CN106890666B - A kind of catalyst of hydrogen chloride Efficient Conversion preparing chlorine gas - Google Patents
A kind of catalyst of hydrogen chloride Efficient Conversion preparing chlorine gas Download PDFInfo
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- CN106890666B CN106890666B CN201710071523.9A CN201710071523A CN106890666B CN 106890666 B CN106890666 B CN 106890666B CN 201710071523 A CN201710071523 A CN 201710071523A CN 106890666 B CN106890666 B CN 106890666B
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- aqueous solution
- hydrogen chloride
- chlorine gas
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- 238000006243 chemical reaction Methods 0.000 title claims abstract description 53
- 239000003054 catalyst Substances 0.000 title claims abstract description 52
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 229910000041 hydrogen chloride Inorganic materials 0.000 title claims abstract description 39
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 title claims abstract description 39
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 title claims abstract description 24
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 13
- 229910052681 coesite Inorganic materials 0.000 claims abstract description 12
- 229910052906 cristobalite Inorganic materials 0.000 claims abstract description 12
- 229910052682 stishovite Inorganic materials 0.000 claims abstract description 12
- 229910052905 tridymite Inorganic materials 0.000 claims abstract description 12
- 239000000460 chlorine Substances 0.000 claims abstract description 11
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 10
- 239000012018 catalyst precursor Substances 0.000 claims abstract description 7
- 239000000203 mixture Substances 0.000 claims abstract description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 36
- 239000007864 aqueous solution Substances 0.000 claims description 32
- 239000000463 material Substances 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 14
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 8
- 229910000040 hydrogen fluoride Inorganic materials 0.000 claims description 8
- 238000007254 oxidation reaction Methods 0.000 claims description 7
- 239000000243 solution Substances 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 230000003647 oxidation Effects 0.000 claims description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 4
- 238000001354 calcination Methods 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 238000007598 dipping method Methods 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 2
- 238000006555 catalytic reaction Methods 0.000 claims description 2
- 229910052731 fluorine Inorganic materials 0.000 claims description 2
- 239000011737 fluorine Substances 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- JBJWASZNUJCEKT-UHFFFAOYSA-M sodium;hydroxide;hydrate Chemical compound O.[OH-].[Na+] JBJWASZNUJCEKT-UHFFFAOYSA-M 0.000 claims 1
- 239000000295 fuel oil Substances 0.000 abstract description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 238000004448 titration Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- KJFMBFZCATUALV-UHFFFAOYSA-N phenolphthalein Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C2=CC=CC=C2C(=O)O1 KJFMBFZCATUALV-UHFFFAOYSA-N 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 239000012086 standard solution Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 239000011651 chromium Substances 0.000 description 3
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 3
- 231100000572 poisoning Toxicity 0.000 description 3
- 230000000607 poisoning effect Effects 0.000 description 3
- 229910052707 ruthenium Inorganic materials 0.000 description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 239000001103 potassium chloride Substances 0.000 description 2
- 235000011164 potassium chloride Nutrition 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229910001868 water Inorganic materials 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- FGUUSXIOTUKUDN-IBGZPJMESA-N C1(=CC=CC=C1)N1C2=C(NC([C@H](C1)NC=1OC(=NN=1)C1=CC=CC=C1)=O)C=CC=C2 Chemical compound C1(=CC=CC=C1)N1C2=C(NC([C@H](C1)NC=1OC(=NN=1)C1=CC=CC=C1)=O)C=CC=C2 FGUUSXIOTUKUDN-IBGZPJMESA-N 0.000 description 1
- 229910000975 Carbon steel Inorganic materials 0.000 description 1
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229910004014 SiF4 Inorganic materials 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001339 alkali metal compounds Chemical class 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical compound ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 description 1
- 229940073608 benzyl chloride Drugs 0.000 description 1
- 239000010962 carbon steel Substances 0.000 description 1
- VYLVYHXQOHJDJL-UHFFFAOYSA-K cerium trichloride Chemical compound Cl[Ce](Cl)Cl VYLVYHXQOHJDJL-UHFFFAOYSA-K 0.000 description 1
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 150000008422 chlorobenzenes Chemical class 0.000 description 1
- 150000001845 chromium compounds Chemical class 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 239000000490 cosmetic additive Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000000645 desinfectant Substances 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 235000013373 food additive Nutrition 0.000 description 1
- 239000002778 food additive Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-M iodide Chemical compound [I-] XMBWDFGMSWQBCA-UHFFFAOYSA-M 0.000 description 1
- 229940006461 iodide ion Drugs 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920005591 polysilicon Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- -1 rare earth compound Chemical class 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000002407 reforming Methods 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- ABTOQLMXBSRXSM-UHFFFAOYSA-N silicon tetrafluoride Chemical compound F[Si](F)(F)F ABTOQLMXBSRXSM-UHFFFAOYSA-N 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- FDRCDNZGSXJAFP-UHFFFAOYSA-M sodium chloroacetate Chemical compound [Na+].[O-]C(=O)CCl FDRCDNZGSXJAFP-UHFFFAOYSA-M 0.000 description 1
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 1
- 235000019345 sodium thiosulphate Nutrition 0.000 description 1
- PANBYUAFMMOFOV-UHFFFAOYSA-N sodium;sulfuric acid Chemical compound [Na].OS(O)(=O)=O PANBYUAFMMOFOV-UHFFFAOYSA-N 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 125000000446 sulfanediyl group Chemical group *S* 0.000 description 1
- DHCDFWKWKRSZHF-UHFFFAOYSA-N sulfurothioic S-acid Chemical compound OS(O)(=O)=S DHCDFWKWKRSZHF-UHFFFAOYSA-N 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 238000009941 weaving Methods 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/18—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the mordenite type
- B01J29/20—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the mordenite type containing iron group metals, noble metals or copper
- B01J29/24—Iron group metals or copper
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/18—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the mordenite type
- B01J29/26—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the mordenite type containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B7/00—Halogens; Halogen acids
- C01B7/01—Chlorine; Hydrogen chloride
- C01B7/03—Preparation from chlorides
- C01B7/04—Preparation of chlorine from hydrogen chloride
-
- 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
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a kind of catalyst of hydrogen chloride Efficient Conversion preparing chlorine gas, it is characterised in that complex catalyst precursor weight percentage composition are as follows: component A:70%~80%；Component B:5%~10%；Component C:1%~2%；Component D:0.1%~0.3%；Surplus is SiO2；Wherein component A is Na- type modenite；Component B is Cu2+；Component C is Cs+;Component D is Re3+Or Ir3+.Heavy oil hydrogenating treatment catalyst of the present invention is suitable for hydrogen chloride high conversion and generates chlorine.
Description
Technical field
The invention belongs to catalyst fields, and in particular to a kind of catalyst of hydrogen chloride Efficient Conversion preparing chlorine gas.
Background technique
Chlorine is a kind of important Elementary Chemical Industry raw material, be widely used in polyurethane, organosilicon, chlorinated hydrocabon, epoxy resin,
The new materials industry such as chlorinated rubber, chlorinated high polymers is applied to the new energy industries such as polysilicon manufacture, applied to disinfectant, washes
Wash the life Fine Chemicals such as agent, food additives, cosmetic additive, be applied to synthetic glycerine, chlorobenzene series, monoxone,
Benzyl chloride, PCl3Equal pesticides/pharmaceuticals industry, and it is applied to the industries such as papermaking, weaving, metallurgy and petrochemical industry.
In reported heavy oil hydrogenating treatment catalyst, active component mainly uses the metallic elements such as copper, chromium, ruthenium.China
Patent CN101125297 is disclosed using silica as carrier, the catalysis of the containing copper chloride, potassium chloride and cerium chloride of phosphoric acid processing
Agent, the catalyst are 1:1 in hydrogen chloride and oxygen molar ratio, and fixed bed reactors temperature is 400 DEG C, and reaction pressure is
0.1Mpa, hydrogen chloride Feed space velocities are 0.8hr-1, the yield of product chlorine is 80.1%.Chinese patent CN101559374 is disclosed
Using silica gel, ReY molecular sieve as carrier, the catalyst of copper chloride, potassium chloride, manganese nitrate and cerous nitrate is loaded, in hydrogen chloride and oxygen
Throughput is 200m1/min, and catalyst amount 25g, reaction temperature is at 380 DEG C, and the conversion ratio of hydrogen chloride is 83.6%.
The problem of all there is reaction temperature height in above-mentioned Cu-series catalyst, active low and active component volatile inactivation.Chinese patent
CN87101999 is disclosed using SiO2For carrier, unbodied Cr in catalyst2O3Content be 20%~90%.Process uses
Fluidized-bed reactor operates, O at 370~420 DEG C2/ HCl is 0.3~0.75, and conversion ratio is 75~80%.Chromium-based catalysts
There is a problem of that reaction temperature height and activity are low, and is easy to produce iron (or a small amount of nickel and titanium) poisoning, it is right in practical applications
The making material requirement of reactor is high, needs using a kind of iron-content in 1% (weight) or lower material as reaction equipment
Material, device fabrication expense are excessively high.Document (Zhang Jun an ancient unit of weight, catalytic oxidation of hydrogen chloride for preparing chlorine gas technical progress, Chinese chlor-alkali [J], 2013
(5): 6-10 point out that SUMITOMO CHEMICAL chemical industry Co., Ltd. discloses one kind with RuO in)2For the catalyst of major constituent.This is urged
Agent is load with titanium oxide, zirconium oxide, aluminium oxide or zeolite etc., wherein with rutile TiO2Catalytic efficiency when doing carrier
Highest, ruthenium are 2%~6% relative to the quality ratio of carrier, the third ingredient other than ruthenium can also be added, such as palladium, copper chemical combination
Object, chromium compound, vfanadium compound, rare earth compound and alkali metal compound etc..Reaction uses fixed bed reactors, reaction temperature
It is 200~380 DEG C, reaction pressure is 101.33~55066.5kPa.The molar feed ratio of hydrogen chloride and oxygen is 0.05~1.25.
Under atmospheric pressure and 20~1000/h space velocities, the conversion ratio of hydrogen chloride can be more than up to 95.9%, the catalyst service life
16000h.The catalyst contains noble metal component, and the catalytic activity of catalyst can gradually be dropped with the extension of the duration of runs
It is low, it is also easy to inactivate because the fault in the impurity and operational process of craft in chlorination hydrogen feedstock causes the poisoning of irreversibility.
Above-mentioned catalyst there are the problem of, it is so serious that hinder the process of industrialization of hydrogen chloride Efficient Conversion preparing chlorine gas.
Summary of the invention
For defect existing for background technique or deficiency, the present invention provides that a kind of low temperature active is high, mithridatism is good, at low cost
The catalyst of long hydrogen chloride Efficient Conversion preparing chlorine gas with the service life.
The present invention is modified on the basis of copper-based active component by addition alkali metal and noble metal, and passes through fluorine
Change hydrogen and SiO2Reaction generates gas SiF4, while a large amount of low temperature active positions are generated in the catalyst, to improve catalyst performance
Can, so that the catalyst of hydrogen chloride Efficient Conversion preparing chlorine gas be prepared.
A kind of catalyst of hydrogen chloride Efficient Conversion preparing chlorine gas, forerunner's weight percentage composition are as follows: component A:70%~
80%；Component B:5%~10%；Component C:1%~2%；Component D:0.1%~0.3%；Surplus is SiO2；Wherein component A is Na- type silk
Geolyte；Component B is Cu2+；Component C is Cs+;Component D is Re3+Or Ir3+;It prepares by the following method:
A) by commercially available Na- type modenite, be added in the NaOH aqueous solution of 0.6 mol/L, Na- type modenite with
The mass ratio of NaOH aqueous solution is 1:4, is heated to the 2h that flows back, is stirred to react, and is filtered, washing to PH=7, drying, 350 DEG C of roastings
6 h are handled, component A is obtained；
B) the resulting component A of step a) is added to containing Cu2+Aqueous solution in, component A and Cu2+The quality of aqueous solution
Than stirring 15 min for 1:10；
C) Cs will be contained+Aqueous solution be added the resulting aqueous solution of above-mentioned steps b) in, component A and Cs+The quality of aqueous solution
Than stirring 15 min for 1:1；
D) Re will be contained3+Or Ir3+Aqueous solution be added the resulting aqueous solution of above-mentioned steps c) in, component A and Re3+Or Ir3+
The mass ratio of aqueous solution is 1:0.5,80 DEG C of dipping 8h, is filtered, and is washed, drying；
E) the resulting material of step d) and SiO2It is uniformly mixed, is granulated, partial size is adjusted to 12~18.5 mesh, the catalyst
Presoma is under the conditions of 400 DEG C of temperature, 8 h of calcination process；
F) in a nitrogen atmosphere by step e) resulting material, react with hydrogen fluoride, nitrogen and hydrogen fluoride molar ratio 20:
1, hydrogen fluoride and step e) resulting material mass ratio 1:20, reaction pressure 1atm, 330 DEG C of reaction temperature, reaction time 2h is obtained high
The hydrogen chloride preparing chlorine gas catalyst of conversion ratio.
The catalyst of hydrogen chloride Efficient Conversion preparing chlorine gas of the present invention is used in various types of reactors, such as fixed
Bed, the anti-device of fluidized bed, trickle bed or slurry bed system etc., preferably fixed bed.
The catalyst of hydrogen chloride Efficient Conversion preparing chlorine gas of the present invention is reacted for catalytic oxidation of hydrogen chloride for preparing chlorine gas,
It is reacted at 80 DEG C~600 DEG C, is reacted at preferably 200~250 DEG C.
Advantages of the present invention is as follows:
(1) hydrogen chloride Efficient Conversion preparing chlorine gas catalyst low-temperature activity of the invention is high, can reach in 220 DEG C of conversion ratios
To 99.1%.The reduction of temperature reduces equipment investment, and conversion ratio raising reduces operating cost, so that remarkable in economical benefits improves.
(2) hydrogen chloride Efficient Conversion preparing chlorine gas catalyst mithridatism of the invention is strong, will not iron poisoning.
(4) hydrogen chloride Efficient Conversion preparing chlorine gas catalyst of the invention is low in cost using base metals such as copper.
(5) hydrogen chloride Efficient Conversion preparing chlorine gas catalyst life of the invention was long, up to 25000 hours.
Specific embodiment
According to the technical solution in the present invention, preparing chlorine by oxidizing hydrogen chloride catalyst activity evaluating apparatus is common fixed bed
Tubular reactor, reactor size are the mm × 6 of 700 mm × 20 mm, material carbon steel.By Catalyst packing into reaction
Device, is heated to reaction temperature, and gas stablizes sampling analysis after reaction by pressure reducing valve and flowmeter rear feeding.
Catalyst activity evaluation experimental condition: 220 DEG C of reaction temperature, molar ratio/volume ratio of hydrogen chloride and oxygen is 4:
1, the inlet amount of hydrogen chloride is 200 mL/min, catalyst 2g, reaction pressure normal pressure.Oxidation reactor outlet is mainly chlorine
Gas, oxygen, hydrogen chloride and water vapour mixture, analyze chlorine content therein and calculate the life of chlorine in certain time interval
Cheng Liang, so that it may the conversion ratio of oxidation reaction is calculated, to investigate the activity of catalyst and the affecting laws of oxidation reaction condition.
According to the principle that chlorine is easily absorbed by liquor kalii iodide, the reproducibility of iodide ion is utilized in other words, and measurement has oxygen
The amount of the chlorine for the property changed.When gas sample is passed through liquor kalii iodide, chlorine is absorbed, and displaces iodine, and the iodine of precipitation is used thio again
The titration of sulfuric acid sodium standard solution, this is iodimetric titration (or indirect iodometric processes, iodometry).Titration process is used as using starch to be referred to
Show agent.Since HCl is highly soluble in water, so in Cl2While absorption by KI solution, HCl is also absorbed simultaneously.Use thiosulfuric acid
After sodium solution titrates, the amount of HCl, the titrimetry phenolphthalein indicator can be titrated with standard solution of sodium hydroxide.
Specific steps are as follows: preparing the KI solution 100 of portion 20% at regular intervals after system stable operation
Ml, switching oxidation reactor export triple valve, mixed gas after reaction are passed into (100 ml) liquor kalii iodide of constant volume,
It absorbs 3 minutes, moves into absorbing liquid in conical flask after absorption, titrated with the sodium thiosulfate standard solution of 0.1 mol/l, to form sediment
Powder makees indicator；Followed by, with phenolphthalein indicator, titrated with 0.1 mol/l standard solution of sodium hydroxide unreacted
HC1。
HCl conversion ratio:
%=b / (b+d)*100%
B indicates that titration consumes Na2S2O3Solution ml, ml
D indicates that titration consumes NaOH solution ml, ml
The present invention is described in further details below with reference to embodiment, but is not limited to the scope of the invention.
Embodiment 1
The catalyst precursor weight percent of embodiment 1 is as follows:
Component A 80%
Component B 10%
Component C 2%
Component D 0.3%
Surplus is SiO2The Na- type modenite that the NaOH aqueous solution that wherein component A is 0.6 mol/L is handled；Component B
For Cu2+；Component C is Cs+；Component D is Ir3+
The catalyst of the present embodiment is prepared by the following method.
A) by commercially available Na- type modenite, be added in the NaOH aqueous solution of 0.6 mol/L, Na- type modenite with
The mass ratio of NaOH aqueous solution is 1:4, is heated to the 2h that flows back, is stirred to react, and is filtered, washing to PH=7, drying, 350 DEG C of roastings
6h is handled, component A is obtained；
B) the resulting component A of step a) is added to containing Cu2+Aqueous solution in, component A and Cu2+The quality of aqueous solution
Than stirring 15min for 1:10；
C) Cs will be contained+Aqueous solution be added the resulting aqueous solution of above-mentioned steps b) in, component A and Cs+The quality of aqueous solution
Than stirring 15min for 1:1；
D) Ir will be contained3+Aqueous solution be added the resulting aqueous solution of above-mentioned steps c) in, component A and Ir3+The matter of aqueous solution
Amount filters, washing, drying than being 1:0.5,80 DEG C of dipping 8h；
E) the resulting material of step d) and SiO2It is uniformly mixed, is granulated, partial size is adjusted to 12~18.5 mesh, the catalyst
Presoma is under the conditions of 400 DEG C of temperature, calcination process 8h；
F) in a nitrogen atmosphere by step e) resulting material, react with hydrogen fluoride, nitrogen and hydrogen fluoride molar ratio 20:
1, hydrogen fluoride and step e) resulting material mass ratio 1:20, reaction pressure 1atm, 330 DEG C of reaction temperature, reaction time 2h is obtained high
The hydrogen chloride preparing chlorine gas catalyst of conversion ratio is labeled as CatB.
Comparative example 1
The catalyst precursor weight percent of embodiment 1 is with embodiment 1, and the preparation method is the same as that of Example 1, except that
Comparative example 1 does not have step f, and catalyst obtained is labeled as CatA0.
Embodiment 2
The catalyst precursor weight percent of embodiment 2 is as follows:
Component A 75%
Component B 17%
Component C 1.5%
Component D 0.15%
Surplus is SiO2
The Na- type modenite that the NaOH aqueous solution that wherein component A is 0.6 mol/L is handled；Component B is Cu2+；Component C
For Cs+；Component D is Ir3+
The preparation method is the same as that of Example 1 for the catalyst of the present embodiment, except that component C is Cs+；Component D is Ir3+,
Catalyst obtained is labeled as CatC.
Embodiment 3
The catalyst precursor weight percent of embodiment 3 is as follows:
Component A 75%
Component B 7%
Component C 1.5%
Component D 0.15%
Surplus is SiO2
The Na- type modenite that the NaOH aqueous solution that wherein component A is 0.6 mol/L is handled；Component B is Cu2+；Component C
For Cs+；Component D is Re3+
The preparation method is the same as that of Example 1 for the catalyst of the present embodiment, except that component C is Cs+；Component D is Re3+,
Catalyst obtained is labeled as CatF.
Embodiment 4
The catalyst precursor weight percent of embodiment 4 is as follows:
Component A 80%
Component B 10%
Component C 1.8%
Component D 0.08%
Surplus is SiO2
The Na- type modenite that the NaOH aqueous solution that wherein component A is 0.6 mol/L is handled；Component B is Cu2+；Component C
For Cs+；Component D is Re3+
The preparation method is the same as that of Example 1 for the catalyst of the present embodiment, except that component C is Cs+；Component D is Re3+,
Catalyst obtained is labeled as CatG.
The application of the catalyst of hydrogen chloride Efficient Conversion preparing chlorine gas of the invention:
Hydrogen chloride reforming catalyst CatB, CatC, CatF, CatG of high conversion prepared by Examples 1 to 4 are loaded
It into fixed-bed tube reactor, is reacted, reaction result is shown in Table 1.
1 catalyst reaction result of table
Claims (2)
1. a kind of catalyst of hydrogen chloride Efficient Conversion preparing chlorine gas, forerunner's weight percentage composition are as follows: component A:70%~
80%；Component B:5%~10%；Component C:1%~2%；Component D:0.1%~0.3%；Surplus is SiO2；Wherein component A is
Na- type modenite；Component B is Cu2+；Component C is Cs+；Component D is Re3+Or Ir3+；It is characterized in that making by the following method
It is standby:
A) it by commercially available Na- type modenite, is added in the NaOH aqueous solution of 0.6mol/L, Na- type modenite and NaOH water
The mass ratio of solution is 1:4, is heated to the 2h that flows back, is stirred to react, and is filtered, washing to PH=7, drying, 350 DEG C of calcination process
6h obtains component A；
B) the resulting component A of step a) is added to containing Cu2+Aqueous solution in, component A and Cu2+The mass ratio of aqueous solution is 1:
10, stir 15min；
C) Cs will be contained+Aqueous solution be added the resulting aqueous solution of above-mentioned steps b) in, component A and Cs+The mass ratio of aqueous solution is
1:1 stirs 15min；
D) Re will be contained3+Or Ir3+Aqueous solution be added the resulting aqueous solution of above-mentioned steps c) in, component A and Re3+Or Ir3+It is water-soluble
The mass ratio of liquid is 1:0.5,80 DEG C of dipping 8h, is filtered, and is washed, drying；
E) the resulting material of step d) and SiO2It is uniformly mixed, is granulated, partial size is adjusted to 12~18.5 mesh, the complex catalyst precursor
Body is under the conditions of 400 DEG C of temperature, calcination process 8h；
F) in a nitrogen atmosphere by step e) resulting material, react with hydrogen fluoride, nitrogen and hydrogen fluoride molar ratio 20:1, fluorine
Change hydrogen and step e) resulting material mass ratio 1:20, reaction pressure 1atm, 330 DEG C of reaction temperature, reaction time 2h obtains high conversion
The hydrogen chloride preparing chlorine gas catalyst of rate.
2. a kind of application of the catalyst of hydrogen chloride Efficient Conversion preparing chlorine gas as described in claim 1, which is characterized in that be used for chlorine
Change hydrogen catalysis oxidation preparing chlorine gas reaction.
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| PCT/CN2017/076452 WO2018145345A1 (en) | 2017-02-09 | 2017-03-13 | Catalyst for efficient conversion of hydrogen chloride to produce chlorine gas |
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| CN106890666A (en) | 2017-06-27 |
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