CN102228838A - 一种硅载体碳酸镧催化裂化微球抗钒助剂及其制备方法 - Google Patents
一种硅载体碳酸镧催化裂化微球抗钒助剂及其制备方法 Download PDFInfo
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- CN102228838A CN102228838A CN 201110100491 CN201110100491A CN102228838A CN 102228838 A CN102228838 A CN 102228838A CN 201110100491 CN201110100491 CN 201110100491 CN 201110100491 A CN201110100491 A CN 201110100491A CN 102228838 A CN102228838 A CN 102228838A
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- vanadium
- catalytic cracking
- heavy
- lanthanum carbonate
- preparation
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- 229910052720 vanadium Inorganic materials 0.000 title claims abstract description 85
- 238000004523 catalytic cracking Methods 0.000 title claims abstract description 58
- NZPIUJUFIFZSPW-UHFFFAOYSA-H lanthanum carbonate Chemical compound [La+3].[La+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O NZPIUJUFIFZSPW-UHFFFAOYSA-H 0.000 title claims abstract description 44
- 229910017569 La2(CO3)3 Inorganic materials 0.000 title claims abstract description 40
- 229960001633 lanthanum carbonate Drugs 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 32
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 title abstract description 37
- 239000003054 catalyst Substances 0.000 claims abstract description 78
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 49
- 238000000034 method Methods 0.000 claims abstract description 46
- 230000008569 process Effects 0.000 claims abstract description 26
- 239000007787 solid Substances 0.000 claims abstract description 23
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 22
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 claims abstract description 18
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910001948 sodium oxide Inorganic materials 0.000 claims abstract description 10
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000000126 substance Substances 0.000 claims abstract description 9
- 239000000203 mixture Substances 0.000 claims abstract description 8
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000000460 chlorine Substances 0.000 claims abstract description 7
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 6
- 230000002378 acidificating effect Effects 0.000 claims abstract description 5
- 229910052814 silicon oxide Inorganic materials 0.000 claims abstract description 4
- 239000012752 auxiliary agent Substances 0.000 claims description 33
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 31
- 229910052710 silicon Inorganic materials 0.000 claims description 31
- 239000010703 silicon Substances 0.000 claims description 31
- 239000002002 slurry Substances 0.000 claims description 12
- 238000010009 beating Methods 0.000 claims description 11
- 239000011230 binding agent Substances 0.000 claims description 10
- 239000000377 silicon dioxide Substances 0.000 claims description 10
- 239000007921 spray Substances 0.000 claims description 9
- 239000000084 colloidal system Substances 0.000 claims description 7
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 claims description 7
- 241000772415 Neovison vison Species 0.000 claims description 6
- 238000000227 grinding Methods 0.000 claims description 5
- 238000007493 shaping process Methods 0.000 claims description 5
- 230000009471 action Effects 0.000 claims description 2
- 235000015110 jellies Nutrition 0.000 claims description 2
- 239000008274 jelly Substances 0.000 claims description 2
- ZCMIMMAVLDEIKH-UHFFFAOYSA-F [V+5].C([O-])([O-])=O.[La+3].C([O-])([O-])=O.C([O-])([O-])=O.C([O-])([O-])=O Chemical compound [V+5].C([O-])([O-])=O.[La+3].C([O-])([O-])=O.C([O-])([O-])=O.C([O-])([O-])=O ZCMIMMAVLDEIKH-UHFFFAOYSA-F 0.000 claims 1
- 238000003825 pressing Methods 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 22
- 238000006243 chemical reaction Methods 0.000 abstract description 19
- 239000000571 coke Substances 0.000 abstract description 14
- 239000000295 fuel oil Substances 0.000 abstract description 10
- 239000002245 particle Substances 0.000 abstract description 9
- 229930195733 hydrocarbon Natural products 0.000 abstract description 7
- 150000002430 hydrocarbons Chemical class 0.000 abstract description 7
- 239000000853 adhesive Substances 0.000 abstract description 2
- 230000001070 adhesive effect Effects 0.000 abstract description 2
- 238000000889 atomisation Methods 0.000 abstract description 2
- 230000000607 poisoning effect Effects 0.000 abstract description 2
- 239000003921 oil Substances 0.000 description 36
- 238000005336 cracking Methods 0.000 description 18
- 229910001385 heavy metal Inorganic materials 0.000 description 16
- 239000000047 product Substances 0.000 description 15
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 8
- 229910052761 rare earth metal Inorganic materials 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 7
- 239000004005 microsphere Substances 0.000 description 7
- 229910052782 aluminium Inorganic materials 0.000 description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 6
- 238000009826 distribution Methods 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 239000004411 aluminium Substances 0.000 description 5
- 230000008859 change Effects 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 239000003502 gasoline Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 150000002910 rare earth metals Chemical class 0.000 description 5
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical group [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 5
- 230000009466 transformation Effects 0.000 description 5
- 239000005995 Aluminium silicate Substances 0.000 description 4
- 239000004215 Carbon black (E152) Substances 0.000 description 4
- 235000012211 aluminium silicate Nutrition 0.000 description 4
- 238000009835 boiling Methods 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 239000003426 co-catalyst Substances 0.000 description 4
- 239000002131 composite material Substances 0.000 description 4
- 239000010779 crude oil Substances 0.000 description 4
- 239000002283 diesel fuel Substances 0.000 description 4
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 4
- 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 4
- 239000007788 liquid Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 239000004576 sand Substances 0.000 description 4
- 238000010008 shearing Methods 0.000 description 4
- 239000000654 additive Substances 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 230000032683 aging Effects 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000005243 fluidization Methods 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 3
- 238000001694 spray drying Methods 0.000 description 3
- WQEVDHBJGNOKKO-UHFFFAOYSA-K vanadic acid Chemical compound O[V](O)(O)=O WQEVDHBJGNOKKO-UHFFFAOYSA-K 0.000 description 3
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000008119 colloidal silica Substances 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 230000006837 decompression Effects 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 239000002010 green coke Substances 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 229910052746 lanthanum Inorganic materials 0.000 description 2
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 239000002808 molecular sieve Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- -1 rare earth salts Chemical class 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 239000004575 stone Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 150000003682 vanadium compounds Chemical class 0.000 description 2
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 208000005374 Poisoning Diseases 0.000 description 1
- 102100035947 S-adenosylmethionine synthase isoform type-2 Human genes 0.000 description 1
- 101710167557 S-adenosylmethionine synthase isoform type-2 Proteins 0.000 description 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 239000002671 adjuvant Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 229910001593 boehmite Inorganic materials 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000006388 chemical passivation reaction Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000000994 depressogenic effect Effects 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 230000035987 intoxication Effects 0.000 description 1
- 231100000566 intoxication Toxicity 0.000 description 1
- 229910052747 lanthanoid Inorganic materials 0.000 description 1
- 150000002602 lanthanoids Chemical class 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 229910001425 magnesium ion Inorganic materials 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- 238000001465 metallisation Methods 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000010773 plant oil Substances 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000011882 ultra-fine particle Substances 0.000 description 1
Landscapes
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
Description
项目 | 结晶保留率% | MA800℃/4小时% | MA微800℃/17小时% |
空白对比 | 18 | 32 | 28 |
+5%实施例1助剂 | 43 | 52 | 40 |
+5%实施例2助剂 | 39 | 49 | 37 |
+5%实施例3助剂 | 44 | 53 | 41 |
+5%实施例4助剂 | 42 | 51 | 39 |
项目 | 空白对比 | +5重%的实施例1助剂 |
干气 | 2.2 | 1.7 |
液化气 | 14.2 | 14.9 |
汽油 | 51.1 | 53.3 |
轻柴油 | 26.5 | 25.5 |
焦炭 | 6.0 | 4.6 |
原料油密度,克/升 | 927.0 |
原料油残炭,重% | 4.0 |
钒含量,微克/克 | 58 |
馏程:初馏点 | 296℃ |
10% | 359.0 |
30% | 420.0 |
50% | 470.0 |
500℃馏出 | 70% |
加工量,吨/小时 | 反应温度,℃ | 主催化剂 |
165.0 | 503 | SDC-D |
粗汽油干点,℃ | 200 | 200 |
柴油凝点,℃ | -2.00 | -1.30 |
油浆密度克/升 | 1060 | 1057 |
汽油辛烷值(RON) | 90.00 | 90.00 |
产品分布,重% | 空白对比 | +5重%的实施例1助剂 |
酸性气 | 0.42 | 0.38 |
干气 | 3.01 | 2.81 |
液化气 | 11.22 | 11.93 |
汽油 | 44.36 | 45.12 |
柴油 | 26.14 | 26.84 |
油浆 | 5.47 | 4.70 |
焦炭 | 9.08 | 7.92 |
损失 | 0.30 | 0.30 |
轻质油 | 70.50 | 71.96 |
轻烃液收 | 81.72 | 83.89 |
转化率 | 68.39 | 68.46 |
轻质油选择性,% | 103.08 | 105.11 |
焦炭选择性,% | 13.28 | 11.57 |
Claims (8)
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CN 201110100491 CN102228838B (zh) | 2011-04-21 | 2011-04-21 | 一种硅载体碳酸镧催化裂化微球抗钒助剂及其制备方法 |
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CN 201110100491 CN102228838B (zh) | 2011-04-21 | 2011-04-21 | 一种硅载体碳酸镧催化裂化微球抗钒助剂及其制备方法 |
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CN102228838A true CN102228838A (zh) | 2011-11-02 |
CN102228838B CN102228838B (zh) | 2012-12-12 |
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Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0189267A2 (en) * | 1985-01-14 | 1986-07-30 | Engelhard Corporation | Fluidizable composition for catalytic cracking |
CN1067670A (zh) * | 1991-06-11 | 1993-01-06 | 中国石油化工总公司石油化工科学研究院 | 含固钒剂的烃类裂化催化剂组合物 |
CN1283667A (zh) * | 1999-07-06 | 2001-02-14 | 中国石油化工集团公司 | 一种催化裂化催化剂的抗钒助剂及其应用 |
-
2011
- 2011-04-21 CN CN 201110100491 patent/CN102228838B/zh active Active
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0189267A2 (en) * | 1985-01-14 | 1986-07-30 | Engelhard Corporation | Fluidizable composition for catalytic cracking |
CN1067670A (zh) * | 1991-06-11 | 1993-01-06 | 中国石油化工总公司石油化工科学研究院 | 含固钒剂的烃类裂化催化剂组合物 |
CN1283667A (zh) * | 1999-07-06 | 2001-02-14 | 中国石油化工集团公司 | 一种催化裂化催化剂的抗钒助剂及其应用 |
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Application publication date: 20111102 Assignee: Leshan run and catalyze New Material Co., Ltd. Assignor: Zhuo Runsheng Contract record no.: 2013510000022 Denomination of invention: Silicon-carrier lanthanum carbonate catalytic cracking microspherical vanadium-resistant aid and preparation method thereof Granted publication date: 20121212 License type: Exclusive License Record date: 20130427 |
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Change date: 20150720 Contract record no.: 2013510000022 Assignee after: Sichuan run and catalyze new materials Limited by Share Ltd Assignee before: Leshan run and catalyze New Material Co., Ltd. |
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Effective date of registration: 20170215 Address after: The three group of Jin Su Zhen Miao Er Cun, Wutongqiao District of Leshan City, Sichuan province 614800 Patentee after: Sichuan run and catalyze new materials Limited by Share Ltd Address before: 266500 Shandong City, Qingdao Province Economic and Technological Development Zone, Jiangshan Road, Jiangshan Rui garden, building 4, room 1, unit 401, room Patentee before: Zhuo Runsheng |
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Address after: 614000 group 3, Miaoer village, Jinsu Town, Wutongqiao District, Leshan City, Sichuan Province Patentee after: Runhe catalyst Co.,Ltd. Address before: 614800 group 3, Miaoer village, Jinsu Town, Wutongqiao District, Leshan City, Sichuan Province Patentee before: SICHUAN REZEL CATALYSTS NEW MATERIAL Co.,Ltd. |
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