CN1286558C - Catalyst filling material for selective hydrogenation - Google Patents
Catalyst filling material for selective hydrogenation Download PDFInfo
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- CN1286558C CN1286558C CN 200310110320 CN200310110320A CN1286558C CN 1286558 C CN1286558 C CN 1286558C CN 200310110320 CN200310110320 CN 200310110320 CN 200310110320 A CN200310110320 A CN 200310110320A CN 1286558 C CN1286558 C CN 1286558C
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- 239000003054 catalyst Substances 0.000 title claims abstract description 85
- 238000011049 filling Methods 0.000 title claims abstract description 34
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 24
- 239000000463 material Substances 0.000 title abstract description 11
- 238000012856 packing Methods 0.000 claims abstract description 30
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 21
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims abstract description 14
- 150000001342 alkaline earth metals Chemical class 0.000 claims abstract description 14
- 229910000480 nickel oxide Inorganic materials 0.000 claims abstract description 7
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims abstract description 7
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 32
- 239000000945 filler Substances 0.000 claims description 32
- 238000000034 method Methods 0.000 claims description 16
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 15
- 238000001035 drying Methods 0.000 claims description 13
- 230000000694 effects Effects 0.000 claims description 13
- 239000000843 powder Substances 0.000 claims description 11
- 238000007598 dipping method Methods 0.000 claims description 8
- 206010013786 Dry skin Diseases 0.000 claims description 7
- 150000001341 alkaline earth metal compounds Chemical class 0.000 claims description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 7
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 6
- 229910001593 boehmite Inorganic materials 0.000 claims description 6
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical group O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 5
- 230000018044 dehydration Effects 0.000 claims description 5
- 238000006297 dehydration reaction Methods 0.000 claims description 5
- 150000002816 nickel compounds Chemical class 0.000 claims description 5
- 229910017604 nitric acid Inorganic materials 0.000 claims description 5
- 229920006395 saturated elastomer Polymers 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 238000001125 extrusion Methods 0.000 claims description 4
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 4
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 claims description 4
- 239000011148 porous material Substances 0.000 claims description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 3
- 229910052749 magnesium Inorganic materials 0.000 claims description 3
- 239000011777 magnesium Substances 0.000 claims description 3
- 229940126214 compound 3 Drugs 0.000 claims description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 2
- 238000007747 plating Methods 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- 125000006850 spacer group Chemical group 0.000 claims description 2
- 244000275012 Sesbania cannabina Species 0.000 claims 1
- 150000002736 metal compounds Chemical class 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 17
- 238000012546 transfer Methods 0.000 abstract description 3
- 238000012545 processing Methods 0.000 abstract description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 abstract 1
- 230000003197 catalytic effect Effects 0.000 description 24
- 238000004821 distillation Methods 0.000 description 24
- 239000002994 raw material Substances 0.000 description 14
- 238000002360 preparation method Methods 0.000 description 10
- 150000001993 dienes Chemical class 0.000 description 9
- 239000001257 hydrogen Substances 0.000 description 9
- 229910052739 hydrogen Inorganic materials 0.000 description 9
- 238000005516 engineering process Methods 0.000 description 7
- 238000005470 impregnation Methods 0.000 description 7
- 229910000510 noble metal Inorganic materials 0.000 description 6
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- 150000001345 alkine derivatives Chemical class 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 230000009467 reduction Effects 0.000 description 5
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- 241000219782 Sesbania Species 0.000 description 4
- 150000001336 alkenes Chemical class 0.000 description 4
- 239000010953 base metal Substances 0.000 description 4
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 4
- -1 hydrogen diene Chemical class 0.000 description 4
- 238000011068 loading method Methods 0.000 description 4
- 231100000572 poisoning Toxicity 0.000 description 4
- 230000000607 poisoning effect Effects 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 229910013553 LiNO Inorganic materials 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 230000029936 alkylation Effects 0.000 description 2
- 238000005804 alkylation reaction Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000006471 dimerization reaction Methods 0.000 description 2
- 238000004508 fractional distillation Methods 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 230000002779 inactivation Effects 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 231100000614 poison Toxicity 0.000 description 2
- 230000007096 poisonous effect Effects 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 238000004230 steam cracking Methods 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 229910000975 Carbon steel Inorganic materials 0.000 description 1
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- XFBXDGLHUSUNMG-UHFFFAOYSA-N alumane;hydrate Chemical compound O.[AlH3] XFBXDGLHUSUNMG-UHFFFAOYSA-N 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000010962 carbon steel Substances 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 238000007233 catalytic pyrolysis Methods 0.000 description 1
- 230000001413 cellular effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- AUZONCFQVSMFAP-UHFFFAOYSA-N disulfiram Chemical compound CCN(CC)C(=S)SSC(=S)N(CC)CC AUZONCFQVSMFAP-UHFFFAOYSA-N 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 238000005194 fractionation Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000007792 gaseous phase Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000001965 increasing effect Effects 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000011344 liquid material Substances 0.000 description 1
- 150000002642 lithium compounds Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 150000002941 palladium compounds Chemical class 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 230000007480 spreading Effects 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 238000004227 thermal cracking Methods 0.000 description 1
- IAQRGUVFOMOMEM-ONEGZZNKSA-N trans-but-2-ene Chemical compound C\C=C\C IAQRGUVFOMOMEM-ONEGZZNKSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
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Abstract
The present invention relates to catalyst filling material for selective hydrogenation, which is composed of the components of the following proportion by weight: 5 to 25 % of nickel oxide, 0.1 to 2.0 % of lithium or alkaline earth metal and aluminum oxide as the rest. A catalyst is in a bulk grid filling material shape or a corrugated plate regular filling material shape. The catalyst filling material for selective hydrogenation not only can avoid huge workload caused by further processing and packing the catalyst, but also can avoid mass transfer influence caused by wire meshes, and simultaneously, the reaction efficiency of the catalyst is enhanced.
Description
Technical field
The present invention relates to a kind of selective hydrocatalyst filler.More particularly, be a kind of catalyst that had both had the selective hydrogenation effect, again can be as a kind of filler.
Background technology
In petrochemical industry, all contain certain diene and alkynes in the alkene that produces in high-temperature steam cracking, catalytic cracking or the thermal cracking process, further needing these dienes and alkynes are reduced to certain concentration content in the processing and utilization, also require to guarantee that alkene does not lose, improve the degree of utilizing of resource.Along with domestic raising to the Fuel Petroleum standard, again because the use of MTBE is subjected to certain forbidding, improves octane number, reduce gasoline Reid vapour pressure (RVP) simultaneously, the technology that has development prospect most is alkylation and butene dimerization.The butylene of FCC and steam cracking can be made the raw material of alkylation and butene dimerization, because the change day by day of catalytic pyrolysis raw material is heavy, the raising day by day of cracking severity contains more diolefin in C 4 fraction or C 5 fraction, need in use the diene in the raw material is removed.As a rule, for producing the high-octane rating product, also wish the butene-1 in the raw material is tautomerized to butene-2.
Remove diene and alkynes, generally adopt process for selective hydrogenation.What the employing of selective hydrogenation both at home and abroad at present was maximum is Fixed Bed Gas Phase or liquid-phase hydrogenatin technology, also has report to carry out selective hydrogenation with catalytic distillation technology.Selective hydrocatalyst has noble metal type and base metal type two classes, and two class catalyst all are that active constituent loading is made on the activated alumina inert carrier.Noble metal catalyst hydrogenation activity component is generally palladium or platinum, such catalyst activity height, so the hydrogenation reaction temperature is low.But the noble metal active component is polluted by the nonmetallic substance in the raw material easily, makes the catalyst poisoning inactivation.The catalyst hydrogenation activity component of base metal type is group VIII and V or VI subgroup metal or a metal oxide in the periodic table of elements, is generally Ni, Co, Mo, W or its oxide.The advantage of base metal type catalyst is a low price, and catalyst is not too responsive to the poisonous substance in the raw material, so the difficult poisoning of catalyst, but its specific activity noble metal type catalyst is low slightly.
A kind of good selective hydrocatalyst not only will have higher hydrogenation activity, and selectivity the more important thing is to have good stable on this basis preferably, that is to say that catalyst will have the ability of anti-impurity and anticol matter.Life of catalyst is prolonged.For increasing activity of such catalysts and stability requirement carrier lower acidity to be arranged,, also require carrier that less specific area and bigger aperture will be arranged simultaneously, to prevent gum deposit to prevent the generation of polymerisation.In addition, in catalyst, add auxiliary agent and also can increase activity of such catalysts and stability.CN1055107C discloses a kind of method for preparing base metal type selective hydrocatalyst, and the catalyst of this method preparation is made up of the aluminium oxide that contains lithium or alkaline-earth metal, nickel oxide.Preparation process is two step dippings, and the first step is with containing lithium or alkaline earth metal compound oxide impregnation alumina supporter, drying and 900～970 ℃ of roastings; Second step was that the carrier after the roasting is flooded with nickeliferous compound solution, and drying is made catalyst 400～500 ℃ of roastings, activates with hydrogen reducing during use.This catalyst is used for the full cut selective hydrogenation of drippolene, and selectivity and stability are preferably just arranged.This catalyst is the spheric catalyst of diameter 1.0～3.0mm, can only be directly used in fixed bed reactors.
CN1242410A discloses a kind of selective hydrocatalyst with catalysis and fractional distillation functions of noble metal type, this Preparation of catalysts be to have cross section be cellular or the alumina support of wheel shape on the carried metal palladium make.Preparation process is: with after aluminium oxide or the aluminium hydrate powder drying in 1100～1300 ℃ of roastings 4～10 hours, in containing the solution of palladium compound, flood then, drying, catalyst is made in 300～600 ℃ of roastings, activates with hydrogen reducing during use.This catalyst can directly be placed in the catalytic distillation tower owing to have certain voidage.The specific area of this catalyst is 15～50m
2/ g, pore volume are 0.2～0.7ml/g.This catalyst can be used for the selective hydrogenation and removing alkynes and the diene of C3, C4, C5 or C5～10 lighter hydrocarbons.But because this activity of such catalysts component is a noble metal, the nonmetallic substance in the easy processed raw material pollutes, and make the catalyst poisoning inactivation, and cost is higher.
Catalytic distillation technology separates catalytic reaction and organically combines with product, selective hydrogenation is had certain facilitation.Be characterized in catalyst is installed in the catalytic distillation tower in some way, can avoid the degree of depth of alkene in the catalytic hydrogenation reaction to transform the shortcoming that causes the catalyst selectivity difference, can simplify separation process simultaneously, save equipment investment.But,, can not realize the counter-current operation in the destilling tower because the voidage of catalyst is too little if directly be seated in the conversion zone of catalytic distillation tower because present catalyst is generally sphere or strip.
For addressing this problem, prior art has two kinds of ways: 1, catalyst granules is filled in the porous container and constitutes the flexible mesh bag of catalyst element as being made by braid such as glass fibre, nylon yarn or stainless steel cloth; The rigid hollow porous cylinder of shutting by two ends such as carbon steel, stainless steels; 2, catalyst is placed directly in the interlayer of two-layer ripple silk net, is arranged in the catalytic distillation tower in some way again.USP6,169,218 disclose a kind of catalytic distillation method to the selective hydrogenation of height unsaturated hydrocarbons, and used catalyst structure is that catalyst is wrapped up into catalytic distillation structure with woven wire in this method.
Difficulty is installed in catalytic distillation structure complex structure, manufacturing used in the described method, expense is higher, and because catalyst is wrapped, and reactant must could contact or leave catalyst through spreading with product, this has also influenced reaction efficiency.
Summary of the invention
The objective of the invention is to provide on the basis of existing technology a kind of selective hydrocatalyst filler, be about to selective hydrocatalyst and be processed into filler, improve the reaction efficiency of catalyst and the mass transfer separating effect between the reaction mass as a kind of catalytic distillation structure.
Selective hydrocatalyst filler provided by the invention is made up of the nickel oxide of 5～25 heavy %, the lithium of 0.1～2.0 heavy % or the aluminium oxide of alkaline-earth metal and surplus, and the shape of catalyst is grid packing type or the structured packing type that looses and pile.
The present invention directly makes the shape of filler with catalyst, not only can avoid catalyst further processed wrapping and the huge workload brought, and the mass transport affects that can avoid woven wire to bring, improves the reaction efficiency of catalyst simultaneously.
Description of drawings
Accompanying drawing is the schematic flow sheet that catalyst filling provided by the present invention uses at catalytic distillation tower.
The specific embodiment
Selective hydrocatalyst filler provided by the invention is made up of the lithium of nickel oxide, 0.1～2.0 heavy % of preferred 10～16 heavy % of 5～25 heavy % preferred 0.3～1.5 heavy % or the aluminium oxide of alkaline-earth metal preferably magnesium and surplus.The shape of catalyst can be the grid packing types such as the Raschig ring of heap, flat Raschig ring, θ ring, cross spacer ring or Pall ring that loose, and also can be corrugated plate regular packing or honeycomb padding.The voidage of this catalyst filling is 60～95%, and crushing strength is 15～80N/mm, and specific area is 50～200m
2/ g, pore volume are 0.2～0.6ml/g.
Selective hydrocatalyst filler of the present invention is that hydrogenation activity component Ni is made on the alumina packing that contains lithium or alkaline-earth metal, and the preparation process that wherein contains the alumina packing of lithium or alkaline-earth metal is:
1, boehmite was dewatered 0.05～0.5 second down at 400～800 ℃, powder after the dehydration is added 0.5～20 heavy % peptizing agent, 0.5～20 heavy % extrusion aid (all accounting for boehmite) make random packing (as grid fillers such as Raschig ring, θ rings) or structured packing (as mellapak packing etc.), after 80～120 ℃ of dryings, roasting is 4～6 hours in 450～500 ℃ of dry air then;
2, with the filler solid after the roasting, the saturated dipping of solution that is mixed with the lithium or the alkaline earth metal compound of scheduled volume, after under 80～120 ℃ dry 4～8 hours, 900～970 ℃ of best 900～970 ℃ of following roastings 4～6 hours, thereby make the alumina packing carrier that contains lithium or alkaline-earth metal.
The preferred nitrate separately of lithium described in the above-mentioned preparation process or alkaline earth metal compound, the compound of alkaline earth metal compound preferably magnesium is preferably magnesium nitrate, preferred lithium nitrate of lithium compound or lithium hydroxide.
Described saturated when dipping lithium or the amount of alkaline earth metal compound be that to make the amount of lithium in the aluminium oxide or alkaline-earth metal be that 0.1～2.0 heavy % is preferably 0.3～1.5 heavy %.
Described peptizing agent is nitric acid or hydrochloric acid; Extrusion aid is citric acid and/or sesbania powder.
The process of hydrogenation activity component Ni on the alumina packing that contains lithium or alkaline-earth metal is: get a certain amount of alumina packing carrier that contains lithium or alkaline-earth metal, the saturated dipping of solution that is made into nickel compound 3～6 hours, the consumption of nickel compound is that to make the content of nickel oxide in the catalyst filling be 5～25 heavy % preferred 10～16 heavy %, filter the dipping back, after under 80～120 ℃ dry 4～8 hours, made the selective hydrocatalyst filler in 4～6 hours 400～500 ℃ of following roastings.The preferred nickel nitrate of described nickel compound.
Selective hydrocatalyst filler of the present invention before use, need 400～450 ℃ with hydrogen reducing 2～4 hours, the volume ratio of hydrogen and catalyst is 50～100: 1 during reduction.
Below in conjunction with accompanying drawing selective hydrocatalyst filler provided by the invention is illustrated in the use of catalytic distillation tower, but not thereby limiting the invention.
In catalytic distillation tower 10, catalyst filling is contained in catalyst zone, at the common filler of the packing area of upper and lower filling.Raw material enters the middle and upper part of catalytic distillation tower 10 through pipeline 1, and hydrogen enters the bottom of catalytic distillation tower 10, the two catalyst zone counter current contacting reaction in tower through pipeline 2.A reacted material part enters condenser 4 condensations through pipeline 3.Condensed material enters return tank 7 through pipeline 5, and material is divided into gas-liquid two-phase in return tank.Gaseous phase materials is through pipeline 6 ejectors.A part is introduced catalytic distillation tower 10 through pipeline 8 as refluxing in the liquid phase material, and through pipeline 14 ejectors, pipeline 14 can not have another part yet as product.Reacted another part material is divided into two-way through pipeline 9, wherein one the tunnel enters reboiler 12 heating after pipeline 11 enters catalytic distillation tower 10, and another Lu Zejing pipeline 13 is as the product ejector.
The present invention directly makes the shape of filler with catalyst, not only can avoid catalyst further processed wrapping and the huge workload brought, and the mass transport affects that can avoid woven wire to bring, improves the reaction efficiency of catalyst simultaneously.
Selective hydrocatalyst filler of the present invention has catalysis and fractional distillation functions simultaneously, can directly be placed in the catalytic distillation tower.This catalyst is a kind of filler, and enough voidages are arranged, and can directly be placed on the effect of playing mass transfer, separation in the catalytic distillation tower.In catalytic distillation tower, vapour-liquid material adverse current directly contacts with catalyst by beds, react simultaneously and the product fractionation, thereby the reaction efficiency height.Catalyst in the conversion zone does not need special inner member, and simple in structure, reduced investment, operating cost are low, easy and simple to handle.Selective hydrocatalyst filler of the present invention is the non-precious metal catalyst catalyst, and is not too responsive to the poisonous substance in the raw material, so catalyst is difficult for poisoning; In conjunction with the characteristics of catalytic distillation technology, can prolong the service life of catalyst simultaneously.Selective hydrocatalyst filler of the present invention is applicable to removing of alkadienes in C3～10 hydrocarbon fraction selective hydrogenation and removing diene and alkynes, particularly FCC butene feedstock.Also can be used for the full cut selective hydrogenation of drippolene simultaneously.
The following examples will give further instruction to this method, but therefore not limit this method.
Embodiment 1
Boehmite was dewatered 0.5 second down at 700 ℃, powder after the dehydration is added the citric acid of 5.0 heavy %, the nitric acid of 2.5 heavy % and the sesbania powder of 1.0 heavy % to mix, (model is B3705 with make-up machine, produce by U.S. Bonnot company, down with) make 4mm * 4mm * 1mm (directly * high * thick) Raschig ring random packing, after 120 ℃ of dryings, roasting made filling carrier in 4 hours in 450 ℃ of dry air then.
With the LiNO of filling carrier after the roasting with preparation
3Solution impregnation 1 hour is after under 120 ℃ dry 4 hours, 900 ℃ of following roastings 4 hours; Again with the Ni (NO for preparing
3)
2Solution impregnation 4 hours after under 120 ℃ dry 4 hours, made the selective hydrocatalyst filler in 4 hours 450 ℃ of following roastings.The composition and the character of this catalyst filling are listed in table 1.
Catalyst filling is contained in the conversion zone at the catalytic distillation tower middle part of diameter 32mm, loadings 100 grams.The random packing of packing area filling φ 4 * 4 metal θ ring.Earlier with catalyst filling reduction 4 hours under 400 ℃, 0.5MPa condition; With the hybrid C 4 is raw material, at 70 ℃ of reaction temperatures, pressure 1.0MPa (gauge pressure), hydrogen diene than 15 (mol/mol), mass space velocity 2.5h
-1Condition under carry out selective hydrogenation.Result of the test is listed in table 2.
Embodiment 2
Boehmite was dewatered 0.5 second down at 700 ℃, powder after the dehydration is added the citric acid of 2.5 heavy %, the nitric acid of 5.0 heavy % and the sesbania powder of 1.5 heavy % to mix, make 4mm * 4mm * 1mm (directly * high * thick) θ with make-up machine and encircle random packing, after 120 ℃ of dryings, roasting made filling carrier in 4 hours in 450 ℃ of dry air then.
With the LiNO of filling carrier after the roasting with preparation
3Solution impregnation 1 hour, drying was 4 hours under 120 ℃, 900 ℃ of following roastings 4 hours; Again with the Ni (NO for preparing
3)
2Solution impregnation 4 hours, drying is 4 hours under 120 ℃, makes the selective hydrocatalyst filler in 4 hours 450 ℃ of following roastings.The composition and the character of this catalyst filling are listed in table 1.
Catalyst filling is contained in the conversion zone at the catalytic distillation tower middle part of diameter 32mm, loadings 100 grams.The random packing of packing area filling φ 4 * 4 metal θ ring.Earlier with catalyst filling reduction 4 hours under 400 ℃, 0.5MPa condition; With the hybrid C 4 is raw material, at 70 ℃ of reaction temperatures, pressure 1.0MPa (gauge pressure), hydrogen diene than 15 (mol/mol), mass space velocity 2.5h
-1Condition under carry out selective hydrogenation.Result of the test is listed in table 2.
Embodiment 3
Boehmite was dewatered 0.5 second down at 700 ℃, powder after the dehydration is added the citric acid of 4.0 heavy %, the nitric acid of 5.0 heavy % and the sesbania powder of 1.0 heavy % to mix, make corrugated plate regular packing with make-up machine, after 120 ℃ of dryings, roasting made filling carrier in 4 hours in 450 ℃ of dry air then.
With the LiNO of filling carrier after the roasting with preparation
3Solution impregnation 1 hour, 120 ℃ of dryings 4 hours, 900 ℃ of roastings 4 hours; Again with the Ni (NO for preparing
3)
2Solution impregnation 4 hours 120 ℃ of dryings 4 hours, made the selective hydrocatalyst filler in 4 hours 450 ℃ of following roastings.The composition and the character of this catalyst filling are listed in table 1.
Catalyst filling is contained in the conversion zone at the catalytic distillation tower middle part of diameter 32mm, loadings 100 grams.The random packing of packing area filling φ 4 * 4 metal θ ring.Earlier with catalyst filling reduction 4 hours under 400 ℃, 0.4～0.5MPa condition; With the hybrid C 4 is raw material, at 70 ℃ of reaction temperatures, pressure 1.0MPa (gauge pressure), hydrogen diene than 15 (mol/mol), mass space velocity 2.5h
-1Condition under carry out selective hydrogenation.Result of the test is listed in table 2.
Embodiment 4
The preparation method of this embodiment catalyst system therefor filler is identical with embodiment 1 with type of feed.Earlier with catalyst filling reduction 4 hours under 400 ℃, 0.4～0.5MPa condition; With the hybrid C 4 is raw material, at 70 ℃ of reaction temperatures, pressure 1.0MPa (gauge pressure), hydrogen diene than 30 (mol/mol), mass space velocity 2.5h
-1Condition under carry out selective hydrogenation.Result of the test is listed in table 2.
Table 1
| Embodiment 1 | Embodiment 2 | Embodiment 3 | |
| Form | |||
| Al 2O 3，m％ | 83.96 | 83.88 | 84.07 |
| NiO，m％ | 15.5 | 15.6 | 15.4 |
| Li，m％ | 0.54 | 0.52 | 0.53 |
| Outward appearance | φ 4 * 4 Raschig rings | φ 4 * 4 θ ring | Corrugated plating |
| Character | |||
| Specific surface, m 2/g | 82 | 83 | 81 |
| Pore volume, ml/g | 0.41 | 0.43 | 0.42 |
| Voidage, % | 68 | 71 | 78 |
| Side pressure strength, N/mm | 28 | 36 | 25 |
Table 2
| Form mol% | Raw material | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 |
| C3H8 | 1.3476 | 0 | 0 | 0 | 0 |
| C3H6 | 0.0308 | 0 | 0 | 0 | 0 |
| i-C4 | 36.7369 | 37.1608 | 37.1761 | 37.1355 | 37.4224 |
| n-C4 | 21.0874 | 22.4938 | 22.4836 | 22.5244 | 22.8639 |
| t-C4＝ | 13.9415 | 22.4884 | 22.5235 | 22.4644 | 22.3027 |
| n-C4＝ | 14.5357 | 3.2373 | 3.2252 | 3.2269 | 3.0117 |
| i-C4＝ | 3.1526 | 3.1734 | 3.1711 | 3.1714 | 3.1749 |
| c-C4＝ | 8.7311 | 11.4422 | 11.4163 | 11.4731 | 11.2218 |
| 1，3-C4＝＝ | 0.4286 | 0.0041 | 0.0042 | 0.0043 | 0.0026 |
| C5＝ | 0.0078 | 0 | 0 | 0 | 0 |
| ∑ | 100 | 100 | 100 | 100 | 100 |
| Olefin(e) centent | 40.3609 | 40.3413 | 40.3361 | 40.3358 | 39.7111 |
| The monoolefine yield, % | 99.95 | 99.94 | 99.94 | 98.39 | |
| The alkadienes removal efficiency, % | 99.04 | 99.02 | 99.00 | 99.39 | |
| Non-1-butylene increment rate, % | 43.67 | 43.70 | 43.69 | 42.11 |
Claims (10)
1, a kind of selective hydrocatalyst filler, form by the nickel oxide of 5～25 heavy %, the lithium of 0.1～2.0 heavy % or the aluminium oxide of alkaline-earth metal and surplus, it is characterized in that catalyst is made filler, described filler voidage is 60～95%, crushing strength is 15～80N/mm, and specific area is 50～200m
2/ g, pore volume are 0.2～0.6ml/g.
2,, it is characterized in that described filler is the grid filler or the structured packing of loosing and piling according to the catalyst filling of claim 1.
3, according to the catalyst filling of claim 2, the grid filler that it is characterized in that described diffusing heap is Raschig ring, flat Raschig ring, θ ring, cross spacer ring or Pall ring.
4,, it is characterized in that described structured packing is corrugated plating or honeycomb padding according to the catalyst filling of claim 2.
5,, it is characterized in that described catalyst is made up of the nickel oxide of 10～16 heavy %, the lithium of 0.3～1.5 heavy % or the aluminium oxide of magnesium and surplus according to the catalyst filling of claim 1.
6, a kind of method for preparing the described catalyst filling of claim 1 is characterized in that with hydrogenation activity component Ni this method comprises on the alumina packing that contains lithium or alkaline-earth metal:
(1) boehmite was dewatered 0.05～0.5 second down at 400～800 ℃, powder after dehydration adding 0.5～20 heavy % peptizing agent, 0.5～20 heavy % extrusion aid are made random packing or structured packing, after 80～120 ℃ of dryings, roasting is 4～6 hours in 450～500 ℃ of dry air then;
(2) with the filler solid after the roasting, the saturated dipping of solution that is mixed with the lithium or the alkaline earth metal compound of scheduled volume, after under 80～120 ℃ dry 4～8 hours,, thereby make the alumina packing carrier that contains lithium or alkaline-earth metal 900～970 ℃ of following roastings 4～6 hours;
(3) the alumina packing carrier that contains lithium or alkaline-earth metal that step (2) is obtained, the saturated dipping of solution that is made into nickel compound 3～6 hours, filter the dipping back, after under 80～120 ℃ dry 4～8 hours, made the selective hydrocatalyst filler in 4～6 hours 400～500 ℃ of following roastings.
7,, it is characterized in that described lithium metal compounds is lithium nitrate or lithium hydroxide according to the method for claim 6.
8,, it is characterized in that described alkaline earth metal compound is a magnesium nitrate according to the method for claim 6.
9,, it is characterized in that described peptizing agent is nitric acid or hydrochloric acid according to the method for claim 6; Extrusion aid is citric acid and/or sesbania powder.
10,, it is characterized in that described nickel compound is a nickel nitrate according to the method for claim 6.
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|---|---|---|---|
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|---|---|---|---|
| CN 200310110320 CN1286558C (en) | 2003-12-30 | 2003-12-30 | Catalyst filling material for selective hydrogenation |
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| CN101822985B (en) * | 2009-03-04 | 2012-07-18 | 中国石油天然气股份有限公司 | Pretreatment method of nickel-based hydrogenation catalyst |
| CN102773101B (en) * | 2012-08-07 | 2014-07-23 | 中国石油化工股份有限公司 | Method for preparing catalyst for dearomatization of solvent oil |
| CN109877313A (en) * | 2019-04-19 | 2019-06-14 | 南京工业大学 | Mesh bag device for hydrogen-containing treatment of titanium alloy powder, preparation method and hydrogen-containing treatment process |
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