CN1307134C - Process for removing less acetylene from ethylene fraction - Google Patents
Process for removing less acetylene from ethylene fraction Download PDFInfo
- Publication number
- CN1307134C CN1307134C CNB2004100395765A CN200410039576A CN1307134C CN 1307134 C CN1307134 C CN 1307134C CN B2004100395765 A CNB2004100395765 A CN B2004100395765A CN 200410039576 A CN200410039576 A CN 200410039576A CN 1307134 C CN1307134 C CN 1307134C
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- Prior art keywords
- magnetic
- particle
- acetylene
- noble metal
- ball type
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Links
- 238000000034 method Methods 0.000 title claims abstract description 37
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 title claims abstract description 34
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 239000005977 Ethylene Substances 0.000 title description 5
- 230000008569 process Effects 0.000 title description 3
- 230000005291 magnetic effect Effects 0.000 claims abstract description 34
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 30
- 238000006243 chemical reaction Methods 0.000 claims abstract description 30
- 239000006249 magnetic particle Substances 0.000 claims abstract description 24
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000003054 catalyst Substances 0.000 claims abstract description 20
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 14
- 229910000510 noble metal Inorganic materials 0.000 claims abstract description 14
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 14
- 239000011247 coating layer Substances 0.000 claims abstract description 8
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052707 ruthenium Inorganic materials 0.000 claims abstract description 7
- 229910052703 rhodium Inorganic materials 0.000 claims abstract description 5
- 239000010948 rhodium Substances 0.000 claims abstract description 5
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000000126 substance Substances 0.000 claims abstract description 5
- 239000001257 hydrogen Substances 0.000 claims description 14
- 229910052739 hydrogen Inorganic materials 0.000 claims description 14
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 10
- 239000002994 raw material Substances 0.000 claims description 9
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 8
- 229910001566 austenite Inorganic materials 0.000 claims description 6
- 239000010970 precious metal Substances 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 5
- 150000002506 iron compounds Chemical class 0.000 claims description 4
- 150000001345 alkine derivatives Chemical class 0.000 abstract description 7
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 4
- 229910052742 iron Inorganic materials 0.000 abstract description 2
- 239000000377 silicon dioxide Substances 0.000 abstract description 2
- 235000012239 silicon dioxide Nutrition 0.000 abstract description 2
- 239000000969 carrier Substances 0.000 abstract 2
- 229910052681 coesite Inorganic materials 0.000 abstract 1
- 229910052906 cristobalite Inorganic materials 0.000 abstract 1
- 229910052682 stishovite Inorganic materials 0.000 abstract 1
- 229910052905 tridymite Inorganic materials 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 14
- 239000000203 mixture Substances 0.000 description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 10
- 238000002360 preparation method Methods 0.000 description 9
- 238000001035 drying Methods 0.000 description 7
- 239000007789 gas Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 5
- 150000001412 amines Chemical class 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 206010013786 Dry skin Diseases 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000004480 active ingredient Substances 0.000 description 3
- 238000003483 aging Methods 0.000 description 3
- 230000032683 aging Effects 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 238000007598 dipping method Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000012530 fluid Substances 0.000 description 3
- 238000010335 hydrothermal treatment Methods 0.000 description 3
- 239000003350 kerosene Substances 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 238000010792 warming Methods 0.000 description 3
- 229910002706 AlOOH Inorganic materials 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 101150003085 Pdcl gene Proteins 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- 229910021417 amorphous silicon Inorganic materials 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000004202 carbamide Substances 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000004312 hexamethylene tetramine Substances 0.000 description 2
- 235000010299 hexamethylene tetramine Nutrition 0.000 description 2
- 238000009775 high-speed stirring Methods 0.000 description 2
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical group O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 230000005415 magnetization Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- -1 nitrogen-containing organic compound Chemical class 0.000 description 2
- 238000003822 preparative gas chromatography Methods 0.000 description 2
- 230000001603 reducing effect Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 230000002829 reductive effect Effects 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 2
- 238000004230 steam cracking Methods 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 235000003140 Panax quinquefolius Nutrition 0.000 description 1
- 240000005373 Panax quinquefolius Species 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- NWGKJDSIEKMTRX-AAZCQSIUSA-N Sorbitan monooleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O NWGKJDSIEKMTRX-AAZCQSIUSA-N 0.000 description 1
- AMXBISSOONGENB-UHFFFAOYSA-N acetylene;ethene Chemical group C=C.C#C AMXBISSOONGENB-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 239000005030 aluminium foil Substances 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 229910052728 basic metal Inorganic materials 0.000 description 1
- 150000003818 basic metals Chemical class 0.000 description 1
- 229910001593 boehmite Inorganic materials 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000007233 catalytic pyrolysis Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000002596 correlated effect Effects 0.000 description 1
- 230000000875 corresponding effect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- LGPMBEHDKBYMNU-UHFFFAOYSA-N ethane;ethene Chemical compound CC.C=C LGPMBEHDKBYMNU-UHFFFAOYSA-N 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 230000005294 ferromagnetic effect Effects 0.000 description 1
- 238000005243 fluidization Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 229910001691 hercynite Inorganic materials 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 150000002505 iron Chemical class 0.000 description 1
- 239000006148 magnetic separator Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- SONJTKJMTWTJCT-UHFFFAOYSA-K rhodium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Rh+3] SONJTKJMTWTJCT-UHFFFAOYSA-K 0.000 description 1
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 229960001866 silicon dioxide Drugs 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 238000001132 ultrasonic dispersion Methods 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
- 239000007762 w/o emulsion Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention relates to a method for eliminating a small quantity of acetylene in ethene fractions through selective hydrogenation. Ethene fractions containing a small quantity of acetylene contact magnetic noble metal catalysts in a magnetic stabilized bed reactor under the conditions that reaction temperature is from 25 to 150 DGE C, reaction pressure is from 0.5 to 5.0MPa, the feeding molar ratio of hydrogen gas to alkyne is 1 to 3: 1, the volume space velocity is from 1000 to 24000 h<-1>, and the magnetic field intensity is from 10 to 1000 oersted. The magnetic noble metal catalysts are composed of spherical carriers and noble metal active components selected from one kind or several kinds of palladium, ruthenium and rhodium, wherein each of the spherical carriers is composed of alumina and magnetic particles, and each magnetic particle is composed of an SiO2 coating layer and a core containing iron substances.
Description
Technical field
The invention relates to the method for a little acetylene in a kind of selective hydrogenation and removing ethene cut.More particularly, be about a kind of in magnetically stabilized bed reactor with the magnetic noble metal catalyst to the ethene cut selective hydrogenation and removing method of a little acetylene wherein.
Background technology
In petrochemical industry, ethene is the monomer of preparation polymkeric substance, and it can be made by steam cracking or catalytic pyrolysis.All contain a spot of acetylene in the ethene cut of Sheng Chaning like this, it is the poisonous substance of the further processing and utilization of ethene, influences the stability of the employed catalyzer of the further course of processing, therefore must be removed.Industrial common employing selects the method for hydrogenation to remove these a spot of acetylene.Selective hydrogenation catalyst generally is made up of inert support and load the 8th family's precious metal thereon, and present industrial multiselect palladium is an active ingredient.Selective hydrogenation is generally carried out in fixed-bed reactor.
USP 5,648, and 576 disclose a kind of C
2Or C
3The alkynes gas phase is selectively hydrogenated into the method for corresponding alkene.This method is in the presence of hydrogen, and gas phase treatment contains C on the catalyzer of sphere or stripe shape
2Or C
3The material of alkynes.Used catalyzer contains palladium and at least a periodic table of elements IB family metal (preferred silver) and aluminum oxide, and wherein the weight ratio of IB family metal and palladium is 0.05-0.4, and at least 80% palladium and at least 80% IB family Metal Distribution are being r by radius
1(mean radius that is equivalent to the catalyzer of sphere or extrusion moulding) and radius are r
2(r
2At least equal 0.8r
1) sphere or catalyst volume that the cylindrical surface limited within.Active component palladium and IB family metal are to adopt pickling process to load on the carrier.
USP 5,847,250 disclose a kind of from C
2The catalyzer of selective hydrogenation and removing acetylene in the hydrocarbon.This catalyzer is carrier with silicon-dioxide, and charge capacity is that the palladium of 0.001-1% is an active ingredient, and basic metal or the alkaline-earth metal conduct of adding 0.005-5% simultaneously help active ingredient.This catalyzer is applicable to that acetylene content is the removing of acetylene in the ethene-ethane mixtures of 0.01-5% (volume).
Summary of the invention
The purpose of this invention is to provide a kind of magnetic noble metal catalyst that in magnetically stabilized bed reactor, uses to the ethene cut selective hydrogenation and removing method of a little acetylene wherein.
Method provided by the invention is that to make the ethene cut that contains a little acetylene and magnetic noble metal catalyst in magnetically stabilized bed reactor be that 25-150 ℃, reaction pressure are that 0.5-5.0MPa, volume space velocity are 1000-24000 hour in temperature of reaction
-1, hydrogen is 1-3 with the acetylene raw materials components mole ratio: 1, contact under the condition of magneticstrength 10-1000 oersted, said magnetic noble metal catalyst is made up of ball type carrier and one or more the noble metal active component that is selected from palladium, ruthenium, the rhodium, ball type carrier wherein is made up of aluminum oxide and magnetic-particle, and magnetic-particle wherein is by SiO
2The kernel of coating layer and iron compound is formed.
The ethene cut that the inventive method is suitable for is from full scale plant, and for example the acetylene content of steam cracking or cat-cracker is the ethene cut of 0.01-5 volume %, wherein can also contain ethane and a spot of propylene, methane, hydrogen etc.
Said magnetically stabilized bed reactor is a kind ofly to exist uniform magnetic field in reactor, have ferromagnetic catalyzer because the existence in this magnetic field and reactor that the interaction stable existence does not flow with reaction mass in reactor in the inventive method.This magnetically stabilized bed reactor is made of reactor and externally-applied magnetic field, externally-applied magnetic field is along the axial uniform steady magnetic field of reactor, uniform magnetic field is by direct supply and a series of and co-axial helmholtz coil of reactor or evenly closely provide around solenoid coil, and other parts of reactor and reactor are made by the good material of magnetic permeability.
The preferred reaction conditions of the inventive method is: temperature of reaction is that 25-100 ℃, reaction pressure are that 1.0-3.0MPa, volume space velocity are 1000-18000 hour
-1, hydrogen and acetylene raw materials components mole ratio be 1-2: 1, magneticstrength 50-800 oersted.
Said magnetic noble metal catalyst is made up of one or more the ball type carrier of precious metal, preferred precious metal palladium and surplus that is selected from palladium, ruthenium, the rhodium that accounts for the heavy % of catalyzer 0.001-0.5, the heavy % of preferred 0.01-0.3 in the inventive method.For the ease of the use in magnetically stabilized bed reactor, the particle diameter of this catalyzer should be advisable between 10 μ m to 1mm.
Wherein said ball type carrier is formed by accounting for the heavy % of carrier 1-50, the magnetic-particle of the heavy % of preferred 2-15 and the aluminum oxide of surplus.Magnetic-particle wherein is (0.05-6) by weight ratio: 1, preferred (0.3-4.0): 1 SiO
2Coating layer and be dispersed in wherein, one or more particle diameters be the 3-30 nanometer, its chemical constitution is for being selected from Fe
3O
4, Fe and γ-Fe
2O
3In the kernel of single domain superparamagnetism particulate of one or more iron compounds form.Aluminum oxide wherein can be any crystalline phase, can be selected from p-, x-, the η of various low temperature transition phases-, gama-alumina, also can be selected from k-, the δ of various high temperature transition phases-, one or more the mixture in θ-aluminum oxide and the Alpha-alumina.
In above-mentioned said magnetic-particle, closely coat the amorphous Si O of kernel
2Coating layer and kernel mortise form magnetic-particle.For the magnetic-particle that kernel has a plurality of particulates, between each particulate because SiO
2Obstruct and uniform distribution.
By vibrating sample magnetometer said ball type carrier is measured, its magnetic hysteresis loop does not have hysteresis; When outside magnetic field exists, good magnetic property is arranged; Adding magnetic field H=0 o'clock, residual magnetization Mr and coercivity H are zero, have superparamagnetism.
The ball type carrier of being made up of magnetic-particle and aluminum oxide has good thermostability and erosion resistance, and because SiO
2The buffer action of coating layer can avoid kernel iron component and alumina catalyst support component at high temperature to form hercynite.
The preparation method of said ball type carrier is as follows in the inventive method:
The preparation of step 1-carrier kernel magnetic-particle: the Fe that contains that alkali is added 50-100 ℃
2+With Fe
3+In the aqueous solution of salt, with sedimentary Fe
3O
4Particle changes in the sodium silicate aqueous solution, under the protection of rare gas element, transfers to pH≤7 with acid, promptly obtains SiO
2Coat Fe
3O
4The particulate magnetic particle.Wherein, said alkali is selected from KOH, NaOH, NH
4OH, Na
2CO
3Or NaHCO
3A kind of or its mixture wherein; Fe in the said iron salt solutions
2+With Fe
3+Mol ratio be 1: (0.5-2.5), preferred 1: (1.5-2); The OH of said alkali
-With ∑ (Fe
2++ Fe
3+) mol ratio be 1: (0.1-1.0); Said water glass and Fe
3O
4Mol ratio be 1: (0.04-5), preferred 1: (0.06-1); Said acid is selected from one or more the mixture in sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid, formic acid or the acetate.
The preparation of step 2-ball type carrier: under 10-35 ℃, with aluminum hydroxide sol, the magnetic particle that organic amine solution and step 1 obtain is according to aluminum hydroxide sol and organic amine solution 1: volume ratio (0.4-3.5), aluminum hydroxide sol and magnetic particle 1: weight ratio (0.02-0.2), the three is mixed and be uniformly dispersed, be 1 with itself and kerosene or vegetables oil with volume ratio then: (3-20), preferred 1: mixed (4-10) forms the water-in-oil-type drop, heating systems makes the aluminum hydroxide sol cure of aqueous phase, pass through again and the identical hydrothermal treatment consists of conventional forming oil column oxygenerating alumina supporter, ageing, dry and calcination steps is handled, and can obtain ball type carrier.Wherein said organic amine is meant that the pH value is near neutral at normal temperatures, but can discharge the nitrogen-containing organic compound of alkaline matter through thermal degradation, as urea or hexamethylenetetramine, they can be used singly or in combination, and the concentration of organic amine solution is that the heavy % of 12-40 is advisable; Said dispersion means can be selected from conventional variety of way, as: stirring, vibration, ultrasonic etc.
Used catalyzer is that drying, roasting, reduction make then with the above-mentioned ball type carrier that makes of steeping fluid dipping that contains precious metal in the inventive method.Said steeping fluid is made into by precious metal salt (as Palladous chloride, ruthenium chloride, rhodium chloride etc.), mineral acid and deionized water, the preferred hydrochloric acid of said mineral acid, and the pH value of steeping fluid is 2-6; Said drying temperature is a room temperature-120 ℃; Said maturing temperature is 150-600 ℃; Said reduction is to carry out under 50-500 ℃ in hydrogen atmosphere, or reduces with reductive agents such as formaldehyde, hydrazine hydrates.
The method that removes acetylene provided by the present invention, owing to used magnetically stabilized bed reactor, and catalyst system therefor has superparamagnetism, thereby has the following advantages:
1, the catalyzer with superparamagnetism is lined up chain in externally-applied magnetic field, and bed is uniform and stable, no channel; But externally-applied magnetic field bubble crushing, realization particulate fluidization, mass transfer, heat transfer efficiency height.
2, externally-applied magnetic field can prevent that catalyzer from taking out of, therefore can use finely grained catalyst, and this not only helps accelerating rate of mass transfer, and can prevent the further deep hydrogenation of ethene, and then obtains the highly selective product.
Embodiment
The present invention is further illustrated below by embodiment, but not thereby limiting the invention.
Embodiment 1
The preparation process of the ball type carrier of catalyst system therefor in present embodiment explanation the inventive method.
With 189g Na
2SiO
39H
2O is dissolved in the 1000mL distilled water, slowly drips 3mol/L HCl solution under agitation condition, and the pH value of solution is transferred to 13, filters afterwards standby.
In the 3L stirring tank that 1200mL distilled water is housed, add 42.2g FeCl
36H
2O and 20.6gFeCl
24H
2O is warming up to 85-90 ℃, adds the NH of 60mL25% in the high-speed stirring process
3H
2O solution, high-speed stirring adopted magnetic separator to isolate Fe after 3 minutes
3O
4Granular product.With the precipitated product ultra-sonic dispersion after cleaning above-mentioned through pretreated Na
2SiO
3In the solution, move into then in the 3L stirring tank, be warming up to 85 ℃, under nitrogen protection and agitation condition, in solution, slowly drip the HCl solution of the about 2mol/L of concentration, in about 3 hours, the pH value of solution is reduced to 6 by 13.Obtain SiO
2Coat Fe
3O
4The particulate magnetic particle.The about 60g of above-mentioned product magnetic particle gross weight wherein contains Fe
3O
4About 20g is coated on Fe
3O
4The SiO on surface
2About 40g is amorphous Si O
2Detect the magnetic hysteresis loop that obtains through vibrating sample magnetometer (VSM) and show that magnetic particle has superparamagnetism.This component brief note is SF.
Take by weighing AlCl
36H
2O 80g, be dissolved in the 600ml deionized water, add the 44g high-purity aluminum foil, kept 60-72 hour down at 80-100 ℃, after making aluminium foil fully be dissolved in the solution, the liquor capacity heating is concentrated into 300ml, obtains clarifying translucent colloidal sol, wherein aluminium/chlorine weight ratio is about 1.5: 1.0, and the aluminium in the colloidal sol is converted to aluminum oxide and is about 100g.This colloidal sol brief note is AL1.
Under 10 ℃, measure 100ml AL1 aluminum hydroxide sol, mix with the organic amine solution (containing hexamethylenetetramine 300g/L and urea 150g/L) of 90ml, stir, add 7.3g SF cladded type magnetic component particle again, pour in the 3L stirring tank that fills 1600ml sulfonated kerosene (the tensio-active agent Span80 that contains 0.05 volume %) after fully stirring.At room temperature, under the rotating speed of 700rpm, be uniformly dispersed, form water-in-oil emulsion, system is warming up to 85-90 ℃ subsequently, keep cooling off, isolate product after 15 minutes, obtain the spherical Al (OH) of magnetic
3This spherical products brief note is AL2.
With the spherical Al (OH) of above-mentioned magnetic
3Product A L2 packs into and fills in the 1L autoclave of 0.7L sulfonated kerosene medium; the following 180 ℃ of hydrothermal treatment consists of nitrogen protection 2 hours; after the product cleaning oil removing; subsequently in the weak ammonia of pH10 (measuring under the room temperature) in 80 ℃ of ageings 5 hours to remove wherein partial impurities; after 60 ℃ of oven dry, can obtain boehmite structure (the spherical Al (OH) of the magnetic of α-AlOOH)
3Product.This product brief note is AL3.AL3 is by α-AlOOH, Fe
3O
4And γ-Fe
2O
3Deng composition, in hydrothermal treatment consists, ageing and drying process, the Fe in the product
3O
4Partial oxidation is γ-Fe
2O
3
Above-mentioned boehmite product A L3 can obtain about 45g and contain γ-Fe through 580 ℃ of air atmosphere sintering 2 hours
2O
3Spherical gamma-the Al of magnetic kernel
2O
3Carrier.
The median size of this ball type carrier is about 200 μ m, and wherein the weight ratio of each component is: γ-Fe
2O
3: SiO
2: Al
2O
3=6: 12: 82, this carrier had the superparamagnetism feature, and specific saturation magnetization is 2.97Am
2/ Kg.The BET specific surface of carrier is 200m
2/ g, pore volume are 0.75mL/g.
Embodiment 2
The preparation process of used palladium catalyst in present embodiment explanation the inventive method.
Get the ball type carrier 10g of embodiment 1 preparation, with PdCl
2Add the dipping solution 30ml that hydrochloric acid is made into Pd content 0.0035wt%, pH4.5, impregnated carrier is 2 hours at normal temperatures, will flood PdCl
2Carrier 70 ℃ of dryings 2 hours in baking oven, 120 ℃ of dryings 2 hours, 300 ℃ of roastings 4 hours in retort furnace then, in 100 ℃ of following hydrogen reducings 4 hours, the catalyzer of preparing note was made catalyzer-1 again, the Pd content in this catalyzer is 0.01wt%.
Embodiment 3
The preparation process of used ruthenium catalyst in present embodiment explanation the inventive method.
Get the ball type carrier 10g of embodiment 1 preparation, with RuCl
3Add the dipping solution 30ml that hydrochloric acid is made into Ru content 0.105wt%, pH4.5, impregnated carrier is 2 hours at normal temperatures, will flood RuCl
3Carrier 70 ℃ of dryings 2 hours in baking oven, 120 ℃ of dryings 2 hours, 300 ℃ of roastings 4 hours in retort furnace then, in 100 ℃ of following hydrogen reducings 4 hours, the catalyzer of preparing note was made catalyzer-2 again, the Ru content in this catalyzer is 0.3wt%.
Embodiment 4-11
These embodiment illustrate the effect that the inventive method is implemented under different air speeds.
Adding the 8g granularity in the reactor of internal diameter 13.5mm is the catalyzer-1 of 60-80 micron.Four internal diameters for the copper coil of 65mm, external diameter 160mm, thickness 60mm, the number of turn 400 along the reactor axial arranging so that uniform magnetic field to be provided, the distance between the coil axle center is 70mm.Reaction mass (gas mixture of ethene and acetylene) by the bottom of reactor enter, top flows out, in temperature of reaction is to carry out selective hydrogenation under 75 ℃, pressure 1.5MPa, magneticstrength 300 oersteds, hydrogen and 1.2: 1 the condition of acetylene raw materials components mole ratio, analyze with vapor-phase chromatography at reactor exit, analyze the gained data and be calculated as follows, gained the results are shown in table 1.
Table 1
| Embodiment | Acetylene content, volume % | Air speed, the time -1 | Conversion of alkyne, % | Ethylene selectivity, % |
| 4 5 6 7 8 9 10 11 | 0.66 0.66 0.66 0.66 1.0 2.0 3.0 4.5 | 6000 9000 12000 18000 7000 5000 3000 2000 | 100.0 99.7 98.3 93.6 100.0 100.0 96.7 92.8 | 82.2 90.3 92.5 93.2 90.2 89.1 90.5 91.6 |
Embodiment 12-17
These embodiment illustrate the effect that the inventive method is implemented down in differential responses condition (magneticstrength, temperature of reaction, reaction pressure).
Carry out selective hydrogenation according to the said method of embodiment 4-11.Contain acetylene 0.66 volume % in the reaction mass (gas mixture of ethene and acetylene), during air speed 9000
-1, hydrogen and acetylene raw materials components mole ratio 1.2: 1.Implementation result under different magnetic field intensity, temperature of reaction, the reaction pressure is listed in table 2.
Table 2
| Embodiment | Temperature, ℃ | Pressure, MPa | Magneticstrength, oersted | Conversion of alkyne, % | Ethylene selectivity, % |
| 12 13 14 15 16 17 | 30 100 75 75 75 75 | 1.5 1.5 0.8 4.0 1.5 1.5 | 300 300 300 300 60 700 | 60.2 100 85.4 100 93.8 89.2 | 98.3 63.2 93.6 81.2 91.3 90.5 |
Embodiment 18
Implementation result when using ruthenium catalyst in present embodiment explanation the inventive method.
According to the said method of embodiment 4-11, adding the 8g granularity in the magnetically stabilized bed reactor of internal diameter 13.5mm is the catalyzer-2 of 60-80 micron.The reaction mass (gas mixture of ethene and acetylene) that contains acetylene 3.0 volume % by the bottom of reactor enter, top flows out, and is 50 ℃ in temperature of reaction, when pressure 1.5MPa, air speed 9000
-1, carry out selective hydrogenation under magneticstrength 300 oersteds, hydrogen and 1.2: 1 the condition of acetylene raw materials components mole ratio.Reaction result is a conversion of alkyne 99.3%, ethylene selectivity 66.2%.
Comparative Examples 1
This Comparative Examples explanation adopts method provided by the invention and commercial catalysts G83-C (Japanese NGC company commodity) to carry out the comparison of selective hydrogenation of acetylene reaction effect in the ethene in fixed-bed reactor.
Reaction mass has identical composition: acetylene content is ethene-acetylene mixture of 0.66 volume %.
When adopting the inventive method, the reaction conditions in the magnetically stabilized bed reactor is 75 ℃ of temperature, pressure 1.5MPa, volume space velocity 9000 hours
-1, hydrogen and acetylene raw materials components mole ratio 1.2: 1, magneticstrength 300 oersteds.
The reaction conditions that is used for correlated fixed-bed reactor is: 75 ℃ of temperature, pressure 1.5MPa, volume space velocity 9000 hours
-1, hydrogen and acetylene raw materials components mole ratio 1.2: 1.
Analyze with vapor-phase chromatography at reactor exit, gained the results are shown in table 3.
Table 3
| Catalyzer | Conversion of alkyne, % | Ethylene selectivity, % |
| Catalyzer-1 G83-C | 99.7 99.5 | 90.3 86.5 |
Claims (8)
1, the method for a little acetylene in a kind of selective hydrogenation and removing ethene cut, being that to make acetylene content in magnetically stabilized bed reactor be the ethene cut of 0.01-5 volume % and magnetic noble metal catalyst in temperature of reaction is that 25-150 ℃, reaction pressure are that 0.5-5.0MPa, hydrogen and acetylene raw materials components mole ratio are 1-3: 1, volume space velocity 1000-24000 hour
-1, magneticstrength 10-1000 oersted condition under contact, said magnetic noble metal catalyst is made up of ball type carrier and one or more the noble metal active component that is selected from palladium, ruthenium, the rhodium, ball type carrier wherein is made up of aluminum oxide and magnetic-particle, and magnetic-particle wherein is by SiO
2The kernel of coating layer and iron compound is formed.
2, according to the said method of claim 1, wherein said temperature of reaction is 25-100 ℃, and reaction pressure is 1.0-3.0MPa, and hydrogen and acetylene raw materials components mole ratio are 1-2: 1, and volume space velocity is 1000-18000 hour
-1, magneticstrength 50-800 oersted.
3, according to the said method of claim 1, wherein said magnetic noble metal catalyst by account for the heavy % of catalyzer 0.001-0.5 be selected from palladium, ruthenium, the rhodium one or more the noble metal active component and the ball type carrier of surplus form.
4, according to the said method of claim 3, precious metal is a palladium in the wherein said catalyzer, accounts for the heavy % of 0.01-0.3 of catalyzer.
5, according to the said method of claim 1, wherein said ball type carrier is made up of the magnetic-particle that accounts for the heavy % of carrier 1-50 and the aluminum oxide of surplus.
6, according to the said method of claim 5, magnetic-particle accounts for the heavy % of 2-15 of carrier in the wherein said ball type carrier.
7, according to claim 1, one of 5 and 6 said methods, the magnetic-particle in the wherein said ball type carrier is (0.05-6) by weight ratio: 1 SiO
2Coating layer and be dispersed in wherein, one or more particle diameters be the 3-30 nanometer, its chemical constitution is for being selected from Fe
3O
4, Fe and γ-Fe
2O
3In the kernel of single domain superparamagnetism particulate of one or more iron compounds form.
8, according to the said method of claim 7, the magnetic-particle in the wherein said ball type carrier is (0.3-4.0) by weight ratio: 1 SiO
2Coating layer and magnetic particle kernel are formed.
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|---|---|---|---|
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5648576A (en) * | 1994-06-09 | 1997-07-15 | Institut Francais Du Petrole | Catalytic hydrogenation process and a catalyst for use in the process |
| US5847250A (en) * | 1995-09-23 | 1998-12-08 | Basf Aktiengesellschaft | Supported palladium catalyst for selective catalytic hydrogenation of acetylene in hydrocarbonaceous streams |
| CN1045305C (en) * | 1995-12-20 | 1999-09-29 | 中国石油化工总公司石油化工科学研究院 | Saturation hydrogenating process for removing olefines from reforming produced oil |
-
2004
- 2004-02-18 CN CNB2004100395765A patent/CN1307134C/en not_active Expired - Lifetime
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5648576A (en) * | 1994-06-09 | 1997-07-15 | Institut Francais Du Petrole | Catalytic hydrogenation process and a catalyst for use in the process |
| US5847250A (en) * | 1995-09-23 | 1998-12-08 | Basf Aktiengesellschaft | Supported palladium catalyst for selective catalytic hydrogenation of acetylene in hydrocarbonaceous streams |
| CN1045305C (en) * | 1995-12-20 | 1999-09-29 | 中国石油化工总公司石油化工科学研究院 | Saturation hydrogenating process for removing olefines from reforming produced oil |
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