the invention is with Al2O3And SiO2Based on the aluminosilicate molecular sieves of formation
Raw material is wanted, is that pore creating material sintering is prepared using cornstarch.Porous zeolite class catalyst carrier provided by the invention has
The advantages that average pore size is small, uniform pore diameter, high percent opening.
The purpose of the present invention is what is be achieved through the following technical solutions:
One aspect of the present invention provides a kind of porous zeolite class catalyst carrier, which is characterized in that the catalyst carries
Body is made of the raw material of following mass fraction: Al2O340~100 parts of powder, SiO28~20 parts of powder, La (NO3)35~10 parts,
10~20 parts of carbon fiber, 2~5 parts of dispersing agent and 10~20 parts of cornstarch；La (the NO3)3Load to Al2O3Powder
End, SiO2Powder, cornstarch, dispersing agent and carbon fiber sintering production porous aluminosilicate molecular sieve surface, formed La2O3
Modified porous aluminosilicate molecular sieve.
An embodiment according to the present invention, the Al2O3And SiO2Powder mixes, the grain of mixed-powder
Diameter is 20~180 μm, wherein particle diameter distribution are as follows: 20~50 μm account for 10~20wt%, and 50~80 μm account for 30~40wt%, 80~
120 μm account for 30~40wt%, and 120~180 μm account for 10~20wt%.
An embodiment according to the present invention, the Al2O3And SiO2Mixed-powder is prepared by the following method: being pressed
Agate ball, Al are added into ball mill according to the ratio of grinding media to material of 36~38:12O3And SiO2Mixed-powder raw material, according to mixed-powder original
16~20% ball-milling additive, the fluid lubricant of 15~20ml/kg and 2.5~3 times of solvent naphtha wet-milling is added in the weight of material,
Drum's speed of rotation be 300~350r/min, ball milling 6~7 hours；Wherein agate ball matches are as follows: diameter is that the agate ball of 18mm accounts for
The 20~22% of agate ball total weight, diameter are that the agate ball of 13~15mm accounts for the 26~28% of agate ball total weight, diameter 8
The agate ball of~10mm accounts for the 28~30% of agate ball total weight, the agate ball that diameter is 5mm account for agate ball total weight 22~
24%.
An embodiment according to the present invention, the partial size of the cornstarch are 50~300nm.
An embodiment according to the present invention, the catalyst carrier are made of the raw material of following mass fraction:
Al2O380 parts of powder, SiO210 parts of powder, La (NO3)38 parts, 15 parts of carbon fiber, 3 parts of dispersing agent and 15 parts of cornstarch；
The Al2O3And SiO2The particle diameter distribution of mixed-powder are as follows: 20~50 μm account for 15wt%, and 50~80 μm account for 35wt%, 80~
120 μm account for 35wt%, and 120~180 μm account for 15wt%.
An embodiment according to the present invention, the SiO2And Al2O3Molar ratio be 10~20.
An embodiment according to the present invention, the dispersing agent are polyacrylic acid, ammonium polyacrylate, Sodium Polyacrylate
Or one of polyacrylic acid potassium.
Another aspect of the present invention additionally provides a kind of preparation method of porous zeolite class catalyst carrier, which is characterized in that
Specific step is as follows:
Step 1: weighing various raw materials according to the proportion of raw material；
Step 2: agate ball, Al are added into ball mill according to the ratio of grinding media to material of 36~38:12O3And SiO2Mixed-powder is former
16~20% ball-milling additive, the fluid lubricant and 2.5 of 15~20ml/kg is added according to the weight of mixed-powder raw material in material
~3 times of solvent naphtha wet-milling, drum's speed of rotation be 300~350r/min, ball milling 6~7 hours；Wherein agate ball matches are as follows: straight
Diameter is that the agate ball of 18mm accounts for the 20~22% of agate ball total weight, and diameter is that the agate ball of 13~15mm accounts for agate ball total weight
26~28%, diameter is that the agate ball of 8~10mm accounts for the 28~30% of agate ball total weight, and diameter is that the agate ball of 5mm accounts for
The 22~24% of agate ball total weight；
Step 3: cornstarch is dispersed in the aqueous solution of ethyl alcohol using ultrasonic wave decentralized processing, then 45
Moisture content is dried under the conditions of~60 DEG C less than 1.0wt%；
Step 4: using mechanical stirring, by the cornstarch and the obtained Al of step 2 after ultrasonic wave decentralized processing2O3With
SiO2Mixed-powder, dispersing agent and carbon fiber, which are uniformly mixed and add distilled water, is made dispersed system；
Step 5: dispersed system obtained by vacuum filtration step 4, then dry under the conditions of 60~80 DEG C by filter cake
It is less than 1.0wt% to moisture content, obtains idiosome；
It is sintered Step 6: the idiosome after drying is put into Muffle furnace, sintering schedule are as follows: first with the liter of 3~5 DEG C/min
Warm rate rises to 240 DEG C from room temperature, then 520 DEG C of heat preservation 0.5h~1h is risen to the heating rate of 1~2 DEG C/min, then with 3
The heating rate of~5 DEG C/min rises to 650 DEG C -750 DEG C, soaking time 1h-3h, and finally cooling obtains porous aluminosilicate point
Son sieve；
Step 7: the porous aluminosilicate molecular sieve that step 6 obtains is immersed in La (NO3)3Aqueous solution in, 90~
It is dried under the conditions of 100 DEG C, 5~6h is then roasted under the conditions of 520~550 DEG C, obtains La2O3Modified porous aluminosilicate point
Son sieve.
Another aspect of the present invention additionally provides a kind of catalyst, it is characterised in that: is catalyzed using above-mentioned porous zeolite class
Agent carrier, and be the calculating of 100 mass fractions, supported active metals Ni 5~10 with the porous zeolite class catalyst carrier
Part, load TiO210~15 parts.
An embodiment according to the present invention, using being sequentially or simultaneously immersed in porous zeolite class catalyst carrier
Method in presoma containing Ni and solution of tetrabutyl titanate, the supported active metals in the porous zeolite class catalyst carrier
Ni and TiO2。
The catalyst carrier and catalyst prepared using method of the invention is had the advantages that
1, the present invention optimizes the composition and proportion of porous zeolite class catalyst carrier by verification experimental verification, in Al2O3Powder
And SiO2Prepared by mixed-powder is added cornstarch as pore creating material in the raw material of aluminosilicate molecular sieves, it reduce sintering temperature
Degree, may be implemented low-temperature sintering；Meanwhile the addition of carbon fiber has greatly taken into account the strong of the aluminosilicate molecular sieves being prepared
Degree and toughness, extend the service life of aluminosilicate molecular sieves.
2, the present invention makes to solve to be influenced by catalyst support material size and pore creating material particle size and shape
The stomata of standby gained porous ceramics is mostly hole of holding one's breath, and aperture is usually 5 μm of -1mm, while the uniformity of gas cell distribution is also poor
Technical problem, the present invention uses grain size distribution principle when selecting raw material, i.e., in the raw material for selecting preparation aluminosilicate molecular sieves
Shi Shouxian is by Al2O3And SiO2Mixed-powder using ball milling method carry out grain size distribution, form four kinds of different particle size distributions
Then the grain size distribution of mixed-powder mixes the cornstarch of Nano grade wherein, the cornstarch of Nano grade can be equal
It is distributed in the gap of the grain size distribution of mixed-powder evenly, is finally sintered to form porous aluminosilicate molecular sieve；It is obtained more
There is diameter be 0.1 μm~300 μm of duct inside the aluminosilicate molecular sieves of hole, internal gutter largely communicate with each other and
It connects with carrier surface；And Kong Rong shared by the duct that 0.1 μm~300 μm of diameter accounts for the 50%~70% of total pore volume；Carrier
Porosity be 20%~30%, the thermal coefficient of carrier is 10~20W/ (mK).
3, Al of the present invention in prepared sizes gradation2O3And SiO2Mixed-powder when use ball grinding method, select different straight
The agate ball of diameter different weight score is used cooperatively and completes Al2O3And SiO2The grain size distribution of mixed-powder.
4, the present invention uses ladder sintering schedule in sintered porous aluminosilicate molecular sieves, and cornstarch is slowly arranged first
Idiosome (rising to 240 DEG C from room temperature with the heating rate of 3~5 DEG C/min) out, then idiosome is rapidly discharged (with 1 in cornstarch
The heating rate of~2 DEG C/min rises to 520 DEG C of heat preservation 0.5h~1h), the step needs slowly heating, prevents idiosome from splitting
Line, and help to form continuous Nano grade through hole inside idiosome, it is finally increased to sintering temperature and completes porous aluminum silicon
The sintering of hydrochlorate molecular sieve is formed.
5, in the molecular sieve carried La of porous aluminosilicate2O3Can significantly improve the catalyst being prepared catalytic activity,
Selectivity and stability, cooperation are supported on the active metal Ni and TiO of porous aluminosilicate molecular sieve catalyst carrier surface2Make
Efficient catalytic activity can be kept in long time by obtaining catalyst.
Specific embodiment
In order to make the objectives, technical solutions, and advantages of the present invention clearer, present invention following specific embodiments
It is illustrated, but the present invention is limited to absolutely not these examples.The following is only the preferred embodiment of the present invention, is used only for explaining
The present invention, it cannot be construed as a limitation to the scope of the present invention.It should be pointed out that all in spirit of the invention
Any modifications, equivalent replacements, and improvements etc. with being done within principle, should all be included in the protection scope of the present invention.
In a specific embodiment, the present invention provides a kind of porous zeolite class catalyst carrier, the catalysis
Agent carrier is made of the raw material of following mass fraction: Al2O340~100 parts of powder, SiO28~20 parts of powder, La (NO3)35~
10 parts, 10~20 parts of carbon fiber, 2~5 parts of dispersing agent and 10~20 parts of cornstarch；La (the NO3)3It loads to
Al2O3Powder, SiO2The porous aluminosilicate molecular sieve surface of powder, cornstarch and carbon fiber sintering production forms La2O3Change
The porous aluminosilicate molecular sieve of property.The Al2O3And SiO2Powder mixes, and the partial size of mixed-powder is 20~180
μm, wherein particle diameter distribution are as follows: 20~50 μm account for 10~20wt%, and 50~80 μm account for 30~40wt%, 80~120 μm account for 30~
40wt%, 120~180 μm account for 10~20wt%.The partial size of the cornstarch is 50~300nm.
In another embodiment, the Al2O3And SiO2Mixed-powder is prepared by the following method: according to
Agate ball, Al are added into ball mill for the ratio of grinding media to material of 36~38:12O3And SiO2Mixed-powder raw material, according to mixed-powder raw material
Weight be added 16~20% ball-milling additive, 15~20ml/kg fluid lubricant and 2.5~3 times of solvent naphtha wet-milling, ball
Mill speed be 300~350r/min, ball milling 6~7 hours；Wherein agate ball matches are as follows: diameter is that the agate ball of 18mm accounts for Ma
The 20~22% of Nao ball total weight, diameter are that the agate ball of 13~15mm accounts for the 26~28% of agate ball total weight, diameter is 8~
The agate ball of 10mm accounts for the 28~30% of agate ball total weight, the agate ball that diameter is 5mm account for agate ball total weight 22~
24%.
In another embodiment, the catalyst carrier is made of the raw material of following mass fraction: Al2O3
80 parts of powder, SiO210 parts of powder, La (NO3)38 parts, 15 parts of carbon fiber, 3 parts of dispersing agent and 15 parts of cornstarch；Described
Al2O3And SiO2The particle diameter distribution of mixed-powder are as follows: 20~50 μm account for 15wt%, and 50~80 μm account for 35wt%, and 80~120 μm account for
35wt%, 120~180 μm account for 15wt%.
In another embodiment, the SiO2And Al2O3Molar ratio be 10~20.
In another embodiment, the dispersing agent be polyacrylic acid, ammonium polyacrylate, Sodium Polyacrylate or
One of polyacrylic acid potassium.
In another embodiment, the present invention also provides a kind of preparation sides of porous zeolite class catalyst carrier
Method, the specific steps are as follows:
Step 1: weighing various raw materials according to the proportion of raw material；
Step 2: agate ball, Al are added into ball mill according to the ratio of grinding media to material of 36~38:12O3And SiO2Mixed-powder is former
16~20% ball-milling additive, the fluid lubricant and 2.5 of 15~20ml/kg is added according to the weight of mixed-powder raw material in material
~3 times of solvent naphtha wet-milling, drum's speed of rotation be 300~350r/min, ball milling 6~7 hours；Wherein agate ball matches are as follows: straight
Diameter is that the agate ball of 18mm accounts for the 20~22% of agate ball total weight, and diameter is that the agate ball of 13~15mm accounts for agate ball total weight
26~28%, diameter is that the agate ball of 8~10mm accounts for the 28~30% of agate ball total weight, and diameter is that the agate ball of 5mm accounts for
The 22~24% of agate ball total weight；
Step 3: cornstarch is dispersed in the aqueous solution of ethyl alcohol using ultrasonic wave decentralized processing, then 45
Moisture content is dried under the conditions of~60 DEG C less than 1.0wt%；
Step 4: using mechanical stirring, by the cornstarch and the obtained Al of step 2 after ultrasonic wave decentralized processing2O3With
SiO2Mixed-powder, dispersing agent and carbon fiber, which are uniformly mixed and add distilled water, is made dispersed system；
Step 5: dispersed system obtained by vacuum filtration step 4, then dry under the conditions of 60~80 DEG C by filter cake
It is less than 1.0wt% to moisture content, obtains idiosome；
It is sintered Step 6: the idiosome after drying is put into Muffle furnace, sintering schedule are as follows: first with the liter of 3~5 DEG C/min
Warm rate rises to 240 DEG C from room temperature, then 520 DEG C of heat preservation 0.5h~1h is risen to the heating rate of 1~2 DEG C/min, then with 3
The heating rate of~5 DEG C/min rises to 650 DEG C -750 DEG C, soaking time 1h-3h, and finally cooling obtains porous aluminosilicate point
Son sieve；
Step 7: the porous aluminosilicate molecular sieve that step 6 obtains is immersed in La (NO3)3Aqueous solution in, 90~
It is dried under the conditions of 100 DEG C, 5~6h is then roasted under the conditions of 520~550 DEG C, obtains La2O3Modified porous aluminosilicate point
Son sieve.
In another embodiment, the present invention also provides a kind of catalyst, using above-mentioned porous zeolite class
Catalyst carrier, and be the calculating of 100 mass fractions, supported active metals Ni 5 with the porous zeolite class catalyst carrier
~10 parts, load TiO210~15 parts.Using porous zeolite class catalyst carrier is sequentially or simultaneously immersed in forerunner containing Ni
Method in body and solution of tetrabutyl titanate, in the porous zeolite class catalyst carrier supported active metals Ni and
TiO2.The Ni presoma is selected from nickel acetate, nickel nitrate and nickel chloride.
Embodiment 1
The preparation method of porous zeolite class catalyst carrier, the specific steps are as follows:
Step 1: weighing various raw materials according to the proportion of raw material；Raw material proportioning are as follows: Al2O3100 parts of powder, SiO2Powder 20
Part, La (NO3)310 parts, 10 parts of carbon fiber, 5 parts of dispersing agent and 20 parts of cornstarch；
Step 2: preparation Al2O3And SiO2Mixed-powder, the partial size of mixed-powder are 20~180 μm, wherein particle diameter distribution
Are as follows: 20~50 μm account for 20wt%, and 50~80 μm account for 30wt%, and 80~120 μm account for 30wt%, and 120~180 μm account for 20wt%；It is beautiful
The partial size of rice starch is 50~300nm.Al2O3And SiO2Mixed-powder is prepared by the following method: according to 36:1 ratio of grinding media to material to
Agate ball, Al are added in ball mill2O3And SiO220% ball is added according to the weight of mixed-powder raw material for mixed-powder raw material
Milling aid, the fluid lubricant of 20ml/kg and 3 times of solvent naphtha wet-milling, drum's speed of rotation 350r/min, ball milling 7 hours；Its
Middle agate ball proportion are as follows: diameter is that the agate ball of 18mm accounts for the 20% of agate ball total weight, and diameter is the agate ball of 13~15mm
The 28% of agate ball total weight is accounted for, diameter is that the agate ball of 8~10mm accounts for the 30% of agate ball total weight, and diameter is the Ma of 5mm
Nao ball accounts for the 22% of agate ball total weight.
Step 3: cornstarch is dispersed in the aqueous solution of ethyl alcohol using ultrasonic wave decentralized processing, then 45
Moisture content is dried under the conditions of~60 DEG C less than 1.0wt%；
Step 4: using mechanical stirring, by the cornstarch and the obtained Al of step 2 after ultrasonic wave decentralized processing2O3With
SiO2Mixed-powder, dispersing agent and carbon fiber, which are uniformly mixed and add distilled water, is made dispersed system；
Step 5: dispersed system obtained by vacuum filtration step 4, then dry under the conditions of 60~80 DEG C by filter cake
It is less than 1.0wt% to moisture content, obtains idiosome；
It is sintered Step 6: the idiosome after drying is put into Muffle furnace, sintering schedule are as follows: first with the heating of 3 DEG C/min
Rate rises to 240 DEG C from room temperature, then 520 DEG C of heat preservation 1h is risen to the heating rate of 1 DEG C/min, then with the liter of 3 DEG C/min
Warm rate rises to 750 DEG C, soaking time 1h, and finally cooling obtains porous aluminosilicate molecular sieve；
Step 7: the porous aluminosilicate molecular sieve that step 6 obtains is immersed in La (NO3)3Aqueous solution in, 90~
It is dried under the conditions of 100 DEG C, then roasts 6h under the conditions of 550 DEG C, obtain La2O3Modified porous aluminosilicate molecular sieve.
It is 50 μm~300 μm of duct, the porosity that porous zeolite class catalyst carrier made from the present embodiment, which has diameter,
Are as follows: 25.0%, the thermal coefficient of carrier reaches 20W/ (mK).
Embodiment 2
A kind of preparation method of porous zeolite class catalyst carrier, the specific steps are as follows:
Step 1: weighing various raw materials according to the proportion of raw material；Al2O360 parts of powder, SiO210 parts of powder, La (NO3)3 5
Part, 10 parts of carbon fiber, 2 parts of dispersing agent and 10 parts of cornstarch；
Step 2: preparation Al2O3And SiO2Agate is added into ball mill according to the ratio of grinding media to material of 36~38:1 for mixed-powder
Ball, Al2O3And SiO216% ball-milling additive, 15ml/kg are added according to the weight of mixed-powder raw material for mixed-powder raw material
Fluid lubricant and 2.5 times of solvent naphtha wet-milling, drum's speed of rotation 300r/min, ball milling 6 hours；Wherein agate ball matches
Are as follows: diameter is that the agate ball of 18mm accounts for the 20% of agate ball total weight, and diameter is that the agate ball of 13~15mm accounts for agate ball gross weight
The 26% of amount, diameter are that the agate ball of 8~10mm accounts for the 30% of agate ball total weight, and diameter is that the agate ball of 5mm accounts for agate ball
The 24% of total weight；Al2O3And SiO2Powder mixes, and the partial size of mixed-powder is 20~180 μm, wherein particle diameter distribution
Are as follows: 20~50 μm account for 10wt%, and 50~80 μm account for 40wt%, and 80~120 μm account for 40wt%, and 120~180 μm account for 10wt%.Institute
The partial size for the cornstarch stated is 50~300nm.
Step 3: cornstarch is dispersed in the aqueous solution of ethyl alcohol using ultrasonic wave decentralized processing, then 45
Moisture content is dried under the conditions of~60 DEG C less than 1.0wt%；
Step 4: using mechanical stirring, by the cornstarch and the obtained Al of step 2 after ultrasonic wave decentralized processing2O3With
SiO2Mixed-powder, dispersing agent and carbon fiber, which are uniformly mixed and add distilled water, is made dispersed system；
Step 5: dispersed system obtained by vacuum filtration step 4, then dry under the conditions of 60~80 DEG C by filter cake
It is less than 1.0wt% to moisture content, obtains idiosome；
It is sintered Step 6: the idiosome after drying is put into Muffle furnace, sintering schedule are as follows: first with the heating of 5 DEG C/min
Rate rises to 240 DEG C from room temperature, then rises to 520 DEG C of heat preservation 1h, the heating of subsequent 5 DEG C/min with the heating rate of 2 DEG C/min
Rate rises to 650 DEG C, soaking time 3h, and finally cooling obtains porous aluminosilicate molecular sieve；
Step 7: the porous aluminosilicate molecular sieve that step 6 obtains is immersed in La (NO3)3Aqueous solution in, 90~
It is dried under the conditions of 100 DEG C, then roasts 5h under the conditions of 520 DEG C, obtain La2O3Modified porous aluminosilicate molecular sieve.
It is 0.1 μm~150 μm of duct, the porosity that porous zeolite class catalyst carrier made from the present embodiment, which has diameter,
Are as follows: 20.3%, the thermal coefficient of carrier reaches 15W/ (mK).
Embodiment 3
Using 100 mass parts of porous zeolite class catalyst carrier of embodiment one, porous zeolite class catalyst carrier is soaked
Enter into nickel acetate and solution of tetrabutyl titanate, the supported active metals Ni 10 in the porous zeolite class catalyst carrier
Part and TiO210 parts.
Embodiment 4
Using 100 mass parts of porous zeolite class catalyst carrier of embodiment one, porous zeolite class catalyst carrier is soaked
Enter into nickel acetate and solution of tetrabutyl titanate, 5 parts of supported active metals Ni in the porous zeolite class catalyst carrier
And TiO215 parts.
The catalytic performance test of above-mentioned catalyst is as follows:
Hydrodesulfurization reaction carries out in a high pressure reaction kettle, 4, the 6- dimethyl dibenzo thiophene of catalytic amount 100g, 60g
Pheno (4,6-DMDBT) is dissolved in 3L solvent, and 260 DEG C of reaction temperature, the gross pressure of system is 65bar in reaction, and stirring rate is
1000rpm, reaction product are quantitative with gas-chromatography.Catalyst and traditional Pd/A1 in embodiment 3 and 42O3Catalyst and non-
The comparison for loading the hydrodesulfurization performance of NiMoW catalyst is shown in Table 1, with traditional Pd/A12O3With unsupported NiMoW catalyst phase
Than the catalyst in embodiment 3 and 4 has higher catalytic activity.
Table 1
| Catalyst | The conversion ratio of 4,6- dimethyl Dibenzothiophene |
| Embodiment 3 | 68.32% |
| Embodiment 4 | 65.86% |
| Traditional Pd/A12O3Catalyst | 42.15% |
| Unsupported NiMoW catalyst | 53.6% |
The above is merely preferred embodiments of the present invention, be not intended to limit the invention, it is all in spirit of the invention and
Made any modifications, equivalent replacements, and improvements etc., should all be included in the protection scope of the present invention within principle.
Claims (10)
1. a kind of porous zeolite class catalyst carrier, which is characterized in that the catalyst carrier by following mass fraction original
Material is made: Al2O340~100 parts of powder, SiO28~20 parts of powder, La (NO3)35~10 parts, 10~20 parts of carbon fiber, dispersion
2~5 parts of agent and 10~20 parts of cornstarch；La (the NO3)3Load to Al2O3Powder, SiO2Powder, cornstarch,
The porous aluminosilicate molecular sieve surface of dispersing agent and carbon fiber sintering production forms La2O3Modified porous aluminosilicate molecule
Sieve, the La2O3The specific preparation step of modified porous aluminosilicate molecular sieve are as follows:
Step 1: weighing various raw materials according to the proportion of raw material；
Step 2: agate ball, Al are added into ball mill according to the ratio of grinding media to material of 36~38:12O3And SiO2Mixed-powder raw material, is pressed
According to mixed-powder raw material weight be added 16~20% ball-milling additive, 15~20ml/kg fluid lubricant and 2.5~3 times
Solvent naphtha wet-milling, drum's speed of rotation be 300~350r/min, ball milling 6~7 hours；Wherein agate ball matches are as follows: diameter 18mm
Agate ball account for the 20~22% of agate ball total weight, the agate ball that diameter is 13~15mm account for agate ball total weight 26~
28%, diameter is that the agate ball of 8~10mm accounts for the 28~30% of agate ball total weight, and diameter is that the agate ball of 5mm accounts for agate ball
The 22~24% of total weight；
Step 3: cornstarch is dispersed in the aqueous solution of ethyl alcohol using ultrasonic wave decentralized processing, then 45~60
Moisture content is dried under the conditions of DEG C less than 1.0wt%；
Step 4: using mechanical stirring, by the cornstarch and the obtained Al of step 2 after ultrasonic wave decentralized processing2O3And SiO2
Mixed-powder, dispersing agent and carbon fiber, which are uniformly mixed and add distilled water, is made dispersed system；
Step 5: dispersed system obtained by vacuum filtration step 4, then dries filter cake under the conditions of 60~80 DEG C to containing
Water rate is less than 10wt%, obtains idiosome；
It is sintered Step 6: the idiosome after drying is put into Muffle furnace, sintering schedule are as follows: first with the heating speed of 3~5 DEG C/min
Rate rises to 240 DEG C from room temperature, then 520 DEG C of heat preservation 0.5h~1h is risen to the heating rate of 1~2 DEG C/min, then with 3~5
DEG C/heating rate of min rises to 650 DEG C -750 DEG C, soaking time 1h-3h, finally cooling obtains porous aluminosilicate molecule
Sieve；
Step 7: the porous aluminosilicate molecule that step 6 obtains is immersed in La (NO3)3Aqueous solution in, 90~100 DEG C of items
It is dried under part, 5~6h is then roasted under the conditions of 520~550 DEG C, obtains La2O3Modified porous aluminosilicate molecular sieve.
2. porous zeolite class catalyst carrier according to claim 1, it is characterised in that: the Al2O3And SiO2Powder
It mixes, the partial size of mixed-powder is 20~180 μm, wherein particle diameter distribution are as follows: 20~50 μm account for 10~20wt%, 50~
80 μm account for 30~40wt%, and 80~120 μm account for 30~40wt%, and 120~180 μm account for 10~20wt%.
3. porous zeolite class catalyst carrier according to claim 2, which is characterized in that the Al2O3And SiO2Mixing
Powder is prepared by the following method: agate ball, Al being added into ball mill according to the ratio of grinding media to material of 36~38:12O3And SiO2Mixing
16~20% ball-milling additive, the fluid lubricant of 15~20ml/kg is added according to the weight of mixed-powder raw material in powder raw material
With 2.5~3 times of solvent naphtha wet-milling, drum's speed of rotation be 300~350r/min, ball milling 6~7 hours；Wherein agate ball matches
Are as follows: diameter is that the agate ball of 18mm accounts for the 20~22% of agate ball total weight, and diameter is that the agate ball of 13~15mm accounts for agate ball
The 26~28% of total weight, diameter are that the agate ball of 8~10mm accounts for the 28~30% of agate ball total weight, and diameter is the Ma of 5mm
Nao ball accounts for the 22~24% of agate ball total weight.
4. porous zeolite class catalyst carrier according to claim 1 or 2, which is characterized in that the cornstarch
Partial size is 50~300nm.
5. porous zeolite class catalyst carrier according to claim 3, which is characterized in that the catalyst carrier is by such as
The raw material of lower mass fraction forms: Al2O380 parts of powder, SiO210 parts of powder, La (NO3)38 parts, 15 parts of carbon fiber, dispersing agent 3
Part and 15 parts of cornstarch；The Al2O3And SiO2The particle diameter distribution of mixed-powder are as follows: 20~50 μm account for 15wt%, and 50
~80 μm account for 35wt%, and 80~120 μm account for 35wt%, and 120~180 μm account for 15wt%.
6. according to claim 1, porous zeolite class catalyst carrier described in 2,3 or 5, it is characterised in that: the SiO2With
Al2O3Molar ratio be 10~20.
7. according to claim 1, porous zeolite class catalyst carrier described in 2,3 or 5, it is characterised in that: the dispersing agent
For one of polyacrylic acid, ammonium polyacrylate, Sodium Polyacrylate or polyacrylic acid potassium.
8. a kind of preparation method of the described in any item porous zeolite class catalyst carriers of claim 1~7, which is characterized in that
Specific step is as follows:
Step 1: weighing various raw materials according to the proportion of raw material；
Step 2: agate ball, Al are added into ball mill according to the ratio of grinding media to material of 36~38:12O3And SiO2Mixed-powder raw material, is pressed
According to mixed-powder raw material weight be added 16~20% ball-milling additive, 15~20ml/kg fluid lubricant and 2.5~3 times
Solvent naphtha wet-milling, drum's speed of rotation be 300~350r/min, ball milling 6~7 hours；Wherein agate ball matches are as follows: diameter 18mm
Agate ball account for the 20~22% of agate ball total weight, the agate ball that diameter is 13~15mm account for agate ball total weight 26~
28%, diameter is that the agate ball of 8~10mm accounts for the 28~30% of agate ball total weight, and diameter is that the agate ball of 5mm accounts for agate ball
The 22~24% of total weight；
Step 3: cornstarch is dispersed in the aqueous solution of ethyl alcohol using ultrasonic wave decentralized processing, then 45~60
Moisture content is dried under the conditions of DEG C less than 1.0wt%；
Step 4: using mechanical stirring, by the cornstarch and the obtained Al of step 2 after ultrasonic wave decentralized processing2O3And SiO2
Mixed-powder, dispersing agent and carbon fiber, which are uniformly mixed and add distilled water, is made dispersed system；
Step 5: dispersed system obtained by vacuum filtration step 4, then dries filter cake under the conditions of 60~80 DEG C to containing
Water rate is less than 10wt%, obtains idiosome；
It is sintered Step 6: the idiosome after drying is put into Muffle furnace, sintering schedule are as follows: first with the heating speed of 3~5 DEG C/min
Rate rises to 240 DEG C from room temperature, then 520 DEG C of heat preservation 0.5h~1h is risen to the heating rate of 1~2 DEG C/min, then with 3~5
DEG C/heating rate of min rises to 650 DEG C -750 DEG C, soaking time 1h-3h, finally cooling obtains porous aluminosilicate molecule
Sieve；
Step 7: the porous aluminosilicate molecule that step 6 obtains is immersed in La (NO3)3Aqueous solution in, 90~100 DEG C of items
It is dried under part, 5~6h is then roasted under the conditions of 520~550 DEG C, obtains La2O3Modified porous aluminosilicate molecular sieve.
9. a kind of catalyst, it is characterised in that: urged using porous zeolite class described in any one of claim 1~7 claim
Agent carrier, and be that 100 mass fractions calculate with the porous zeolite class catalyst carrier, supported active metals Ni 5~
10 parts, load TiO210~15 parts.
10. catalyst according to claim 9, it is characterised in that: use and be sequentially or simultaneously catalyzed porous zeolite class
Agent carrier is immersed in the method in presoma containing Ni and solution of tetrabutyl titanate, in the porous zeolite class catalyst carrier
Supported active metals Ni and TiO2。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710152348.6A CN107138180B (en) | 2017-03-15 | 2017-03-15 | A kind of porous zeolite class catalyst carrier and preparation method thereof and catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710152348.6A CN107138180B (en) | 2017-03-15 | 2017-03-15 | A kind of porous zeolite class catalyst carrier and preparation method thereof and catalyst |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107138180A CN107138180A (en) | 2017-09-08 |
| CN107138180B true CN107138180B (en) | 2019-08-02 |
Family
ID=59784097
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710152348.6A Active CN107138180B (en) | 2017-03-15 | 2017-03-15 | A kind of porous zeolite class catalyst carrier and preparation method thereof and catalyst |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107138180B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110385123B (en) * | 2019-08-02 | 2022-02-08 | 山东众皓环保科技有限公司 | Denitration catalyst capable of effectively resisting ammonium bisulfate poison and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1262307A (en) * | 2000-01-14 | 2000-08-09 | 上海交通大学 | Process for preparing city gas catalyst carrier by cracking heavy oil |
| CN102441412A (en) * | 2010-10-12 | 2012-05-09 | 中国石油化工股份有限公司 | Aromatization catalyst and application thereof in highly selective preparation of p-xylene |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SG186715A1 (en) * | 2010-06-23 | 2013-02-28 | Agency Science Tech & Res | Method of producing alkenes by dehydration of a mixture of alcohols |
-
2017
- 2017-03-15 CN CN201710152348.6A patent/CN107138180B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1262307A (en) * | 2000-01-14 | 2000-08-09 | 上海交通大学 | Process for preparing city gas catalyst carrier by cracking heavy oil |
| CN102441412A (en) * | 2010-10-12 | 2012-05-09 | 中国石油化工股份有限公司 | Aromatization catalyst and application thereof in highly selective preparation of p-xylene |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107138180A (en) | 2017-09-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| WO2017197980A1 (en) | Integral iron cobalt bimetallic fischer-tropsch synthesis catalyst and preparation method therefor | |
| CN102151587B (en) | Process for preparing catalyst powder | |
| CN106179382A (en) | A kind of preparation method of body phase hydrotreating catalyst | |
| CN106179386B (en) | The preparation method of Hydrobon catalyst | |
| CN101254471B (en) | Modified molecular screen base precious metal diesel oil deepness hydrogenation dearomatization catalyst and method of preparing the same | |
| CN102513137B (en) | Catalyst used in preparation of acrylic acid and/or acrylic acid ester from lactic acid or lactate through dehydration | |
| CN106179474B (en) | A kind of Hydrobon catalyst and its preparation method | |
| CN107952476B (en) | Catalyst for preparing gasoline blending component by coupling alcohol naphtha, preparation method and application thereof | |
| CN101254470A (en) | Catalyst for preparing propylene with ethylene and butene inverse-disproportionation and method of preparing the same | |
| CN106669778A (en) | Light oil type hydrocracking catalyst and preparation method thereof | |
| CN107899619A (en) | A kind of preparing propylene by dehydrogenating propane composite alumina support catalyst and preparation method thereof | |
| CN105363446A (en) | Naphtha reforming catalyst and preparation method | |
| CN104549245B (en) | A kind of preparation method of dehydrogenation | |
| Rodrıguez-Castellón et al. | Textural and structural properties and surface acidity characterization of mesoporous silica-zirconia molecular sieves | |
| CN107138180B (en) | A kind of porous zeolite class catalyst carrier and preparation method thereof and catalyst | |
| CN113000059A (en) | Nickel-based catalyst for dry reforming of methane and carbon dioxide and preparation method and application thereof | |
| CN104971767B (en) | A kind of embedded catalyst for methanation in presence of sulfur and preparation method and application | |
| CN104556081A (en) | Modified kaolin as well as preparation method and application thereof | |
| WO2011150834A1 (en) | Regular catalyst for synthesizing oxalate by carbon monoxide gaseous-phase coupling, preparation method and use thereof | |
| CN100493705C (en) | Swollen vermiculite loading NiB amorphous alloy catalyst preparation method and application | |
| CN107344115B (en) | Modified Y-Beta composite molecular sieve and preparation method and application thereof | |
| CN114192184B (en) | Cracking catalyst and preparation method and application thereof | |
| CN101357876B (en) | Method for conveying C<+>9 heavy aromatics to light aromatics | |
| CN106179388A (en) | A kind of preparation method of hydrotreating catalyst | |
| CN103111304B (en) | A kind of non-supported hydrogenation catalyst for demetalation and preparation method thereof |
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 | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20180111 Address after: Jintang Industrial Park, Shaowu City, Nanping, Fujian Applicant after: Shao Wuyongtai high tech materials Co Ltd Address before: Huangyan Jiangkou street in Taizhou city of Zhejiang Province on the 317016 Nian Cun Applicant before: ZHEJIANG YONGTAI NEW MATERIAL CO., LTD. Applicant before: Zhejiang Yongtai Technology Co., Ltd. |
|
| TA01 | Transfer of patent application right | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |