CN1319631C - Agent with three effect, sulphur transfers, denitrification and combustion supporting as well as its preparing method - Google Patents
Agent with three effect, sulphur transfers, denitrification and combustion supporting as well as its preparing method Download PDFInfo
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- CN1319631C CN1319631C CNB021532842A CN02153284A CN1319631C CN 1319631 C CN1319631 C CN 1319631C CN B021532842 A CNB021532842 A CN B021532842A CN 02153284 A CN02153284 A CN 02153284A CN 1319631 C CN1319631 C CN 1319631C
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- effect agent
- triple effect
- combustion
- denitrogenation
- sulphur
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- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 107
- 230000000694 effects Effects 0.000 title claims description 101
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims description 61
- 239000005864 Sulphur Substances 0.000 title claims description 42
- 238000012546 transfer Methods 0.000 title claims description 28
- 238000000034 method Methods 0.000 title claims description 18
- 238000002485 combustion reaction Methods 0.000 title abstract description 3
- 239000003054 catalyst Substances 0.000 claims abstract description 40
- 229910020068 MgAl Inorganic materials 0.000 claims abstract description 35
- 230000003647 oxidation Effects 0.000 claims abstract description 34
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 34
- 239000000843 powder Substances 0.000 claims abstract description 33
- 238000002360 preparation method Methods 0.000 claims abstract description 27
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 24
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 23
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims abstract description 17
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 16
- 150000002910 rare earth metals Chemical class 0.000 claims abstract description 16
- 150000001875 compounds Chemical class 0.000 claims abstract description 11
- 238000004523 catalytic cracking Methods 0.000 claims abstract description 10
- 229910002091 carbon monoxide Inorganic materials 0.000 claims abstract description 9
- 239000002994 raw material Substances 0.000 claims abstract description 8
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical compound S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000002131 composite material Substances 0.000 claims abstract description 5
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 123
- 239000002002 slurry Substances 0.000 claims description 83
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 76
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 67
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 64
- 239000003463 adsorbent Substances 0.000 claims description 60
- 229910052749 magnesium Inorganic materials 0.000 claims description 55
- 239000011777 magnesium Substances 0.000 claims description 55
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 49
- 235000012245 magnesium oxide Nutrition 0.000 claims description 45
- 239000000395 magnesium oxide Substances 0.000 claims description 41
- 235000006408 oxalic acid Nutrition 0.000 claims description 41
- 239000007864 aqueous solution Substances 0.000 claims description 40
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical group [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims description 36
- 229960000583 acetic acid Drugs 0.000 claims description 34
- 239000003292 glue Substances 0.000 claims description 33
- 239000000047 product Substances 0.000 claims description 32
- 239000000203 mixture Substances 0.000 claims description 29
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 28
- 239000012362 glacial acetic acid Substances 0.000 claims description 26
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 21
- 238000006243 chemical reaction Methods 0.000 claims description 21
- 238000001035 drying Methods 0.000 claims description 18
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 claims description 16
- 239000007848 Bronsted acid Substances 0.000 claims description 15
- 229910001593 boehmite Inorganic materials 0.000 claims description 13
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims description 13
- 230000008929 regeneration Effects 0.000 claims description 13
- 238000011069 regeneration method Methods 0.000 claims description 13
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 12
- 239000002253 acid Substances 0.000 claims description 12
- 159000000003 magnesium salts Chemical class 0.000 claims description 12
- 229910017604 nitric acid Inorganic materials 0.000 claims description 12
- 239000000126 substance Substances 0.000 claims description 10
- 229910052746 lanthanum Inorganic materials 0.000 claims description 8
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 8
- 239000000347 magnesium hydroxide Substances 0.000 claims description 8
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 8
- 229910001404 rare earth metal oxide Inorganic materials 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 8
- SMYKVLBUSSNXMV-UHFFFAOYSA-K aluminum;trihydroxide;hydrate Chemical compound O.[OH-].[OH-].[OH-].[Al+3] SMYKVLBUSSNXMV-UHFFFAOYSA-K 0.000 claims description 7
- -1 compound fluorine cerium oxide Chemical class 0.000 claims description 6
- 150000002505 iron Chemical class 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 150000007524 organic acids Chemical class 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- 239000011265 semifinished product Substances 0.000 claims description 5
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 4
- 238000009826 distribution Methods 0.000 claims description 4
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 claims description 4
- 238000001694 spray drying Methods 0.000 claims description 4
- 239000000725 suspension Substances 0.000 claims description 4
- 229910052723 transition metal Inorganic materials 0.000 claims description 4
- 150000003624 transition metals Chemical class 0.000 claims description 4
- 230000008020 evaporation Effects 0.000 claims description 3
- 238000001704 evaporation Methods 0.000 claims description 3
- 239000003517 fume Substances 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 2
- 229940093915 gynecological organic acid Drugs 0.000 claims description 2
- UEGPKNKPLBYCNK-UHFFFAOYSA-L magnesium acetate Chemical compound [Mg+2].CC([O-])=O.CC([O-])=O UEGPKNKPLBYCNK-UHFFFAOYSA-L 0.000 claims description 2
- 239000011654 magnesium acetate Substances 0.000 claims description 2
- 235000011285 magnesium acetate Nutrition 0.000 claims description 2
- 229940069446 magnesium acetate Drugs 0.000 claims description 2
- 235000005985 organic acids Nutrition 0.000 claims description 2
- 238000000643 oven drying Methods 0.000 claims description 2
- 239000012266 salt solution Substances 0.000 claims description 2
- 238000005245 sintering Methods 0.000 claims description 2
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 claims 7
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 abstract description 9
- 230000003197 catalytic effect Effects 0.000 abstract description 6
- 239000012752 auxiliary agent Substances 0.000 abstract description 5
- AHGFPNNPTLFRAA-UHFFFAOYSA-N [F].[O-2].[Ce+3].[O-2].[O-2].[Ce+3] Chemical compound [F].[O-2].[Ce+3].[O-2].[O-2].[Ce+3] AHGFPNNPTLFRAA-UHFFFAOYSA-N 0.000 abstract description 4
- 238000005504 petroleum refining Methods 0.000 abstract description 4
- 239000000779 smoke Substances 0.000 abstract description 2
- 239000011344 liquid material Substances 0.000 abstract 2
- TXKMVPPZCYKFAC-UHFFFAOYSA-N disulfur monoxide Inorganic materials O=S=S TXKMVPPZCYKFAC-UHFFFAOYSA-N 0.000 abstract 1
- 239000003208 petroleum Substances 0.000 abstract 1
- 238000007670 refining Methods 0.000 abstract 1
- 229910052815 sulfur oxide Inorganic materials 0.000 abstract 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 51
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 31
- 229910052782 aluminium Inorganic materials 0.000 description 24
- 238000003756 stirring Methods 0.000 description 24
- 239000004411 aluminium Substances 0.000 description 23
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 23
- 229910052717 sulfur Inorganic materials 0.000 description 20
- 239000011593 sulfur Substances 0.000 description 20
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 18
- 239000000654 additive Substances 0.000 description 14
- 239000003546 flue gas Substances 0.000 description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 13
- 230000000996 additive effect Effects 0.000 description 13
- 239000000243 solution Substances 0.000 description 13
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 12
- 206010013786 Dry skin Diseases 0.000 description 11
- 238000005336 cracking Methods 0.000 description 11
- 238000010521 absorption reaction Methods 0.000 description 9
- 238000003795 desorption Methods 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- 238000001179 sorption measurement Methods 0.000 description 8
- 239000007789 gas Substances 0.000 description 6
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Chemical compound O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 229910000421 cerium(III) oxide Inorganic materials 0.000 description 5
- 238000006477 desulfuration reaction Methods 0.000 description 5
- 229960003753 nitric oxide Drugs 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 229910052720 vanadium Inorganic materials 0.000 description 5
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 4
- 230000023556 desulfurization Effects 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 238000004231 fluid catalytic cracking Methods 0.000 description 3
- 239000003595 mist Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 231100000331 toxic Toxicity 0.000 description 3
- 230000002588 toxic effect Effects 0.000 description 3
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 229910001882 dioxygen Inorganic materials 0.000 description 2
- 230000005496 eutectics Effects 0.000 description 2
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 2
- 235000019341 magnesium sulphate Nutrition 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 230000001172 regenerating effect Effects 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-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
- 208000037656 Respiratory Sounds Diseases 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000002671 adjuvant Substances 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- 150000001785 cerium compounds Chemical class 0.000 description 1
- 229910000420 cerium oxide Inorganic materials 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 239000004567 concrete Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000011005 laboratory method Methods 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- 230000000505 pernicious effect Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 230000009719 regenerative response Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 238000002910 structure generation Methods 0.000 description 1
- 150000003463 sulfur Chemical class 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
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- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The present invention relates to an auxiliary agent used in catalytic crackers for refining petroleum and a preparation method thereof. The three-effect agent comprises an adsorbing agent, cerium dioxide and vanadium pentoxide used as oxidation catalysts, and fluorine cerium oxide used as a structural auxiliary agent, wherein the oxidation catalysts and the structural auxiliary agent are dispersed in the adsorbing agent; the adsorbing agent is a spinel-like composite oxide having the general formula of MgAl(2-x)FexO4. yMgO, x is from 0.01 to 0.5, and y is from 0.2 to 1.2. The compound containing cerium (rare earth) in the three-effect agent uses bastnaesite powder as the raw material. The preparation method of the three-effect agent comprises: relevant components for preparing the finished product are respectively dissolved or dispersed to form a liquid material; the liquid materials are mixed, dries and calcined to obtain the three-effect agent. The three-effect agent of the present invention is used for adsorbing and desorbing sulfur oxide with high efficiency, supporting combustion of carbon monoxide, and reducing oxynitrides for sulfur oxides in smoke gas regenerated from catalytic cracking in petroleum refining; the preparation method of the three-effect agent is low in cost.
Description
Technical field
The present invention relates to a kind of auxiliary agent in the petroleum refining catalytic cracking and its production and use.Specifically, this auxiliary agent is used for the reduction of combustion-supporting and nitrogen oxide of transfer, the carbon monoxide of regeneration fume from catalytic cracking sulphur oxide.
Background technology
Fluid catalytic cracking (FCC) is most important a kind of secondary operations means in the petroleum refining industry, be the important source of light-end products, but it contains a large amount of pernicious gases in the regenerated flue gas of airborne release, as NO
X, SO
XWith CO etc.SO wherein
XBe the SO in the atmosphere
XOne of main source accounts among the whole human lives SO to airborne release
X3% to 4% of total amount.Catalytic cracking is one of important means of China's heavy oil secondary operations, the total working ability of catalytic cracking accounts for more than 1/3rd of crude capacity at present, heaviness and poor qualityization along with catalytically cracked material, impurity contents such as the sulphur in the raw material, nitrogen constantly increase, have many refineries that the phenomenon of regenerative system equipment corrosion cracking has taken place, serious threat is kept the safety in production.Generally believe at present, under the operating condition of oxygen enrichment regeneration, the NO that sulphur, oxygen generate in catalyst regeneration process
X, SO
XDeng sour gas, the insulating and wearing-resistant lining that sees through equipment arrives the equipment metal inner surface, and with flue gas in the steam effect, generate acid solution in the wall condensation, thereby cause the corrosion of equipment.For addressing the above problem the NO of people in reducing regenerated flue gas
XAnd SO
XCarried out a large amount of work Deng the content of acid gas aspect.Generally adopt sulfur transfer additive to carry out the method for oxidation absorption for the oxysulfide in the regenerator flue gas, the sulfur transfer additive of absorption oxysulfide enters riser reactor with the Cracking catalyst of regeneration, this sulfur transfer additive obtains regeneration under the reducing environment of riser reactor, the sulfur transfer additive after the regeneration enters regenerator with Cracking catalyst and recycles.Research to sulfur transfer additive can be divided into solid sulfur transfer agent and liquid sulfur transfer agent two classes.From the research and development of domestic and international sulfur transfer additive, nearly all commercial sulfur transfer agent all has been written into vanadium, and this is because vanadium has the catalytic action of uniqueness to the redox of sulphur.But vanadium is to the toxic effect of FCC catalyst (or claim catalytic cracking catalyst, be designated hereinafter simply as Cracking catalyst), and the liquid sulfur transfer agent can be strengthened this toxic action because of having dispersiveness highly.Therefore, the solid sulfur transfer agent should be the main direction of development.Before the eighties,, be starting point with the metal oxide for the selection of sulfur transfer additive, original adoption Al
2O
3, MgO or its mixture be as sulfur transfer additive, but performance is undesirable.Al
2(SO
4)
3At high temperature has thermal instability, though and MgO has good desulfurization performance, its sulfate MgSO
4Heat endurance, but regeneration effect is bad.The mid-80 owing to find the suction sulphur and the desorption performance of spinelle uniqueness, mainly transfers spinelle or spinel-like (mainly being the solid solution spinelle of rich MgO) series to the research of sulfur transfer additive.The sulfur transfer additive research direction is how to make spinelle have higher desulfuration performance and regenerability in recent years, U.S. Pat P5,108,979 have proposed to generate simultaneously the sulfur transfer additive of ceria and vanadic anhydride when forming spinelle or spinel-like structural, but the document does not provide the parameter of desulfurization performance and regenerability, and is higher by the cost of the resulting sulfur transfer additive of embodiment yet.Also there is document to mention some sulfur transfer additive and has nitrogen and the combustion-supporting effect of falling, still do not provide the concrete chemical formula or the structural formula of these sulfur transfer additives.
Summary of the invention
The objective of the invention is, provide a kind of sulphur that can efficiently reduce regeneration fume from catalytic cracking sulphur oxide, nitrogen oxide and carbon monoxide content to shift the combustion-supporting triple effect agent of denitrogenation and a kind of lower-cost preparation method and purposes.
Sulphur provided by the invention shifts the combustion-supporting triple effect agent of denitrogenation and comprises adsorbent and oxidation catalyst, and oxidation catalyst is dispersed in the adsorbent, and oxidation catalyst comprises vanadic anhydride and contains the compound ceria of rare earth cerium; It is characterized in that: also have the compound fluorine cerium oxide that the structural promoter that is dispersed in the adsorbent contains the rare earth cerium; Adsorbent is that to have general formula be AB
2-xB '
xO
4The spinel-like composite oxides of yAO.A in the formula is alkali earth metal Mg, B is the metal element A l of IIIA family, B ' is transition metal Fe, and x is 0.01～0.5, preferred 0.05～0.4, further preferred 0.05～0.20, and y is 0.2～1.2, preferred 0.4～1.2, further preferred 0.8～1.0.
The composition of above-mentioned adsorbent is MgAl
1.99Fe
0.01O
4MgO, MgAl
1.95Fe
0.05O
4MgO, MgAl
1.90Fe
0.10O
4MgO, MgAl
1.85Fe
0.15O
4MgO, MgAl
1.80Fe
0.20O
4MgO, MgAl
1.60Fe
0.40O
4MgO, MgAl
1.80Fe
0.20O
40.4MgO, MgAl
1.80Fe
0.20O
40.6MgO, MgAl
1.80Fe
0.20O
40.8MgO, MgAl
1.80Fe
0.20O
41.0MgO or MgAl
1.80Fe
0.20O
41.2MgO.
The percentage by weight that the compound that contains the rare earth cerium in the above-mentioned triple effect agent accounts for the triple effect agent is 20% to 35%, and the percentage by weight that the vanadic anhydride in the oxidation catalyst accounts for the triple effect agent is 2% to 4%, and all the other are adsorbent.
The used raw material of the compound that contains the rare earth cerium in the above-mentioned triple effect agent is the bastnaesite powder.The used raw material of vanadic anhydride in the oxidation catalyst is an ammonium metavanadate.
The method for preparing the combustion-supporting triple effect agent of sulphur transfer denitrogenation provided by the invention, described sulphur shifts the combustion-supporting triple effect agent of denitrogenation and comprises adsorbent and the oxidation catalyst and the structural promoter that are dispersed in the adsorbent, and oxidation catalyst comprises vanadic anhydride and contains the compound ceria of rare earth cerium; Structural promoter is the compound fluorine cerium oxide that contains the rare earth cerium; Adsorbent is that to have general formula be AB
2-xB '
xO
4The spinel-like composite oxides of yAO, in the formula: A is alkali earth metal Mg, and B is the metal element A l of IIIA family, and B ' is transition metal Fe, and x is 0.01～0.5, y is 0.2～1.2; This method has following steps: it is stand-by 1. bastnaesite powder and water to be mixed the suspension that obtains the bastnaesite powder; It is stand-by that ammonium metavanadate and water and organic acid are mixed the aqueous solutions of organic acids that obtains ammonium metavanadate; The hydrate of aluminium oxide and water and single Bronsted acid stirred to obtain aluminium hydroxide gel stand-by; Light magnesium oxide and water, single Bronsted acid stirred to obtain the magnesium salts slurry stand-by; Light magnesium oxide and water stirred to obtain the magnesium hydroxide slurry stand-by; Soluble in water to obtain the ferric aqueous solution stand-by with trivalent iron salt; Wherein the consumption of bastnaesite powder by the compound that contains the rare earth cerium in the finished product account for the finished product gross weight 20% to 35% and decide, the consumption of ammonium metavanadate by vanadic anhydride in the finished product account for the finished product gross weight 2% to 4% and decide, the consumption of the hydrate of aluminium oxide, light magnesium oxide and trivalent iron salt is by required AB
2-xB '
xO
4In the chemical composition of yAO and the finished product adsorbent account for the finished product gross weight 61% to 78% and decide; 2. 1. suspension, ammonium metavanadate organic acid soln and the ferric salt solution of aluminium hydroxide gel, magnesium salts slurry, magnesium hydroxide slurry, the bastnaesite powder of gained are mixed and are obtained mixed liquor with step; 3. mixed liquor is carried out drying, obtain semi-finished product; 4. semi-finished product were obtained finished product in 1～2 hour 400～800 ℃ of following roastings.
In the bastnaesite powder of above-mentioned steps in 1., chemical formula is (Ce, La) (CO
3) content 〉=93% (weight) of bastnaesite of F, the rare earth oxide content in the bastnaesite powder 〉=70% (weight), the content of rare earth Ce in the rare earth oxide＞＞La, Ce 〉=45% (weight).The organic acid that step is mixed with ammonium metavanadate in 1. is an oxalic acid, and the amount of oxalic acid all is dissolved as lower limit with ammonium metavanadate in water.
Above-mentioned steps 1. in by boehmite and the sub-acid reaction of simple substance, to make the glue acid number be 2～6 (every gram aluminium oxide Al in the system
2O
3The mM number of corresponding single Bronsted acid), solid content is the aluminium hydroxide gel of 15% to 25% (weight), Al in one-tenth glue rate 〉=95% of boehmite wherein, the boehmite
2O
3H
2The content of O 〉=70% (weight), single Bronsted acid wherein is nitric acid or acetic acid.Mixing speed when boehmite mixes with single Bronsted acid is that per minute 300 to 600 changes.Single Bronsted acid is preferably nitric acid, and the glue acid number is 3～5.
The preparation magnesium salts slurry of above-mentioned steps in 1. and the specific area 〉=100m of the light magnesium oxide of preparation magnesium hydroxide slurry
2/ g, MgO content 〉=95% (weight), single Bronsted acid of preparation magnesium salts slurry is that acetic acid is or/and nitric acid, acetic acid is or/and the mol ratio that the used amount of nitric acid is fully reacted according to itself and MgO and deciding, and the solid content of magnesium salts slurry and magnesium hydroxide slurry is 10%～14% (weight).During preparation magnesium salts slurry, earlier light magnesium oxide and water are stirred the back, add glacial acetic acid again and make magnesium acetate or/and magnesium nitrate or/and nitric acid and magnesia react completely, glacial acetic acid is or/and nitric acid and the magnesia mixing speed when reacting is per minute 300 to 600 commentaries on classics.The trivalent iron salt of step in 1. is ferric nitrate.
Mixing speed when above-mentioned steps is mixed in 2. is that per minute 300 to 600 changes.
The drying of above-mentioned steps in 3. is spray-drying, and tower top temperature is 300 to 350 ℃, and pressure is 3.0 to 5.0Mpa, and evaporation capacity is 50 to 150Kg/h, and half-finished particle diameter is distributed in content 〉=80% (weight) of the part of 80～120 μ m.
The drying of above-mentioned steps in 3. also can be oven drying, and temperature is 100 to 150 ℃.
The 4. middle roasting process of above-mentioned steps adopts the method that slowly heats up, and sintering temperature is preferably 400～500 ℃, and roasting time is preferably 80 to 100 minutes.
When the combustion-supporting triple effect agent of sulphur transfer denitrogenation of the present invention is used in the petroleum refining catalytic cracking process, enter long-pending in the regenerator sulphur, the nitrogen oxide that contains some in the Cracking catalyst to be generated of coke arranged, Cracking catalyst to be generated contacts with air from regenerator bottoms and forms fluidized-bed layer and carry out regenerative response, wherein contained sulphur then generates sulfur dioxide with airborne oxygen reaction, and carbon wherein and oxygen reaction generate carbon monoxide; Under the vanadic anhydride in triple effect agent of the present invention and the catalytic action of ceria, sulfur dioxide and oxygen reaction generate sulfur trioxide.For ceria not only catalysis the oxidation of sulfur dioxide, and catalysis the oxidation of carbon monoxide; In catalytic process, ceria is oxidized to sulfur trioxide and carbon dioxide with sulfur dioxide and carbon monoxide, and self is reduced into cerium sesquioxide, thereby has realized falling sulphur and combustion-supporting.The cerium sesquioxide of this moment is oxidized because of having reproducibility.Most of cerium sesquioxide is when being become ceria by dioxygen oxidation, and a part of cerium sesquioxide makes nitric oxide reduction become nitrogen, and self is oxidized to ceria, thereby has realized falling nitrogen.Nitrogen and carbon dioxide are discharged as the part of regenerated flue gas, the sulfur trioxide that is generated is by the adsorbents adsorb in the triple effect agent of the present invention, and generate magnesium sulfate, thereby make triple effect agent of the present invention carry out effective catalytic oxidation and absorption to the sulfur dioxide in the regenerated flue gas with the reaction of wherein magnesia.After triple effect agent of the present invention enters riser reactor with the Cracking catalyst of regenerating, magnesium sulfate in the triple effect agent and hydrogen reaction, generate magnesia and hydrogen sulfide, hydrogen sulfide then enters next procedure with reaction oil gas, magnesian generation then makes the adsorbent in the triple effect agent of the present invention obtain regeneration, and the triple effect agent after the regeneration enters regenerator with Cracking catalyst and recycles.Relevant reaction equation is as follows:
After the triple effect agent of having adsorbed oxysulfide enters reactor, following reaction takes place discharge H
2S self also obtains regeneration.
At stripping section,, also there is following reaction because of the participation of steam:
Ceria in the triple effect agent can be reduced to cerium sesquioxide by sulfur dioxide and carbon monoxide:
The trivalent cerium oxide can be a quadrivalent cerium by nitric oxide or dioxygen oxidation:
The present invention has positive effect: the adsorbent of the rich MgO spinel-like structural that (1) the present invention is selected has good desulfurization performance, but also effective regeneration.Because MgO can with V
2O
5Interact, generate (MgO)
3V
2O
8So, have the very strong vanadium ability of catching, thereby suppress the toxic action of vanadium Cracking catalyst.(2) the present invention selects for use the bastnaesite powder as the raw material that the cerium compound catalyst is provided, because of the structure of spinel-like and fluorine cerium oxide and ceria generate simultaneously, thereby improved the capacity of MgO in the spinel-like, can make MgO content superfluous 400% and do not dissociate out, thereby improve the activity that product sulphur shifts greatly.Selecting the bastnaesite powder for use is that raw material has also reduced production cost of products.(3) introduce transition elements iron in the adsorbent of triple effect agent of the present invention, made spinel structure generation distortion of lattice, increased substantially the product desulfurization performance.(4), use triple effect agent of the present invention can make SO in first regenerator flue gas according to relevant test
XRemoval efficiency 〉=60% makes the SO in second regenerator flue gas
XSO in the flue gas of removal efficiency 〉=80%, the second regenerator
XContent average out to≤5mg/m
3, NO in second regenerated flue gas
XRemoval efficiency 〉=90%, obvious to the combustion-supporting effect of carbon monoxide, need not re-use the platinum combustion adjuvant.(5) use triple effect agent of the present invention after, the acid dew-point temperature of regenerated flue gas reduces, two again by 122 ℃ drop to≤60 ℃, simultaneously two again the pH value of flue gas lime set significantly improve, bring up to about 5.4 by 2; Because corrosive substance content reduces in the regenerated flue gas, eliminated the environment that produces the nitrate stress corrosion cracking, have the effect that suppresses the regenerator crackle.(6) use triple effect agent of the present invention that the main quality index of distribution of catalytic cracking product and product is not had tangible influence, and discharge amount of pollution significantly descend.
Description of drawings
Fig. 1 is triple effect agent absorption SO of the present invention
XPreceding X-ray diffractogram.Ge1 wherein represents the eutectic thing of ceria and fluorine cerium oxide, and P represents magnesia, and S represents spinelle.
Fig. 2 is triple effect agent absorption SO of the present invention
XAfter X-ray diffractogram.Ce2 wherein represents ceria, and S represents spinelle.
The specific embodiment
The preparation method of triple effect agent lifts the following example it is described, but is not limited only to these embodiment.
(embodiment 1)
In agitator, add 99.84 gram water successively, 3.73 gram glacial acetic acid and 18.28 gram boehmites, the speed high-speed stirred of changeing with per minute 400 30 minutes, aluminium glue A.Add 26.88 gram water and 6.17 gram light magnesium oxides in agitator successively, the back (about 5 minutes) that stirs slowly adds 18.37 gram glacial acetic acid, the speed high-speed stirred of changeing with per minute 400 30 minutes, magnesium slurry M1.In agitator, add 45.26 gram water and 6.17 gram light magnesium oxides successively, stir, get magnesium slurry M2.With 0.615 gram Fe (NO
3)
39H
2O and 12 gram bastnaesite powder are made 50% the aqueous solution respectively.1.029 gram ammonium metavanadates are put into the water of about 9 times of weights, put into oxalic acid until all dissolvings and make 10% oxalic acid aqueous solution of ammonium metavanadate.The oxalic acid solution of the aqueous solution of above-mentioned aluminium glue A, magnesium slurry M1, magnesium slurry M2, ferric nitrate and bastnaesite, ammonium metavanadate added in the agitator successively mix, with the speed high-speed stirred of per minute 400 commentaries on classics 30 minutes.The gained slurry in 120 ℃ of dryings, then in 500 ℃ of roastings 80 minutes, is promptly got triple effect agent finished product.The composition of the adsorbent after the roasting in the prepared triple effect agent is MgAl
1.99Fe
0.01O
4MgO is as the CeO of oxidation catalyst
2And V
2O
5Be dispersed in the adsorbent, also be dispersed in the adsorbent as the CeFO of structural promoter.
(embodiment 2)
In agitator, add 97.22 gram water successively, 3.63 gram glacial acetic acid and 17.80 gram boehmites, the speed high-speed stirred of changeing with per minute 350 30 minutes, aluminium glue A.Add 26.71 gram water and 6.13 gram light magnesium oxides in agitator successively, the back (about 5 minutes) that stirs slowly adds 18.26 gram glacial acetic acid, the speed high-speed stirred of changeing with per minute 350 30 minutes, magnesium slurry M1.In agitator, add 44.97 gram water and 6.13 gram light magnesium oxides successively, stir, get magnesium slurry M2.With 3.073 gram Fe (NO
3)
39H
2O and 12 gram bastnaesite powder are made 50% the aqueous solution respectively.1.029 gram ammonium metavanadates are put into the water of about 9 times of weights, put into oxalic acid until all dissolvings and make 10% oxalic acid aqueous solution of ammonium metavanadate.The oxalic acid solution of the aqueous solution of above-mentioned aluminium glue A, magnesium slurry M1, magnesium slurry M2, ferric nitrate and bastnaesite, ammonium metavanadate added in the agitator successively mix, with the speed high-speed stirred of per minute 350 commentaries on classics 30 minutes.The gained slurry in 120 ℃ of dryings, then in 500 ℃ of roastings 80 minutes, is promptly got triple effect agent finished product.The composition of the adsorbent after the roasting in the prepared triple effect agent is MgAl
1.95Fe
0.05O
4MgO is as the CeO of oxidation catalyst
2And V
2O
5Be dispersed in the adsorbent, also be dispersed in the adsorbent as the CeFO of structural promoter.
(embodiment 3)
In agitator, add 93.99 gram water successively, 3.51 gram glacial acetic acid and 17.21 gram boehmites, the speed high-speed stirred of changeing with per minute 350 30 minutes, aluminium glue A.Add 26.51 gram water and 6.09 gram light magnesium oxides in agitator successively, the back (about 5 minutes) that stirs slowly adds 18.12 gram glacial acetic acid, the speed high-speed stirred of changeing with per minute 350 30 minutes, magnesium slurry M1.In agitator, add 44.62 gram water and 6.09 gram light magnesium oxides successively, stir, get magnesium slurry M2.With 6.097 gram Fe (NO
3)
39H
2O and 12 gram bastnaesite powder are made 50% the aqueous solution respectively.1.029 gram ammonium metavanadates are put into the water of about 9 times of weights, put into oxalic acid until all dissolvings and make 10% oxalic acid aqueous solution of ammonium metavanadate.The oxalic acid solution of the aqueous solution of above-mentioned aluminium glue A, magnesium slurry M1, magnesium slurry M2, ferric nitrate and bastnaesite, ammonium metavanadate added in the agitator successively mix, with the speed high-speed stirred of per minute 350 commentaries on classics 30 minutes.With 120 ℃ of dryings of gained slurry,, promptly get triple effect agent finished product then in 500 ℃ of roastings 80 minutes.The composition of the adsorbent after the roasting in the prepared triple effect agent is MgAl
1.90Fe
0.10O
4MgO is as the CeO of oxidation catalyst
2And V
2O
5Be dispersed in the adsorbent, also be dispersed in the adsorbent as the CeFO of structural promoter.
(embodiment 4)
In agitator, add 90.81 gram water successively, 3.39 gram glacial acetic acid and 16.62 gram boehmites, the speed high-speed stirred of changeing with per minute 350 30 minutes, aluminium glue A.Add 26.30 gram water and 6.04 gram light magnesium oxides in agitator successively, the back (about 5 minutes) that stirs slowly adds 17.98 gram glacial acetic acid, the speed high-speed stirred of changeing with per minute 350 30 minutes, magnesium slurry M1.In agitator, add 44.28 gram water and 6.04 gram light magnesium oxides successively, stir, get magnesium slurry M2.With 9.075 gram Fe (NO
3)
39H
2O and 12 gram bastnaesite powder are made 50% the aqueous solution respectively.1.029 gram ammonium metavanadates are put into the water of about 9 times of weights, put into oxalic acid until all dissolvings and make 10% oxalic acid aqueous solution of ammonium metavanadate.The oxalic acid solution of the aqueous solution of above-mentioned aluminium glue A, magnesium slurry M1, magnesium slurry M2, ferric nitrate and bastnaesite, ammonium metavanadate added in the agitator successively mix, with the speed high-speed stirred of per minute 350 commentaries on classics 30 minutes.The gained slurry in 120 ℃ of dryings, then in 500 ℃ of roastings 80 minutes, is promptly got triple effect agent finished product.The composition of the adsorbent after the roasting in the prepared triple effect agent is MgAl
1.85Fe
0.15O
4MgO is as the CeO of oxidation catalyst
2And V
2O
5Be dispersed in the adsorbent, also be dispersed in the adsorbent as the CeFO of structural promoter.
(embodiment 5)
In agitator, add 87.68 gram water successively, 3.27 gram glacial acetic acid and 16.05 gram boehmites, the speed high-speed stirred of changeing with per minute 350 30 minutes, aluminium glue A.Add 26.10 gram water and 5.99 gram light magnesium oxides in agitator successively, the back (about 5 minutes) that stirs slowly adds 17.84 gram glacial acetic acid, the speed high-speed stirred of changeing with per minute 350 30 minutes, magnesium slurry M1.In agitator, add 43.94 gram water and 5.99 gram light magnesium oxides successively, stir, get magnesium slurry M2.With 12.008 gram Fe (NO
3)
39H
2O and 12 gram bastnaesite powder are made 50% the aqueous solution respectively.1.029 gram ammonium metavanadates are put into the water of about 9 times of weights, put into oxalic acid until all dissolvings and make 10% oxalic acid aqueous solution of ammonium metavanadate.The oxalic acid solution of the aqueous solution of above-mentioned aluminium glue A, magnesium slurry M1, magnesium slurry M2, ferric nitrate and bastnaesite, ammonium metavanadate added in the agitator successively mix, with the speed high-speed stirred of per minute 350 commentaries on classics 30 minutes.The gained slurry in 120 ℃ of dryings, then in 500 ℃ of roastings 80 minutes, is promptly got triple effect agent finished product.The composition of the adsorbent after the roasting in the prepared triple effect agent is MgAl
1.80Fe
0.20O
4MgO is as the CeO of oxidation catalyst
2And V
2O
5Be dispersed in the adsorbent, also be dispersed in the adsorbent as the CeFO of structural promoter.
(embodiment 6)
In agitator, add 75.62 gram water successively, 2.82 gram glacial acetic acid and 13.84 gram boehmites, the speed high-speed stirred of changeing with per minute 350 30 minutes, aluminium glue A.Add 25.32 gram water and 5.81 gram light magnesium oxides in agitator successively, the back (about 5 minutes) that stirs slowly adds 17.31 gram glacial acetic acid, the speed high-speed stirred of changeing with per minute 350 30 minutes, magnesium slurry M1.In agitator, add 42.63 gram water and 5.81 gram light magnesium oxides successively, stir, get magnesium slurry M2.With 23.301 gram Fe (NO
3)
39H
2O and 12 gram bastnaesite powder are made 50% the aqueous solution respectively.1.029 gram ammonium metavanadates are put into the water of about 9 times of weights, put into oxalic acid until all dissolvings and make 10% oxalic acid aqueous solution of ammonium metavanadate.The oxalic acid solution of the aqueous solution of above-mentioned aluminium glue A, magnesium slurry M1, magnesium slurry M2, ferric nitrate and bastnaesite, ammonium metavanadate added in the agitator successively mix, with the speed high-speed stirred of per minute 350 commentaries on classics 30 minutes.The gained slurry in 120 ℃ of dryings, then in 500 ℃ of roastings 80 minutes, is promptly got triple effect agent finished product.The composition of the adsorbent after the roasting in the prepared triple effect agent is MgAl
1.60Fe
0.40O
4MgO is as the CeO of oxidation catalyst
2And V
2O
5Be dispersed in the adsorbent, also be dispersed in the adsorbent as the CeFO of structural promoter.
(embodiment 7)
In agitator, add 84.41 gram water successively, 4.54 gram glacial acetic acid and 22.24 gram boehmites, the speed high-speed stirred of changeing with per minute 350 30 minutes, aluminium glue A.Add 25.31 gram water and 5.81 gram light magnesium oxides in agitator successively, the back (about 5 minutes) that stirs slowly adds 17.30 gram glacial acetic acid, the speed high-speed stirred of changeing with per minute 500 30 minutes, magnesium slurry M1.In agitator, add 42.61 gram water and 5.81 gram light magnesium oxides successively, stir, get magnesium slurry M2.With 13.447 gram Fe (NO
3)
39H
2O and 15 gram bastnaesite powder are made 50% the aqueous solution respectively.1.607 gram ammonium metavanadates are put into the water of about 9 times of weights, put into oxalic acid until all dissolvings and make 10% oxalic acid aqueous solution of ammonium metavanadate.The oxalic acid solution of the aqueous solution of above-mentioned aluminium glue A, magnesium slurry M1, magnesium slurry M2, ferric nitrate and bastnaesite, ammonium metavanadate added in the agitator successively mix, with the speed high-speed stirred of per minute 500 commentaries on classics 30 minutes.The gained slurry in 120 ℃ of dryings, then in 500 ℃ of roastings 80 minutes, is promptly got triple effect agent finished product.The composition of the adsorbent after the roasting in the prepared triple effect agent is MgAl
1.8Fe
0.2O
40.4MgO, as the CeO of oxidation catalyst
2And V
2O
5Be dispersed in the adsorbent, also be dispersed in the adsorbent as the CeFO of structural promoter.
(embodiment 8)
In agitator, add 80.59 gram water successively, 4.33 gram glacial acetic acid and 21.23 gram boehmites, the speed high-speed stirred of changeing with per minute 350 30 minutes, aluminium glue A.Add 27.62 gram water and 6.34 gram light magnesium oxides in agitator successively, the back (about 5 minutes) that stirs slowly adds 18.88 gram glacial acetic acid, the speed high-speed stirred of changeing with per minute 350 30 minutes, magnesium slurry M1.In agitator, add 46.49 gram water and 6.34 gram light magnesium oxides successively, stir, get magnesium slurry M2.With 12.950 gram Fe (NO
3)
39H
2O and 15 gram bastnaesite powder are made 50% the aqueous solution respectively.1.607 gram ammonium metavanadates are put into the water of about 9 times of weights, put into oxalic acid until all dissolvings and make 10% oxalic acid aqueous solution of ammonium metavanadate.The oxalic acid solution of the aqueous solution of above-mentioned aluminium glue A, magnesium slurry M1, magnesium slurry M2, ferric nitrate and bastnaesite, ammonium metavanadate added in the agitator successively mix, with the speed high-speed stirred of per minute 350 commentaries on classics 30 minutes.The gained slurry in 120 ℃ of dryings, then in 500 ℃ of roastings 80 minutes, is promptly got triple effect agent finished product.The composition of the adsorbent after the roasting in the prepared triple effect agent is MgAl
1.8Fe
0.2O
40.6MgO, as the CeO of oxidation catalyst
2And V
2O
5Be dispersed in the adsorbent, also be dispersed in the adsorbent as the CeFO of structural promoter.
(embodiment 9)
In agitator, add 77.10 gram water successively, 4.14 gram glacial acetic acid and 20.31 gram boehmites, the speed high-speed stirred of changeing with per minute 350 30 minutes, aluminium glue A.Add 29.72 gram water and 6.82 gram light magnesium oxides in agitator successively, the back (about 5 minutes) that stirs slowly adds 20.32 gram glacial acetic acid, the speed high-speed stirred of changeing with per minute 350 30 minutes, magnesium slurry M1.In agitator, add 50.04 gram water and 6.82 gram light magnesium oxides successively, stir, get magnesium slurry M2.With 12.489 gram Fe (NO
3)
39H
2O and 15 gram bastnaesite powder are made 50% the aqueous solution respectively.1.607 gram ammonium metavanadates are put into the water of about 9 times of weights, put into oxalic acid until all dissolvings and make 10% oxalic acid aqueous solution of ammonium metavanadate.The oxalic acid solution of the aqueous solution of above-mentioned aluminium glue A, magnesium slurry M1, magnesium slurry M2, ferric nitrate and bastnaesite, ammonium metavanadate added in the agitator successively mix, with the speed high-speed stirred of per minute 350 commentaries on classics 30 minutes.The gained slurry in 120 ℃ of dryings, then in 500 ℃ of roastings 80 minutes, is promptly got triple effect agent finished product.The composition of the adsorbent after the roasting in the prepared triple effect agent is MgAl
1.8Fe
0.2O
40.8MgO, as the CeO of oxidation catalyst
2And V
2O
5Be dispersed in the adsorbent, also be dispersed in the adsorbent as the CeFO of structural promoter.
(embodiment 10)
In agitator, add 73.90 gram water successively, 3.97 gram glacial acetic acid and 19.47 gram boehmites, the speed high-speed stirred of changeing with per minute 350 30 minutes, aluminium glue A.Add 31.65 gram water and 7.27 gram light magnesium oxides in agitator successively, the back (about 5 minutes) that stirs slowly adds 21.64 gram glacial acetic acid, the speed high-speed stirred of changeing with per minute 350 30 minutes, magnesium slurry M1.In agitator, add 53.29 gram water and 7.27 gram light magnesium oxides successively, stir, get magnesium slurry M2.With 12.059 gram Fe (NO
3)
39H
2O and 15 gram bastnaesite powder are made 50% the aqueous solution respectively.1.607 gram ammonium metavanadates are put into the water of about 9 times of weights, put into oxalic acid until all dissolvings and make 10% oxalic acid aqueous solution of ammonium metavanadate.The oxalic acid solution of the aqueous solution of above-mentioned aluminium glue A, magnesium slurry M1, magnesium slurry M2, ferric nitrate and bastnaesite, ammonium metavanadate added in the agitator successively mix, with the speed high-speed stirred of per minute 350 commentaries on classics 30 minutes.The gained slurry in 120 ℃ of dryings, then in 500 ℃ of roastings 80 minutes, is promptly got triple effect agent finished product.The composition of the adsorbent after the roasting in the prepared triple effect agent is MgAl
1.8Fe
0.2O
4MgO is as the CeO of oxidation catalyst
2And V
2O
5Be dispersed in the adsorbent, also be dispersed in the adsorbent as the CeFO of structural promoter.
(embodiment 11)
In agitator, add 70.95 gram water successively, 3.81 gram glacial acetic acid and 18.69 gram boehmites, the speed high-speed stirred of changeing with per minute 350 30 minutes, aluminium glue A.Add 33.43 gram water and 7.68 gram light magnesium oxides in agitator successively, the back (about 5 minutes) that stirs slowly adds 22.85 gram glacial acetic acid, the speed high-speed stirred of changeing with per minute 350 30 minutes, magnesium slurry M1.In agitator, add 56.28 gram water and 7.68 gram light magnesium oxides successively, stir, get magnesium slurry M2.With 11.658 gram Fe (NO
3)
39H
2O and 15 gram bastnaesite powder are made 50% the aqueous solution respectively.1.607 gram ammonium metavanadates are put into the water of about 9 times of weights, put into oxalic acid until all dissolvings and make 10% oxalic acid aqueous solution of ammonium metavanadate.The oxalic acid solution of the aqueous solution of above-mentioned aluminium glue A, magnesium slurry M1, magnesium slurry M2, ferric nitrate and bastnaesite, ammonium metavanadate added in the agitator successively mix, with the speed high-speed stirred of per minute 350 commentaries on classics 30 minutes.The gained slurry in 120 ℃ of dryings, then in 500 ℃ of roastings 80 minutes, is promptly got triple effect agent finished product.The composition of the adsorbent after the roasting in the prepared triple effect agent is MgAl
1.8Fe
0.2O
41.2MgO, as the CeO of oxidation catalyst
2And V
2O
5Be dispersed in the adsorbent, also be dispersed in the adsorbent as the CeFO of structural promoter.
Embodiment 1 to embodiment 11 is a prepared in laboratory triple effect agent method, is common drying.In the bastnaesite powder that is wherein adopted, chemical formula is (Ce, La) (CO
3) content 〉=93% (weight) of bastnaesite of F, the rare earth oxide content in the bastnaesite powder 〉=70% (weight), the ree distribution pattern Ce in the rare earth oxide＞＞La, Ce 〉=45% (weight).Acid number (every gram aluminium oxide Al in the system by boehmite and the sub-acid reaction of simple substance, the aluminium hydroxide glue that makes
2O
3The mM number of corresponding single Bronsted acid) be 3～5, solid content is 15% to 25%, Al in one-tenth glue rate 〉=95% of used boehmite, the boehmite
2O
3H
2The content of O 〉=70% (weight).Specific area 〉=the 100m of the light magnesium oxide that preparation magnesium slurry M1 and magnesium slurry M2 are used
2/ g, MgO content 〉=95%.
The method of embodiment 1 to embodiment 11 prepared triple effect agent sample being estimated in the laboratory is as follows:
Sulphur shifts to be estimated: experimental provision is a quartz tube reactor, internal diameter 11mm, and fixed bed is got 0.2 gram sample evaluation.Be SO
2When absorption is estimated, total gas flow rate 200ml/min, wherein air mass flow 40ml/min (O
2Account for 4%), SO
2Flow 2～4ml/min accounts for 1%～2%, with N
2Balance.Adsorption time is generally at 30min, saturated basically absorption, 700 ℃ of temperature.During desorb, desorption gas is H
2, flow 40ml/min.Desorption time 30min, temperature is divided 540 ℃ and 700 ℃ two kinds.Absorption, desorb so repeatedly, cycle-index reaches more than six times, and the triple effect agent is to SO under mensuration uniform temperature and the atmospheric condition
2Average adsorption rate and average desorption efficiency, judge its quality good or not with this.Adsorption rate and desorption efficiency are high more, and triple effect agent performance is good more.
Under identical condition, the laboratory records the Canadian triple effect agent that is used for the refinery, Fujian, and it is to SO
2Saturated adsorption rate be 45%.
Fall the combustion-supporting evaluation of nitrogen: experimental provision is a quartz tube reactor, and ebullated bed is got 3 gram sample evaluations during experiment.When estimating at its CO combustion-supporting effect, mist is CO content 10000ppmv, O
2Content 1%, N
2The mist of balance.At NO
xDuring degradation experiment, mist is CO content 10000ppmv, NO content 200ppmv, O
2Content 0.3%, N
2Balance.Measure the composition after the gas reaction under the different temperatures, i.e. its conversion ratio as can be known.Table 3 and table 4 are 50% and the corresponding temperature of 90% o'clock different instances sample for conversion ratio.Temperature is low more, illustrates that to fall the combustion-supporting activity of nitrogen strong more.
Measured adsorption rate and desorption efficiency when table 1 shifts test for the sample of embodiment 1 to embodiment 11 gained being carried out sulphur.
Table 1
| Embodiment | 1 | 2 | 3 | 4 | 5 | 6 |
| Adsorption rate (%) | 63 | 68.9 | 69.5 | 69.6 | 63.1 | 64.7 |
| Desorption efficiency (%) | 101.5 | 102.6 | 101.7 | 104.2 | 101.9 | 98.5 |
| Embodiment | 7 | 8 | 9 | 10 | 11 | |
| Adsorption rate (%) | 66.1 | 66.0 | 69.7 | 75.0 | 73.5 | |
| Desorption efficiency (%) | 98.1 | 100.8 | 102.2 | 102.3 | 101.8 |
Table 2 carries out NO for the sample to embodiment 1 to embodiment 11 gained
xMeasured conversion ratio is the data of 50%, 90% o'clock corresponding temperature during with the conversion test of CO.
Table 2
| The combustion-supporting experiment of CO | The NO degradation experiment | |||
| Embodiment | 50% conversion temperature T 50 | 90% conversion temperature T 90 | 50% conversion temperature T 50 | 90% conversion temperature T 90 |
| 1 | 395 | 475 | 447 | 481 |
| 2 | 378 | 455 | 425 | 460 |
| 3 | 367 | 445 | 419 | 451 |
| 4 | 360 | 440 | 410 | 445 |
| 5 | 390 | 472 | 445 | 480 |
| 6 | 384 | 467 | 436 | 472 |
| 7 | 380 | 455 | 431 | 465 |
| 8 | 382 | 451 | 427 | 471 |
| 9 | 363 | 440 | 417 | 453 |
| 10 | 342 | 415 | 403 | 439 |
| 11 | 350 | 428 | 412 | 447 |
Embodiment 12 is an industrial preparation triple effect agent method, is spray-drying, is example with the 50Kg finished product.
(embodiment 12)
In stirred tank, add 73.90 kg water successively, 3.97 kg of ice acetic acid and 19.47 kilograms of boehmites, the speed high-speed stirred of changeing with per minute 350 30 minutes, glue acid number (every gram aluminium oxide Al in the system
2O
3The mM number of corresponding single Bronsted acid) be 4, solid content is 20% aluminium hydroxide gel A, Al in one-tenth glue rate 〉=95% of the boehmite that is adopted, the boehmite
2O
3H
2The content of O 〉=70% (weight).Add 31.65 kg water and 7.27 kilograms of light magnesium oxides in stirred tank successively, the back (about 5 minutes) that stirs slowly adds 21.64 kg of ice acetic acid, the speed high-speed stirred of changeing with per minute 350 30 minutes, magnesium slurry M1.In stirred tank, add 53.29 kg water and 7.27 kilograms of light magnesium oxides successively, stir, get magnesium slurry M2.Specific area 〉=the 100m of the light magnesium oxide that magnesium slurry M1 and M2 are used
2/ g, MgO content 〉=95%.With 12.059 kilograms of Fe (NO
3)
39H
2O and 15 kilograms of bastnaesite powder are made 50% the aqueous solution respectively.Wherein in the bastnaesite powder, chemical formula is (Ce, La) (CO
3) content 〉=93% (weight) of bastnaesite of F, the rare earth oxide content in the bastnaesite powder 〉=70% (weight), the ree distribution pattern Ce in the rare earth oxide＞＞La, Ce 〉=45% (weight).1.607 kilograms of ammonium metavanadates are dissolved in oxalic acid, and the amount of oxalic acid is all dissolved in water with ammonium metavanadate and is exceeded, and makes 10% oxalic acid aqueous solution.The oxalic acid solution of the aqueous solution of above-mentioned aluminium glue A, magnesium slurry M1, magnesium slurry M2, ferric nitrate and bastnaesite, ammonium metavanadate added in the stirred tank successively mix, with the speed high-speed stirred of per minute 350 commentaries on classics 30 minutes.In 300 ℃ of spray-dryings, pressure 4MPa, evaporation capacity are 50 to 150Kg/h with the gained slurry, and the semi-finished product particle diameter is distributed in content 〉=80% (weight) of the part of 80～120 μ m.In 500 ℃ of roastings 80 minutes, promptly get triple effect agent finished product then.The one-tenth 1 of the adsorbent after the roasting in the prepared triple effect agent is divided into MgAl
1.8Fe
0.2O
4MgO is as the CeO of oxidation catalyst
2And V
2O
5Be dispersed in the adsorbent, also be dispersed in the adsorbent as the CeFO of structural promoter.
The triple effect agent that will make by the condition of present embodiment is applied in the cracking of oil Catalytic processes, not add any triple effect agent is reference standards, after using triple effect agent of the present invention (its reserve accounts for general reserve 2%), comparing with reference standards of sulfur in smoke of first order regenerator outlet is 0.33, so triple effect agent of the present invention is 67% to the removal efficiency again and again of sulfur dioxide; Triple effect agent of the present invention to sulfur dioxide two removal efficiency is higher again, be 81%.And under identical condition, the Canadian triple effect agent that is used for the refinery, Fujian is 40% to the removal efficiency again and again of sulfur dioxide.Triple effect agent of the present invention is to two flue gas NO again
xRemoval efficiency is 92%.
The X-ray diffraction test is carried out in the triple effect agent of present embodiment gained obtained X-ray diffractogram shown in Figure 1.When adsorbing SO by the above-mentioned laboratory method that agent is estimated to triple effect
2After, adsorption time is 30 minutes, obtains X-ray diffractogram shown in Figure 2.From two diffraction patterns as can be known: triple effect agent absorption SO
2After, the characteristic peak of the eutectic thing of ceria and fluorine cerium oxide disappears, only the characteristic peak of remaining ceria; Magnesian characteristic peak disappears; The characteristic peak of spinelle does not become.
Claims (21)
1, a kind of sulphur shifts the combustion-supporting triple effect agent of denitrogenation, comprises adsorbent and oxidation catalyst, and oxidation catalyst is dispersed in the adsorbent, and oxidation catalyst comprises vanadic anhydride and contains the compound ceria of rare earth cerium; It is characterized in that: also have the compound fluorine cerium oxide that the structural promoter that is dispersed in the adsorbent contains the rare earth cerium; Adsorbent is the spinel-like composite oxides with following formula:
AB
2-xB′
xO
4·yAO
In the formula, A is alkali earth metal Mg, and B is the metal element A l of IIIA family, and B ' is transition metal Fe, and x is 0.01～0.5, and y is 0.2～1.2.
2, sulphur according to claim 1 shifts the combustion-supporting triple effect agent of denitrogenation, and it is characterized in that: x is 0.05～0.4, and y is 0.4～1.2.
3, sulphur according to claim 2 shifts the combustion-supporting triple effect agent of denitrogenation, and it is characterized in that: x is 0.05～0.20, and y is 0.8～1.0.
4, sulphur according to claim 1 shifts the combustion-supporting triple effect agent of denitrogenation, and it is characterized in that: the composition of adsorbent is MgAl
1.99Fe
0.01O
4MgO, MgAl
1.95Fe
0.05O
4MgO, MgAl
1.90Fe
0.10O
4MgO, MgAl
1.85Fe
0.15O
4MgO, MgAl
1.80Fe
0.20O
4MgO, MgAl
1.60Fe
0.40O
4MgO, MgAl
1.80Fe
0.20O
40.4MgO, MgAl
1.80Fe
0.20O
40.6MgO, MgAl
1.80Fe
0.20O
40.8MgO, MgAl
1.80Fe
0.20O
41.0MgO or MgAl
1.80Fe
0.20O
41.2MgO.
5, sulphur according to claim 1 shifts the combustion-supporting triple effect agent of denitrogenation, it is characterized in that: the percentage by weight that the compound that contains the rare earth cerium in the combustion-supporting triple effect agent of sulphur transfer denitrogenation accounts for the combustion-supporting triple effect agent of sulphur transfer denitrogenation is 20% to 35%, the percentage by weight that vanadic anhydride in the oxidation catalyst accounts for the combustion-supporting triple effect agent of sulphur transfer denitrogenation is 2% to 4%, and all the other are adsorbent.
6, sulphur according to claim 5 shifts the combustion-supporting triple effect agent of denitrogenation, it is characterized in that: the used raw material of the compound that contains the rare earth cerium that sulphur shifts in the combustion-supporting triple effect agent of denitrogenation is the bastnaesite powder.
7, sulphur according to claim 5 shifts the combustion-supporting triple effect agent of denitrogenation, and it is characterized in that: the used raw material of the vanadic anhydride in the oxidation catalyst is an ammonium metavanadate.
8, a kind of method for preparing the combustion-supporting triple effect agent of sulphur transfer denitrogenation, described sulphur shifts the combustion-supporting triple effect agent of denitrogenation and comprises adsorbent and the oxidation catalyst and the structural promoter that are dispersed in the adsorbent, and oxidation catalyst comprises compound ceria and the vanadic anhydride that contains the rare earth cerium; Structural promoter is the compound fluorine cerium oxide that contains the rare earth cerium; Adsorbent is that to have general formula be AB
2-xB '
xO
4The spinel-like composite oxides of yAO, in the formula: A is alkali earth metal Mg, and B is the metal element A l of IIIA family, and B ' is transition metal Fe, and x is 0.01～0.5, y is 0.2～1.2; This method has following steps: it is stand-by 1. bastnaesite powder and water to be mixed the suspension that obtains the bastnaesite powder; It is stand-by that ammonium metavanadate and water and organic acid are mixed the aqueous solutions of organic acids that obtains ammonium metavanadate; The hydrate of aluminium oxide and water and single Bronsted acid stirred to obtain aluminium hydroxide gel stand-by; Light magnesium oxide and water, single Bronsted acid stirred to obtain the magnesium salts slurry stand-by; Light magnesium oxide and water stirred to obtain the magnesium hydroxide slurry stand-by; Soluble in water to obtain the ferric aqueous solution stand-by with trivalent iron salt; Wherein the consumption of bastnaesite powder by the compound that contains the rare earth cerium in the finished product account for the finished product gross weight 20% to 35% and decide, the consumption of ammonium metavanadate by vanadic anhydride in the finished product account for the finished product gross weight 2% to 4% and decide, the consumption of the hydrate of aluminium oxide, light magnesium oxide and trivalent iron salt is by required AB
2-xB '
xO
4In the chemical composition of yAO and the finished product adsorbent account for the finished product gross weight 61% to 78% and decide; 2. 1. suspension, ammonium metavanadate organic acid soln and the ferric salt solution of aluminium hydroxide gel, magnesium salts slurry, magnesium hydroxide slurry, the bastnaesite powder of gained are mixed and are obtained mixed liquor with step; 3. mixed liquor is carried out drying, obtain semi-finished product; 4. semi-finished product were obtained finished product in 1～2 hour 400～800 ℃ of following roastings.
9, sulphur according to claim 8 shifts the preparation method of the combustion-supporting triple effect agent of denitrogenation, it is characterized in that: in the bastnaesite powder of step in 1., chemical formula is (Ce, La) (CO
3) content 〉=93% (weight) of bastnaesite of F, the rare earth oxide content in the bastnaesite powder 〉=70% (weight), the ree distribution pattern Ce in the rare earth oxide＞＞La, Ce 〉=45% (weight).
10, sulphur according to claim 8 shifts the preparation method of the combustion-supporting triple effect agent of denitrogenation, it is characterized in that: the organic acid that step is mixed with ammonium metavanadate in 1. is an oxalic acid, and the amount of oxalic acid all is dissolved as lower limit with ammonium metavanadate in water.
11, sulphur according to claim 8 shifts the preparation method of the combustion-supporting triple effect agent of denitrogenation, it is characterized in that: step 1. in by boehmite and the sub-acid reaction of simple substance, make that the glue acid number is 2～6, solid content is the aluminium hydroxide gel of 15% to 25% (weight), Al in one-tenth glue rate 〉=95% of boehmite wherein, the boehmite
2O
3H
2The content of O 〉=70% (weight), single Bronsted acid wherein is nitric acid or acetic acid.
12, sulphur according to claim 11 shifts the preparation method of the combustion-supporting triple effect agent of denitrogenation, it is characterized in that: the mixing speed the when boehmite of step in 1. mixes with single Bronsted acid is per minute 300 to 600 commentaries on classics.
13, sulphur according to claim 11 shifts the preparation method of the combustion-supporting triple effect agent of denitrogenation, and it is characterized in that: single Bronsted acid is a nitric acid, and the glue acid number is 3～5.
14, sulphur according to claim 8 shifts the preparation method of the combustion-supporting triple effect agent of denitrogenation, it is characterized in that: the preparation magnesium salts slurry of step in 1. and the specific area 〉=100m of the light magnesium oxide of preparation magnesium hydroxide slurry
2/ g, MgO content 〉=95% (weight), single Bronsted acid of preparation magnesium salts slurry is that acetic acid is or/and nitric acid, acetic acid is or/and the mol ratio that the used amount of nitric acid is fully reacted according to itself and MgO and deciding, and the solid content of magnesium salts slurry and magnesium hydroxide slurry is 10%～14% (weight).
15, sulphur according to claim 14 shifts the preparation method of the combustion-supporting triple effect agent of denitrogenation, it is characterized in that: during the 1. middle preparation magnesium salts of step slurry, earlier light magnesium oxide and water are stirred the back, add glacial acetic acid again and make magnesium acetate or/and magnesium nitrate or/and nitric acid and magnesia react completely, glacial acetic acid is or/and nitric acid and the magnesia mixing speed when reacting is per minute 300 to 600 commentaries on classics.
16, sulphur according to claim 8 shifts the preparation method of the combustion-supporting triple effect agent of denitrogenation, it is characterized in that: the trivalent iron salt of step in 1. is ferric nitrate.
17, shift the preparation method of the combustion-supporting triple effect agent of denitrogenation according to Claim 8 to one of 16 described sulphur, it is characterized in that: the mixing speed when step is mixed in 2. is that per minute 300 to 600 changes.
18, shift the preparation method of the combustion-supporting triple effect agent of denitrogenation according to Claim 8 to one of 16 described sulphur, it is characterized in that: the drying of step in 3. is spray-drying, temperature is 300 to 350 ℃, pressure is 3.0 to 5.0Mpa, evaporation capacity is 50 to 150Kg/h, and half-finished particle diameter is distributed in content 〉=80% (weight) of the part of 80～120 μ m.
19, shift the preparation method of the combustion-supporting triple effect agent of denitrogenation according to Claim 8 to one of 16 described sulphur, it is characterized in that: the drying of step in 3. is oven drying, and temperature is 100 to 150 ℃.
20, shift the preparation method of the combustion-supporting triple effect agent of denitrogenation according to Claim 8 to one of 16 described sulphur, it is characterized in that: step 4. in roasting process adopt the method that slowly heats up, 400～500 ℃ of sintering temperatures, roasting time is 80 to 100 minutes.
21, by the described triple effect agent of claim 1, the application in oxysulfide, nitrogen oxide and the carbon monoxide content in reducing regeneration fume from catalytic cracking.
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|---|---|---|---|
| CNB021532842A CN1319631C (en) | 2002-11-26 | 2002-11-26 | Agent with three effect, sulphur transfers, denitrification and combustion supporting as well as its preparing method |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021532842A CN1319631C (en) | 2002-11-26 | 2002-11-26 | Agent with three effect, sulphur transfers, denitrification and combustion supporting as well as its preparing method |
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| CN1319631C true CN1319631C (en) | 2007-06-06 |
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| CN115318275A (en) * | 2022-08-30 | 2022-11-11 | 青岛惠城环保科技集团股份有限公司 | Preparation method of catalytic cracking flue gas treatment three-effect auxiliary agent |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5108979A (en) * | 1991-02-25 | 1992-04-28 | Intercat, Inc. | Synthetic spinels and processes for making them |
| US5422332A (en) * | 1993-07-30 | 1995-06-06 | Intercat, Inc. | Processes for reacting bastnaesite with metal oxides |
| US5914293A (en) * | 1994-06-01 | 1999-06-22 | Bp Amoco Corporation | Absorbent and process for removing sulfur oxides from a gaseous mixture |
-
2002
- 2002-11-26 CN CNB021532842A patent/CN1319631C/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5108979A (en) * | 1991-02-25 | 1992-04-28 | Intercat, Inc. | Synthetic spinels and processes for making them |
| US5422332A (en) * | 1993-07-30 | 1995-06-06 | Intercat, Inc. | Processes for reacting bastnaesite with metal oxides |
| US5914293A (en) * | 1994-06-01 | 1999-06-22 | Bp Amoco Corporation | Absorbent and process for removing sulfur oxides from a gaseous mixture |
Non-Patent Citations (4)
| Title |
|---|
| FCC再生烟气的脱硫助剂研究进展 朱仁发 李承烈，化工进展，第3期 2000 * |
| FCC再生烟气的脱硫助剂研究进展 朱仁发 李承烈，化工进展，第3期 2000;调变组分对流化催化裂化助剂脱硫性能的影响 朱仁发 谭乐成 王金安，华东理工大学学报，第26卷第2期 2000;流化催化裂化脱硫添加剂的研究进展 朱仁发 李承烈，化工科技，第8卷第1期 2000 * |
| 流化催化裂化脱硫添加剂的研究进展 朱仁发 李承烈，化工科技，第8卷第1期 2000 * |
| 调变组分对流化催化裂化助剂脱硫性能的影响 朱仁发 谭乐成 王金安，华东理工大学学报，第26卷第2期 2000 * |
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