CN103013561B - By lightweight C 5 fraction Hydrogenation ethylene cracking material - Google Patents
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- CN103013561B CN103013561B CN201110290478.9A CN201110290478A CN103013561B CN 103013561 B CN103013561 B CN 103013561B CN 201110290478 A CN201110290478 A CN 201110290478A CN 103013561 B CN103013561 B CN 103013561B
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Abstract
By a method for lightweight C 5 fraction Hydrogenation ethylene cracking material, comprise by the lightweight C 5 fraction raw material of hydrogenation and carry out hydrogenation reaction by hydrogenation catalyst fixed bed so that the unsaturated hydrocarbons in lightweight C 5 fraction raw material is converted into saturated hydrocarbons under the existence of hydrogen. Hydrogenation products part is common by hydrogenation catalyst fixed bed after returning and mixing with raw material as solvent, and the latter and the former weight ratio that feeds intake are 1: (6～10). Before mixing with raw material as the hydrogenation products of solvent, first carry out desulfurization by desulfurizing agent fixed bed, desulfurizing agent is for using Cu2+The Y zeolite of modification, Cu in molecular sieve2+Content be 1.6～4.8wt%. The lightweight C 5 fraction material that the present invention can be 0.02wt ‰ left and right to active sulfide content carries out hydrogenation, and desulfurizing agent and hydrogenation catalyst all can ensure long-term operation.
Description
Technical field
The present invention relates to a kind of method of hydrotreating of the C 5 fraction that contains unsaturated hydrocarbons, particularly will contain unsaturated hydrocarbons and containThe C 5 fraction that has an active sulfide is the method for the preparation of the raw material of cracking ethylene preparation through hydrogenation reaction.
Background technology
The traditional raw material of industrial preparing ethylene by steam cracking is naphtha, along with day by day shortage of petroleum resources, oil refining processThe lighter hydrocarbons resource taking C4～C6 as main component producing is also more come to be the more used. With respect to naphtha, lighter hydrocarbons due toComponent is lighter, therefore can obtain higher ethene and propene yield. But, in this light hydrocarbon materials, contain higher unsaturated hydrocarbons,Mainly comprise the alkynes of alkene, alkadienes and small amount, under the hot environment of pyrolysis furnace, unsaturated hydrocarbons will occur polymerization,Thereby the reaction such as cyclisation or condensation causes producing a large amount of cokings, therefore these light hydrocarbon materials must first make insatiable hunger through hydrogenation reactionBe converted into hydrocarbon the raw material that just can be used as preparing ethylene by steam cracking after saturated hydrocarbons. As " C4 hydrogenation of olefins is produced the work of feed ethyleneSkill research " (" petrochemical technology and application ", the 22nd the 5th phase of volume, in September, 2004) literary composition introduced and how catalysis splitThe C4 fraction that gasifying device produces is prepared ethylene cracking material after hydrogenation, and article has also systematically carried out technique and catalystThe investigation of stability.
The a considerable amount of C 5 fractions of byproduct in process of naphtha steam cracking ethene processed, current C 5 fraction most worthyComprehensive utilization is to produce by separation of extractive distillation pentadiene, isoprene and the dicyclopentadiene that wherein economic worth is higherThree kinds of diolefins. Before C 5 fraction separation of extractive distillation diolefin, must first a part be contained to carbon five materials of carbon four lighter hydrocarbonsSeparate, this part material accounts for about 20wt% of C 5 fraction total amount, industrially conventionally this material is called to lightweightC 5 fraction. Lightweight C 5 fraction is also a kind of lighter hydrocarbons that can be used as preparing ethylene by steam cracking, wherein contains equally higherSaturated hydrocarbons, also must be through hydrogenation reaction to remove unsaturated hydrocarbons before cracking.
The desirable catalyst of hydrogenation reaction of unsaturated hydrocarbon is the loaded catalyst taking Metal Palladium or metallic nickel as active component, warpAllusion quotation as Pd/Al2O3Catalyst, Ni/ diatomite catalyst etc. But day by day serious along with petroleum resources in poor quality trend,Oil refining adopts the proportion of high sulfur content crude oil obviously to increase, enrichment in the light hydrocarbon materials that above-mentioned oil refining process producesA considerable amount of active sulfides, as methyl mercaptan, ethyl mercaptan, carbon disulfide and methyl sulfide etc., and Metal Palladium or metallic nickel pairActive sulfide is very responsive, in the time that the content of active sulfide in hydrogenation material exceedes 0.003wt ‰, and Pd/Al2O3、Ni/ diatomite one class hydrogenation catalyst is just easy to poisoning and loses activity.
" C4 hydrogenation of olefins is produced the technical study of feed ethylene " literary composition has been introduced and has been adopted the catalyst of vulcanization type common to tackleMetal active constituent compared with the easy and problem of inactivation poisoning by active sulfide, but this catalyst is for the hydrogenation of diolefinCan be obviously not ideal enough, as described herein, when in C4 fraction, contain little amount 1,3-butadiene time, whole hydrogenation processMust divide two sections and carry out, first alkadienes is converted into the hydrogenation that carries out again monoolefine after monoolefine. First paragraph hydrogenation reaction forAvoid the autohemagglutination of diolefin, hydrogenation process must be controlled under the reaction condition that intensity is very low carries out. And in lightweight C 5 fractionThe content of diolefin and alkynes is conventionally up to 35wt% left and right, and the catalyst of this vulcanization type is not obviously suitable for lightweight carbon fiveThe hydrogenation of fraction.
There is the desulfur technology of multiple maturation in prior art, as adopted molecular sieve as desulfurizing agent, the material of sulfur compound to be enteredRow desulfurization processing. Molecular sieve has catalysis and suction-operated concurrently in sweetening process, and common molecular sieve is for H2S mono-class inorganic sulfurHave higher removal efficiency, and to organic sulfur, particularly the effect that removes of lower boiling organic sulfur is relatively poor. Prior artGenerally make to introduce the metal ions such as copper, zinc, silver, rare earth in molecular sieve by ion-exchange molecular sieve carried out to modification,To improve its catalytic adsorption performance to organic sulfur. As document " copper-loaded 5A molecular sieve desulfurization performance in gasoline simulated systemResearch. " [" chemistry of fuel journal " 2006,34 (1)] and " in CuHY molecular sieve, the distribution of copper ion is de-with absorptionSulphur performance " [" SCI " 2008,29 (9)] all describe Cu in detail2+Right after ion introducing molecular sieveIn the result of study of molecular sieve sweetneing performance improvement.
But suitable high temperature is favourable for the desulfurization of modified molecular screen, and as previously mentioned, contains in lightweight C 5 fractionThere is under relatively large room temperature the diene such as 1,3-butadiene, isoprene, cyclopentadiene and 2-butine that autohemagglutination just very easily occursHydrocarbon and alkynes, metal ion can catalysis accelerate the polymerisation of diolefin and alkynes in addition, and the generation of sweetening process oligomer willCannot avoid. These oligomer can gather on modified molecular screen, cover catalytic active site and the obstruction on modified molecular screen surfaceThe duct of molecular sieve, modified molecular screen is by catalysis and the adsorption function lost very soon sulfide.
Summary of the invention
The invention provides a kind of method by lightweight C 5 fraction Hydrogenation ethylene cracking material, hydrogenation reaction adopts activityHigh Ni/ diatomite catalyst, the present invention coordinates conventional molecular sieve sweetneing technology, has designed a kind of new hydrogenation technique streamJourney, technical problem to be solved is in the time that active sulfide content is higher in raw material, still to carry out smoothly hydrogenation, and hydrogenation is urgedAgent can keep hydrogenation activity for a long time.
Below the concrete technical scheme of the present invention:
By a method for lightweight C 5 fraction Hydrogenation ethylene cracking material, the method comprises by the lightweight C 5 fraction of hydrogenationRaw material under the existence of hydrogen, by hydrogenation catalyst fixed bed carry out hydrogenation reaction so that in lightweight C 5 fraction raw material notSaturated hydrocarbons is converted into saturated hydrocarbons. The product part of hydrogenation reaction is returned as solvent with mixed by the lightweight C 5 fraction raw material of hydrogenationClose rear common by hydrogenation catalyst fixed bed, by the lightweight C 5 fraction raw material of hydrogenation and hydrogenation reaction product as solventThe weight ratio that feeds intake be 1: (6～10).
The present invention is different from prior art, as the hydrogenation products of solvent with mixed by the lightweight C 5 fraction raw material of hydrogenationFrontly first carry out desulfurization by desulfurizing agent fixed bed. The process conditions of desulfurization are: volume liquid hourly space velocity (LHSV) is 3.0～16.0hr-1，System pressure is 0.2～0.6MPaG, and feeding temperature is 5～60 DEG C, and desulfurizing agent is for using Cu2+The Y zeolite of modification, itsParticle diameter is 3～6mm, Cu in molecular sieve2+Content be 1.6～4.8wt%.
Volume liquid hourly space velocity (LHSV) in above-mentioned sulfur removal technology condition is preferably 4.0～12.0hr-1; System pressure is preferably 0.3～0.5MPaG; Feeding temperature is preferably 10～40 DEG C.
Above-mentioned hydrogenation reaction can adopt conventional process conditions, is generally: volume liquid hourly space velocity (LHSV) is 4.0～20.0hr-1, beSystem pressure is 1.0～4.0MPaG, and feeding temperature is 20～100 DEG C, by the lightweight C 5 fraction raw material of hydrogenation with wherein notThe total amount meter of saturated hydrocarbons, hydrogen be (2～5) by the molar ratio of the lightweight C 5 fraction raw material of hydrogenation: 1. ThisThe hydrogenation catalyst of bright recommendation is the loaded catalyst taking Ni as active constituent and taking diatomite as carrier, catalysisIn agent, the content of Ni is 30～50wt%.
In the process conditions of above-mentioned hydrogenation reaction, volume liquid hourly space velocity (LHSV) is preferably 6.0～12.0hr-1; System pressure is bestBe 1.5～3.0MPa; Feeding temperature is preferably 30～60 DEG C; Hydrogen and feeding intake by the lightweight C 5 fraction raw material of hydrogenationMol ratio is preferably (3～4): 1; Throwing by the lightweight C 5 fraction raw material of hydrogenation with the hydrogenation reaction product as solventMaterial weight ratio is preferably 1: (7～9).
In technical scheme provided by the invention, the Ni/ diatomite catalyst of employing is classical hydrogenation of unsaturated hydrocarbons catalyst,This is a kind of loaded catalyst taking Ni as active constituent and taking diatomite as carrier. Catalyst can adopt conventional soakingStain method is prepared, and first diatomite is configured as to particle and makes carrier, then by the solution impregnation that contains Ni salt, Ni is negativeBe downloaded on carrier, then drying, high-temperature roasting, reduction are processed and are sieved and make catalyst finished product.
The preparation of desulfurizing agent also adopts conventional method, as being mixed with ion-exchange with water miscible Cu salt (as copper nitrate)Liquid, adopt the commercially available former powder of Powdered Y zeolite by ion-exchange process by Cu2+Introduce molecular sieve, then through moulding,Dry, roasting and sieve and make granular desulfurizing agent finished product.
Because hydrogenation process is exothermic reaction, conventionally need to by the raw material of hydrogenation, added solvent remove reaction heat withControl the temperature of beds. To adopt the alkane of C4～C6 be all suitable in the present invention in theory, and directly adopt hydrogenationProduct is as obviously economical rationality the most of solvent, and this is also industrial conventional operational means. The present invention has utilized this justPoint, its key problem in technology is to have changed the traditional habit of raw material being carried out desulfurization processing before hydrogenation, and desulfurization processing is placed on and is addedAfter H-H reaction, carry out for this part hydrogenation products returning as solvent. Unsaturated owing to substantially not containing in hydrogenation productsHydrocarbon, this has just been avoided the catalytic active site on the modified molecular screen surface occurring because of gathering of oligomer in sweetening process cappedBlocked with the duct of molecular sieve, desulfurizing agent can keep higher sulfur removal rate for a long time.
On the other hand, through the hydrogenation products of desulfurization processing as solvent with mixed by required technological requirement by the raw material of hydrogenationAfter, enter active sulfide content in the material of hydrogenation catalyst fixed bed and significantly reduce. Generally lightweight C 5 fractionThe active sulfide containing in Hydrogenation ethylene cracking material is 0.02wt ‰ left and right, according to the required solvent adding amount of routine,Enter active sulfide content in the material of hydrogenation catalyst fixed bed and can guarantee to be reduced to 0.003wt below ‰, this just protectsDemonstrate,prove the ground stable operation of hydrogenation catalyst energy long period.
Compared with prior art advantage of the present invention is very remarkable, can be the light of 0.02wt ‰ left and right to active sulfide contentMatter C 5 fraction material carries out hydrogenation, and desulfurizing agent and hydrogenation catalyst all can ensure long-term operation. Operation 500 continuouslyHour back end hydrogenation beds hydrogenation activity still can remain unchanged substantially, and desulfurizing agent has also still kept higher sulfur removal rate,Can reach more than 8000 hours the actual life of hydrogenation catalyst and desulfurizing agent.
Lightweight C 5 fraction material carbon four unsaturated hydrocarbons wherein after hydrogenation are converted into butane, and chain carbon five and straight chain carbon five are notSaturated hydrocarbons is separately converted to isopentane and pentane. Result of practical application shows, hydrogenation products is for raw with steam cracking processProduce ethene, yield of ethene reaches 35% left and right, and propene yield reaches 18% left and right.
Below by specific embodiment, the invention will be further described, in an embodiment, and volume liquid hourly space velocity (LHSV), noThe definition of the saturation factor of saturated hydrocarbons is respectively:
Note: hydrogenation material is to comprise as the hydrogenation products of solvent with by the mixture of the lightweight C 5 fraction raw material of hydrogenation.
Detailed description of the invention
The lightweight C 5 fraction raw material components that embodiment adopts sees the following form:
[embodiment 1～10]
Hydrogenation reaction is carried out in stainless steel tubular type reactor, and reactor is that one ruler cun is the stainless of φ 25mm × 1000mmSteel pipe type reactor. In reaction tube, load 100mL hydrogenation catalyst and form fixed bed, hydrogenation catalyst is taking Ni as activeComponent and the loaded catalyst taking diatomite as carrier, in catalyst, the weight percentage of Ni is 30～50%, anti-Answer device bottom filling inert ceramic balls. Before charging, need with hydrogen, fresh catalyst to be activated.
The desulfurization of hydrogenation products is processed in the very little stainless steel tubular type reactor for φ 25mm × 1000mm of one ruler and is carried out. ?In reactor, load 200mL desulfurizing agent and form fixed bed. Desulfurizing agent is for using Cu2+The Y zeolite of modification, its particle diameter is 3～6mm, Cu in molecular sieve2+Content in table 2. Desulfurizing agent first carried out processed, the high temperature of available 250 DEG C before operationNitrogen blowing bed, nitrogen flow is set as 1000NmL/min, and purge time is 12 hours, after processing finishes, is down to chamberTemperature is for subsequent use. The hydrogenation products pump that previously experiment had prepared is sent into reactor and is carried out desulfurization processing from bottom.
Lightweight C 5 fraction raw material mixes in required ratio with the hydrogenation products of process desulfurization processing, uses pump to set after preheatingSpeed send into hydrogenation reactor by top, hydrogen enters in reactor by gas distributor, lightweight C 5 fraction raw material withAfter the mixed material of the hydrogenation products of desulfurization processing and hydrogen mix, enter hydrogenation catalyst bed layer and carry out hydrogenation reaction. AddHydrogen product enters a gas-liquid separator by hydrogenation reactor bottom, and liquid phase material enters product storage tank. Separated by gas-liquid separatorUnreacting hydrogen after control valve decompression, enter after wet-test meter metering emptying, or Returning reacting system after compression.
A part of hydrogenation products in product storage tank is sent into desulfurization reactor, after desulfurization is processed, sends into hydrogenation reaction as solventMaterial allocation system, whole device so starts normal operating operation.
The hydrogenation reaction that each embodiment is concrete and desulfurization treatment process condition are respectively in table 1 and table 2.
Table 1.
* carbon five is lightweight C 5 fraction raw material, and in the total amount of unsaturated hydrocarbons wherein;
* carbon five is lightweight C 5 fraction raw material;
* * solvent is hydrogenation products.
Table 2.
Get respectively the hydrogenation products that hydrogenation reaction has been carried out 72 hours and 500 hours, carry out composition analysis by gas chromatographyAnd calculate saturation factor. And get respectively hydrogenation reaction and carried out 72 hours and entered for 500 hours the material of hydrogenation reactor,As the hydrogenation products of solvent and by the mixture of the lightweight C 5 fraction raw material of hydrogenation, by chromatogram-atomic emission spectrum methodMeasure active sulfide content. The results are shown in Table 3.
Table 3.
Claims (10)
1. by a method for lightweight C 5 fraction Hydrogenation ethylene cracking material, the method comprises by the lightweight carbon five of hydrogenationFraction raw material carries out hydrogenation reaction by hydrogenation catalyst fixed bed so that in lightweight C 5 fraction raw material under the existence of hydrogenUnsaturated hydrocarbons be converted into saturated hydrocarbons, the product part of hydrogenation reaction return as solvent with former by the lightweight C 5 fraction of hydrogenationMaterial is common by hydrogenation catalyst fixed bed after mixing, by the lightweight C 5 fraction raw material of hydrogenation and hydrogenation reaction as solventThe weight ratio that feeds intake of product is 1: (6～10), is characterized in that:
Before mixing with by the lightweight C 5 fraction raw material of hydrogenation as the hydrogenation products of solvent, first undertaken by desulfurizing agent fixed bedDesulfurization, the process conditions of desulfurization are: volume liquid hourly space velocity (LHSV) is 3.0～16.0hr-1, system pressure is 0.2～0.6MPaG,Feeding temperature is 5～60 DEG C, and desulfurizing agent is for using Cu2+The Y zeolite of modification, its particle diameter is 3～6mm, Cu in molecular sieve2+Content be 1.6～4.8wt%.
2. the method by lightweight C 5 fraction Hydrogenation ethylene cracking material according to claim 1, is characterized in thatVolume liquid hourly space velocity (LHSV) in described sulfur removal technology condition is 4.0～12.0hr-1。
3. the method by lightweight C 5 fraction Hydrogenation ethylene cracking material according to claim 1, is characterized in thatSystem pressure in described sulfur removal technology condition is 0.3～0.5MPaG.
4. the method by lightweight C 5 fraction Hydrogenation ethylene cracking material according to claim 1, is characterized in thatFeeding temperature in described sulfur removal technology condition is 10～40 DEG C.
5. the method by lightweight C 5 fraction Hydrogenation ethylene cracking material according to claim 1, is characterized in thatThe process conditions of described hydrogenation reaction are: volume liquid hourly space velocity (LHSV) is 4.0～20.0hr-1, system pressure is 1.0～4.0MPaG, feeding temperature is 20～100 DEG C, by the lightweight C 5 fraction raw material of hydrogenation in the total amount of unsaturated hydrocarbons wherein, hydrogenGas be (2～5) by the molar ratio of the lightweight C 5 fraction raw material of hydrogenation: 1, hydrogenation catalyst be taking Ni as activityComponent and the loaded catalyst taking diatomite as carrier, in catalyst, the content of Ni is 30～50wt%.
6. the method by lightweight C 5 fraction Hydrogenation ethylene cracking material according to claim 5, is characterized in thatDescribed volume liquid hourly space velocity (LHSV) is 6.0～12.0hr-1。
7. the method by lightweight C 5 fraction Hydrogenation ethylene cracking material according to claim 5, is characterized in thatDescribed system pressure is 1.5～3.0MPa.
8. the method by lightweight C 5 fraction Hydrogenation ethylene cracking material according to claim 5, is characterized in thatDescribed feeding temperature is 30～60 DEG C.
9. the method by lightweight C 5 fraction Hydrogenation ethylene cracking material according to claim 5, is characterized in thatDescribed hydrogen be (3～4) by the molar ratio of the lightweight C 5 fraction raw material of hydrogenation: 1.
10. according to claim 1 or 5 by the method for lightweight C 5 fraction Hydrogenation ethylene cracking material, its featureDescribed in being is 1 by the lightweight C 5 fraction raw material of hydrogenation with the weight ratio that feeds intake of the hydrogenation reaction product as solvent:(7～9)。
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| US4064152A (en) * | 1975-06-16 | 1977-12-20 | Union Oil Company Of California | Thermally stable nickel-alumina catalysts useful for methanation |
| CN1699309A (en) * | 2004-05-20 | 2005-11-23 | 中国石化上海石油化工股份有限公司 | Process for preparing pentane from light C5 distillate |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4064152A (en) * | 1975-06-16 | 1977-12-20 | Union Oil Company Of California | Thermally stable nickel-alumina catalysts useful for methanation |
| CN1699309A (en) * | 2004-05-20 | 2005-11-23 | 中国石化上海石油化工股份有限公司 | Process for preparing pentane from light C5 distillate |
Non-Patent Citations (2)
| Title |
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| CuHY分子筛中铜离子的分布与吸附脱硫性能;范闽光等;《高等学校化学学报》;20080930;第29卷(第9期);第1834-1840页 * |
| 载铜5A分子筛在汽油模拟体系中脱硫性能的研究;冯辉等;《燃料化学学报》;20060228;第34卷(第1期);第117-119页 * |
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