CN107999086A - A kind of preparation method of catalytic cracking regeneration flue gas sulphur transfer agent - Google Patents
A kind of preparation method of catalytic cracking regeneration flue gas sulphur transfer agent Download PDFInfo
- Publication number
- CN107999086A CN107999086A CN201711171604.2A CN201711171604A CN107999086A CN 107999086 A CN107999086 A CN 107999086A CN 201711171604 A CN201711171604 A CN 201711171604A CN 107999086 A CN107999086 A CN 107999086A
- Authority
- CN
- China
- Prior art keywords
- preparation
- slurries
- sulfur transfer
- flue gas
- transfer additive
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 238000012546 transfer Methods 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 title claims abstract description 12
- 239000003546 flue gas Substances 0.000 title claims abstract description 12
- 239000005864 Sulphur Substances 0.000 title claims abstract description 11
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 10
- 238000004523 catalytic cracking Methods 0.000 title claims abstract description 8
- 230000008929 regeneration Effects 0.000 title claims abstract description 8
- 238000011069 regeneration method Methods 0.000 title claims abstract description 8
- 239000002002 slurry Substances 0.000 claims abstract description 23
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 22
- 239000011593 sulfur Substances 0.000 claims abstract description 22
- 239000000654 additive Substances 0.000 claims abstract description 21
- 230000000996 additive effect Effects 0.000 claims abstract description 21
- 239000000843 powder Substances 0.000 claims abstract description 8
- 229910001593 boehmite Inorganic materials 0.000 claims abstract description 7
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims abstract description 7
- 229910052500 inorganic mineral Inorganic materials 0.000 claims abstract description 6
- 239000011707 mineral Substances 0.000 claims abstract description 6
- 238000001694 spray drying Methods 0.000 claims abstract description 6
- 239000000395 magnesium oxide Substances 0.000 claims abstract description 5
- 238000005360 mashing Methods 0.000 claims abstract description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 12
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 6
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 3
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 3
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- 229910021577 Iron(II) chloride Inorganic materials 0.000 claims description 2
- 229910052593 corundum Inorganic materials 0.000 claims description 2
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 2
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Inorganic materials [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 claims description 2
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 9
- 239000011777 magnesium Substances 0.000 abstract description 8
- 229910052596 spinel Inorganic materials 0.000 abstract description 7
- 229910052749 magnesium Inorganic materials 0.000 abstract description 6
- 239000011029 spinel Substances 0.000 abstract description 5
- 229910052720 vanadium Inorganic materials 0.000 abstract description 5
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 abstract description 5
- -1 magnesium aluminate Chemical class 0.000 abstract description 4
- 238000005299 abrasion Methods 0.000 abstract description 2
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 abstract description 2
- 239000000292 calcium oxide Substances 0.000 abstract description 2
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 abstract description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 abstract 2
- 231100000614 poison Toxicity 0.000 abstract 1
- 230000007096 poisonous effect Effects 0.000 abstract 1
- 239000007787 solid Substances 0.000 abstract 1
- 238000000034 method Methods 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 5
- 239000003921 oil Substances 0.000 description 5
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 2
- 229910026161 MgAl2O4 Inorganic materials 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229910001425 magnesium ion Inorganic materials 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- XOCUXOWLYLLJLV-UHFFFAOYSA-N [O].[S] Chemical compound [O].[S] XOCUXOWLYLLJLV-UHFFFAOYSA-N 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000000505 pernicious effect Effects 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical compound S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/889—Manganese, technetium or rhenium
- B01J23/8892—Manganese
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
- C10G11/02—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils characterised by the catalyst used
- C10G11/04—Oxides
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
- C10G11/14—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils with preheated moving solid catalysts
- C10G11/18—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils with preheated moving solid catalysts according to the "fluidised-bed" technique
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Materials Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a kind of preparation method of catalytic cracking regeneration flue gas sulphur transfer agent, step are as follows：(1) white clouds mineral powder mashing acidifying；(2) a certain proportion of boehmite is added in slurries in (1)；(3) II A races element, VIII race's element, VII race's element are sequentially added in slurries in (2)；(4) by above-mentioned slurries spray drying forming, the catalyst is made.The preparation method of the present invention, magnesia in white clouds ore, which can form active component magnesium aluminate spinel, calcium oxide, can play solid vanadium performance, and the stable structure of itself, improve the abrasion index of sulfur transfer additive, poisonous vanadium is substituted with ferrimanganic, is poisoned during reduction preparation and use.
Description
Technical field
The present invention relates to a kind of assistant for calalytic cracking, relates in particular to a kind of catalytic cracking regeneration flue gas sulphur transfer agent
Preparation method.
Background technology
With the fast development of various countries' industry, environmental pollution becomes increasingly conspicuous, its sulphur oxide is that world today's environment is dirty
One of main pernicious gas of dye.For Petrochemical Enterprises, substantial amounts of sulphur oxygen can be produced in oil major catalyst regenerative process
Compound, has an immense impact on human body and its ecology.The method mainly hydrogenation for reducing FCC regenerated flue gas SOx discharges at present is de-
Sulphur, flue gas washing desulphurization and uses sulfur transfer additive.As its simple and convenient, economical and effective of addition of auxiliary agent.
It is reported that the sulphur for having 5-15% in raw material can be deposited on coke, and burn with reclaimable catalyst into regenerator
It is oxidized to SOx and (about contains 90%SO in SOx2And 10%SO3)。
In sulfur transfer additive, Mg is the main active component of chemisorbed SOx.The work for absorbing SOx is played in a regenerator
With the element such as Ce, V and Fe can be such that sulfate is reduced at lower temperatures.
The external research for being directed to reduce FCC flue gas SOx pollutant auxiliary agents since the 1970s, and achieve
Good results of industrial application.It mainly includes two types, magnesium aluminate spinel type and houghite and is answered for prepared by presoma
And oxide type.
The advantages that magnesium aluminate spinel is good with heat endurance, and specific surface area is big, but simple MgAl2O4Due to containing for MgO
Measure it is low, it is low there is also Sulfur capacity, inactivate the shortcomings that fast.Therefore it is more using rich magnesium types magnesium aluminate spinel (MgAl2O4yMgO).But with
The increase of content of magnesium, the mechanical strength and reducing/regenerating ability of sulfur transfer additive are decreased obviously.
The content of the invention
In view of the deficiencies of the prior art, the present invention provides a kind of preparation of catalytic cracking regeneration flue gas sulphur transfer agent
Method：
A kind of preparation method of catalytic cracking regeneration flue gas sulphur transfer agent, it is characterised in that preparation process is as follows：
(1) white clouds mineral powder mashing acidifying；
(2) a certain proportion of boehmite is added in slurries in (1)；
(3) II A races element, VIII race's element, VII race's element are sequentially added in slurries in (2)；
(4) by above-mentioned slurries spray drying forming.
White clouds miberal powder in step (1) is chemical composition CaMg (CO3)2Ore through crushing it is levigate, 600 mesh of particle diameter-
1000 mesh.
Acidifying in step (1), using hydrochloric acid and/or nitric acid, it is 2-4 to adjust slurries pH.
Boehmite additional proportion in step (2) is with Al2O3Meter accounts for the 20-30wt% of sulfur transfer additive wgt dry basis by total.
II A races element in step (3) is Mg, can be MgCl2、Mg(NO3)2One or two kinds of mixing, additional proportion
The 10-20wt% of sulfur transfer additive wgt dry basis by total is accounted in terms of MgO.
VIII race's element in step (3) is Fe, can be FeCl2、Fe(NO3)2One or two kinds of mixing, additional proportion
With Fe2O3Meter accounts for the 1-8wt% of sulfur transfer additive wgt dry basis by total.
VII race's element in step (3) is Mn, is MnO2, additional proportion is with MnO2Meter accounts for sulfur transfer additive wgt dry basis by total
1-4wt%.
The catalytic cracking regeneration flue gas sulphur transfer agent that the above method is prepared.
The beneficial effect of technology provided by the invention：
(1) magnesium carbonate, calcium carbonate, after acidified, the magnesium ion and boehmite of ionic state are contained in white clouds ore
With reference to forming magnesia-alumina spinel structure after roasting.
(2) customary preparation methods can use vanadium as active component, but vanadium has necessarily during preparation and use
Toxic, this method replaced using iron oxide, it is engaged with manganese oxide not only can guarantee that performance but also reduced murder by poisoning.
(3) acidizing degree of white clouds ore is controlled, certain magnesium ion can be discharged and keep it
Original structure, can be effectively improved the abrasion index of sulfur transfer additive.
(4) calcium oxide in white clouds ore has in use necessarily consolidates vanadium performance, and fixed v element can partly be made
For active component, the performance of sulfur transfer additive can be improved to a certain extent.
Embodiment
Analysis test assessment method used in the embodiment of the present invention and comparative example：
(1) chemical composition：Xray fluorescence spectrometer
(2) surface is compared：Nitrogen adsorption instrument
(3) performance evaluation：Sulfur transfer additive performance, catalyst are evaluated using FFB small fixed flowing beds evaluating apparatus
Reserve 180g, heavy oil air speed 20h-1。
Raw materials used specification in the embodiment of the present invention and comparative example：
(1) white clouds ore：It is commercially available, the particle diameter mesh of 600 mesh -1000, igloss 10%.
(2) magnesium chloride：It is commercially available, it is deployed into the solution of the 350g/L in terms of MgO.
(3) frerrous chloride：It is commercially available, it is deployed into Fe2O3Count the solution of 400g/L
(4) hydrochloric acid：Analyze pure.
(5) manganese oxide：It is commercially available, igloss 5%.
(6) boehmite：It is commercially available, igloss 35wt%.
The present invention is further illustrated for the following examples, but does not therefore limit the present invention.
Embodiment 1：
(1) 6.11 kilograms of white clouds mineral powders are beaten, slurries pH is adjusted to 3 with hydrochloric acid.
(2) 3.08 kilograms of boehmites are added in slurries in (1)
(3) in (2) 4.29LMgCl is sequentially added in slurries2Solution, 2.00LFeCl2Solution, 0.21 kilogram of MnO, are stirred
Mix.
(4) by above-mentioned slurries spray drying forming, sulfur transfer additive is obtained, is denoted as sample LJ-1.
Embodiment 2：
(1) 4.44 kilograms of white clouds mineral powders are beaten, slurries pH is adjusted to 2.5 with hydrochloric acid.
(2) 4.62 kilograms of boehmites are added in slurries in (1)
(3) in (2) 5.71LMgCl is sequentially added in slurries2Solution, 1.50LFeCl2Solution, 0.42 kilogram of MnO, are stirred
Mix.
(4) by above-mentioned slurries spray drying forming, sulfur transfer additive is obtained, is denoted as sample LJ-2.
Embodiment 3：
(1) 6.67 kilograms of white clouds mineral powders are beaten, slurries pH is adjusted to 3 with hydrochloric acid.
(2) 3.85 kilograms of boehmites are added in slurries in (1)
(3) in (2) 2.86LMgCl is sequentially added in slurries2Solution, 1.00LFeCl2Solution, 0.11 kilogram of MnO, are stirred
Mix.
(4) by above-mentioned slurries spray drying forming, sulfur transfer additive is obtained, is denoted as sample LJ-3.
The analysis result of sulfur transfer additive is as follows in example
The analysis result of 1 sulfur transfer additive of table
Catalyst aging：The catalyst of preparation is spare after hydro-thermal process 17h under 800 DEG C, 100% water vapor conditions.
Evaluating catalyst：The evaluation of catalyst carries out evaluation progress on FFB is fixed fluidized bed.Feedstock oil chooses certain refinery
Mixed material oil, feedstock property is shown in Table 2, host agent AIC-950, the production of Qingdao Hui Cheng environmental protection Science and Technology Co., Ltd., sulphur
Transfer agent adding proportion 5%, reaction temperature are 520 DEG C, oil ratio 4.95, catalyst inventory 180g, air speed 20h-1, evaluation knot
Fruit is shown in Table 3.
2. raw material oil nature of table.
Table 3.FFB small fixed flowing bed evaluation results.
As can be seen from Table 3, the sulfur transfer additive prepared with the method for the present invention, sulfureous in flue gas content reduce respectively
81.6%, 84.0% and 86.5%, positive effect, realizes the purpose of the present invention.
Although the above-mentioned embodiment to the present invention is described, not to the limit of the scope of the present invention
System, those skilled in the art should understand that, on the basis of technical scheme, those skilled in the art need not pay
Go out various modifications or deformation that creative work can make still within protection scope of the present invention.
Claims (7)
1. a kind of preparation method of catalytic cracking regeneration flue gas sulphur transfer agent, it is characterised in that preparation process is as follows：
(1) white clouds mineral powder mashing acidifying；
(2) a certain proportion of boehmite is added in slurries in (1)；
(3) II A races element, VIII race's element, VII race's element are sequentially added in slurries in (2)；
(4) by above-mentioned slurries spray drying forming.
2. preparation method according to claim 1, it is characterised in that the white clouds miberal powder in step (1) is chemical composition CaMg
(CO3)2Ore through crushing levigate, the particle diameter mesh of 600 mesh -1000.
3. preparation method according to claim 1, it is characterised in that the acidifying in step (1), uses hydrochloric acid and/or nitre
Acid, it is 2-4 to adjust slurries pH.
4. preparation method according to claim 1, it is characterised in that boehmite additional proportion in step (2) with
Al2O3Meter accounts for the 20-30wt% of sulfur transfer additive wgt dry basis by total.
5. preparation method according to claim 1, it is characterised in that II A races element in step (3) is Mg, Ke Yishi
MgCl2、Mg(NO3)2One or two kinds of mixing, additional proportion accounts for the 10-20wt% of sulfur transfer additive wgt dry basis by total in terms of MgO.
6. preparation method according to claim 1, it is characterised in that VIII race's element in step (3) is Fe, Ke Yishi
FeCl2、Fe(NO3)2One or two kinds of mixing, additional proportion is with Fe2O3Meter accounts for the 1-8wt% of sulfur transfer additive wgt dry basis by total.
7. preparation method according to claim 1, it is characterised in that VII race's element in step (3) is Mn, is MnO2, add
Enter ratio with MnO2Meter accounts for the 1-4wt% of sulfur transfer additive wgt dry basis by total.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711171604.2A CN107999086A (en) | 2017-11-22 | 2017-11-22 | A kind of preparation method of catalytic cracking regeneration flue gas sulphur transfer agent |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711171604.2A CN107999086A (en) | 2017-11-22 | 2017-11-22 | A kind of preparation method of catalytic cracking regeneration flue gas sulphur transfer agent |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN107999086A true CN107999086A (en) | 2018-05-08 |
Family
ID=62053339
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201711171604.2A Withdrawn CN107999086A (en) | 2017-11-22 | 2017-11-22 | A kind of preparation method of catalytic cracking regeneration flue gas sulphur transfer agent |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107999086A (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1890021A (en) * | 2003-12-05 | 2007-01-03 | 英特凯特公司 | Mixed metal oxide sorbents |
| CN105664680A (en) * | 2016-03-29 | 2016-06-15 | 黄河三角洲京博化工研究院有限公司 | Liquid FCC regenerative flue gas sulfur transfer agent |
-
2017
- 2017-11-22 CN CN201711171604.2A patent/CN107999086A/en not_active Withdrawn
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1890021A (en) * | 2003-12-05 | 2007-01-03 | 英特凯特公司 | Mixed metal oxide sorbents |
| CN105664680A (en) * | 2016-03-29 | 2016-06-15 | 黄河三角洲京博化工研究院有限公司 | Liquid FCC regenerative flue gas sulfur transfer agent |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102151484B (en) | Catalytic cracking regenerated flue gas sulfur transfer agent and preparation method thereof | |
| Liu et al. | Preparation and desulfurization performance of LaMeOx/SBA-15 for hot coal gas | |
| CN104069802B (en) | A kind of sulfur method of the gas sweetening adsorbing composition and preparation method thereof with sulfurous gas | |
| CA2387986C (en) | Desulfurization and novel sorbents for same | |
| US10569251B2 (en) | Desulphurisation material comprising copper supported on zinc oxide | |
| SA110310032B1 (en) | Desulfurizing Adsorbent, Preparing Process and Use Thereof | |
| CN101648107A (en) | Catalytic oxidation adsorption desulfurizer and preparation method thereof | |
| CN103084147A (en) | Iron oxide magnetic nano particle, preparation method and application method thereof in desulfurization | |
| CN101766985A (en) | Desulfurizing sorbent and preparation method and application thereof | |
| CN107497283A (en) | A kind of big air speed Fe-series desulfurizing agent and preparation method and application | |
| CN101102839B (en) | Desulfurization and novel process for same | |
| Li et al. | Synergetic utilization of microwave-modified fly ash and carbide slag for simultaneous desulfurization and denitrification | |
| US7754650B2 (en) | Trifunctional catalyst for sulphur transfer, denitrogenation and combustion promoting and a method for preparing the same | |
| CN107999086A (en) | A kind of preparation method of catalytic cracking regeneration flue gas sulphur transfer agent | |
| Chen et al. | Application of modified coke to NOx reduction with recycling flue gas during iron ore sintering process | |
| CN104475077B (en) | Preparation method of catalytic cracking flue gas desulfurization agent | |
| CN105080487B (en) | Load active carbon desulfurization adsorbent of phthalocyanine cobalt sulfonate and copper and preparation method thereof | |
| Zheng et al. | Study on desulfurization performance of Cu modified red mud-fly ash sorbent | |
| Xing et al. | Mechanism and experimental study of desulfurizing agent based on Mn/Ce-Ca for sintering flue gas desulfurization (FGD) | |
| CN103769038B (en) | A kind of gas sweetening adsorbent, its preparation method and application | |
| CN108187681A (en) | A kind of zirconium boride auxiliary agent denitration desulphurization catalyst and preparation method | |
| CN105688648A (en) | Smoke plume removal agent for FCC flue gas wet desulfurization process as well as preparation method and application of smoke plume removal agent | |
| ES2318887T3 (en) | WEAR RESISTANT REDUCED SULBUR SURPRISES CONTAINING ZINC TITANATE. | |
| CN113663491A (en) | Desulfurizing agent composition and preparation method thereof | |
| CN105080488B (en) | Load phthalocyanine cobalt sulfonate active carbon desulfurization adsorbent and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WW01 | Invention patent application withdrawn after publication | ||
| WW01 | Invention patent application withdrawn after publication |
Application publication date: 20180508 |