CN103182291A - Preparation method and application of deep desulfurization absorbent in splitting C5 distillate oil - Google Patents
Preparation method and application of deep desulfurization absorbent in splitting C5 distillate oil Download PDFInfo
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Abstract
The invention relates to a preparation method and application of a deep desulfurization absorbent in splitting C5 distillate oil. The method is characterized in that the process comprises the following steps: 1), carrier preparation: taking pseudo-boehmite powder, adding a binder and an extrusion assistant, conducting extrusion moulding or rotary pelleting, and drying and roasting to obtain a strip-shaped or ball-shaped gamma-Al2O3 carrier; and 2), Zn, Cu, and metal in the IA group or IIA group soaking: loading metal salt through a co-soaking method; taking Zn, Cu and the metal in the IA group or IIA group out after soaking and filtering at the room temperature, then drying and roasting, and then cooling naturally, wherein the mass percent of ZnO in the absorbent is 5-15%, the mass percent of CuO in the absorbent is 2-8%, the content of the metallic oxide in the IA group or the IIA group is 1-5%, and the balance is alumina carrier, and the at least one metal in the IA group or the IIA group is any one and/or combination of potassium, sodium and calcium. The application is the application of the prepared desulfurization absorbent in the deep desulfurization reaction of splitting C5 distillate oil.
Description
Technical field
The present invention relates to the purification techniques field of petroleum hydrocarbon product cut oil, be specially a kind of method for making and purposes of cracked C 5 fraction oil deep desulfurization absorbent.Specifically, the present invention relates to the preparation method of the desulfuration adsorbent that a kind of Zn, Cu and at least a IA family or IIA family metallic element and alumina support form, and to application purpose and the regeneration treating method of cracked C 5 fraction oil adsorption desulfurize process.
Background technology
The a large amount of C5 fraction of by-product in the time of petroleum cracking ethene processed, its output is about 10%～20% of ethylene production capacity.The composition of C 5 fraction is very complicated, and 30 various ingredients are arranged approximately, and wherein alkadienes total amounts such as isoprene, pentadiene and cyclopentadiene account for 40%～60% of cracking c5 cut.These alkadienes are the important source material of producing synthetic rubber, plastics, Petropols and various fine chemical products.Utilization for the cracking c5 cut draws attention just day by day, can be used for producing high value-added product-hydrogenated petroleum resin on the one hand, can obtain effective monomers such as isoprene, pentadiene and cyclopentadiene after separating on the other hand.Meanwhile, in cracked C 5 fraction oil, contain trace (10～200 μ g/g) sulfur-containing compound, cos, mercaptan, thioether, disulphide and thiophene etc. are arranged usually.The existence of these sulfur-containing compounds, can cause utilizing the poisoning of some noble metal hydrogenation catalysts in the following process processing procedure to take place for cracked C 5 fraction oil, and the quality of high value added product when influencing monomer deep processing such as isoprene, pentadiene and cyclopentadiene.
Except hydrofinishing technology commonly used, at present domestic a lot of for removing in the distillate sulfide reported method, as hydrofinishing method, complexing removal method, refining, the physisorphtion of hydramine, chemiadsorption, catalytic oxidation etc., but remove the effective removal methods of Shang Weiyou for sulfide in the cracked C 5 fraction oil, be difficult to the sulphur in the distillate is taken off to 1 μ g/g.
In the existing industrial production, take traditional hydrodesulfurization technology can remove sulfide in the distillate effectively, namely under higher temperature and pressure, hydrodesulfurization reaction takes place to generate hydrogen sulfide at Co (or Ni) Mo (or W) hydrogenation catalyst, hydrogen sulfide changes into elemental sulfur by claus process again.But owing to contain alkadienes, the monoolefine of mass efficient in the cracked C 5 fraction oil, under hydroconversion condition, though sulfide can be removed by hydrogenation, be easy to take place olefin saturation simultaneously, this has not only increased the hydrogen consumption greatly, and greatly reduces the content of effective alkene.
For other single sweetening process, can not remove various sulfide simultaneously, often need to unite several sulfur methods of use.And there is weak point in these sulfur methods: at first, no matter be that hydramine is refining, catalytic oxidation desulfurization, but in the raw material total sulfur content when high, bad desulfurization effects, and, the easy inactivation of employed catalyst; In addition, better for the inorganic sulfur removal effect, and relatively poor for the removal effect of organic sulfur, particularly for the bigger organic sulfur compound of molecular weight, as mercaptan, thioether, thiophene etc.; In addition, existing method also exists waste liquid and the reluctant problem of waste residue.
The at present industrial a kind of mercaptan removal technique that generally adopts is the alkali-free sweetening technology.Be characterized in raw material oil product and activator solution after blender fully mixes, react to remove mercaptan with air during by beds.The preparation method of the described fixed bed catalyst impregnating solution of Chinese patent CN1248609A is that compound with phthalocyanine cobalt class is dissolved in the aqueous solution of 0.5～2% alkali metal oxide.Because solution is strong basicity, the compound of phthalocyanine cobalt class can transform to inactive ingredients, makes that the compound concentration of active phthalocyanine cobalt class reduces in the maceration extract.The preparation method of US Patent No. 4913802 disclosed maceration extracts adds the compound that phthalocyanine bores class in the quaternary ammonium base mixed liquor of 2% ammoniacal liquor and 1%, although can slow down the compound of phthalocyanine cobalt class transforms to inactive ingredients, but the catalyst with this maceration extract preparation still runs off in deodorising process easily, unfriendly to environment on the one hand, easily form and pollute, can cause bed shorter service life on the other hand.
The described oxidation deodorizing sulfur method of Chinese patent CN101063042A is as homogeneous catalyst with heteropoly acid and heteropolyacid salt, in having the efficient mass transfer reactor of strengthening the turbulent flow inner member, react, obtain the high-quality oil product of odorless, but the shortcoming of this method is to remove thiophenic sulfur, and has separation problem.
Purposes when Chinese patent CN1011632934A discloses a kind of refining C 5 fraction hydrogenation prerefining Preparation of catalysts method and carried out selective hydrogenation.For satisfying subsequent production high-quality hydrogenated carbon five petroleum resin arts demand, when this catalyst carried out selective hydrogenation, alkynes hydrogenation conversion 〉=50%, diene hydrogenation conversion ratio were 15～35%, sulfur content in the hydrogenation tails oil＜10 μ g/g, nitrogen content＜10 μ g/g.
Chinese patent CN101450303A discloses a kind of carbon containing five conjugated diene hydrocarbon feed ultra-deep desulfurization absorbents and method for making and application, and used desulfuration adsorbent has going back ortho states VIII group 4 transition metal, going back ortho states IB group 4 transition metal and alumina support is formed of activation sulfur-containing molecules by being selected from.When this adsorbent was used for carbon containing five conjugated diene raw material sulfide and removes, what can obtain that sulfur content is lower than 10 μ g/g contained the C 5 diene raw material.But the use of this adsorbent still is difficult to sulfur content in the raw material is removed to the level that is lower than 1 μ g/g; Because adsorption process under hydro condition, adopts and goes back the VIII group 4 transition metal that ortho states has hydrogenation activity, be difficult to guarantee that the hydrogenation saturated reaction does not take place diolefin in addition.
The Catalyst And Method that the alkynes that is present in the C5 fraction is carried out selective hydrogenation, prior art can't satisfy at alkadienes to be had under an amount of saturated situation, reduce amount of alkene maximized requirement in α position in the surplus of alkynes and the product simultaneously, how the sulphur nitrogen impurity is removed in the C5 fraction method and effect are not more arranged.
In sum, prior art can't satisfy the requirement of cracked C 5 fraction oil ultra-deep desulfurization, and sulfide removes technology and has following problems in the existing distillate, as: 1, desulfurization depth is not enough, is difficult to sulphur is taken off to being lower than 1 μ g/g from 10～200 μ g/g; 2, in the sweetening process, alkadienes generation saturated reaction, its content has loss; 3, sweetening process is unfriendly to environment.Researcher of the present invention is in experimentation, the unexpected desulfuration adsorbent of finding to use the present invention's preparation, under selected adsorption conditions, can realize deep desulfuration for cracked C 5 fraction oil, alkadienes loses hardly simultaneously, and selected regeneration techniques can make the absorption property of adsorbent be restored in addition.
Summary of the invention
The object of the present invention is to provide a kind of preparation method and application of cracked C 5 fraction oil deep desulfurization absorbent.
The present invention is a kind of method for making and purposes of cracked C 5 fraction oil deep desulfurization absorbent, it is characterized in that:
Technical process comprises:
1) preparing carriers: get the boehmite powder, add a certain amount of binding agent, extrusion aid, extruded moulding or rotation granulation, 100～150 ℃ of dryings 6～12 hours, 450～600 ℃ of following roastings 2～6 hours, cool naturally then again, obtain bar shaped or spherical gamma-Al
2O
3Carrier;
2) dipping Zn, Cu, IA family or IIA family metal: adopt the co-impregnation loading metal-salt, nitrate with zinc nitrate, copper nitrate and IA family or IIA family metal under the normal temperature is made into the finite concentration dipping solution, will be through 1) carrier impregnation that obtains of step is in metal salt solution, at room temperature flooded 2～6 hours, filtering the back takes out, dry down more than 12 hours at 120～150 ℃, again 350～480 ℃ of following roastings 2～6 hours, cooling naturally then;
Wherein ZnO shared mass percent in adsorbent is that 5～15%, CuO shared mass percent in adsorbent is 2～8%, and IA family or IIA family metal oxide content are 1～5%, and all the other are alumina support;
Described at least a IA family or IIA family metal are the combinations of any one and/or they in potassium, sodium, the calcium.
According to method for making of the present invention, it is characterized in that; The fixed bed reactors operation is adopted in the application of prepared desulfuration adsorbent in the deep desulfuration reaction of cracked C 5 fraction oil, and the adsorption operations condition is as follows: 30～50 ℃ of adsorption temps, normal pressure～0.5MPa, volume space velocity 0.5～2h during liquid
-1, adsorbent activates 2～6 hours before using under 150～300 ℃ of nitrogen atmospheres.
According to method for making of the present invention, it is characterized in that, the renovation process of described cracked C 5 fraction oil deep desulfurization absorbent, when sulfur content is higher than 1 μ g/g in the reactor outlet cracked C 5 fraction oil, the desulfuration adsorbent processing of regenerating, the regenerative operation condition is as follows: be that solvent carries out desorption and handles 120～150 ℃ of regeneration temperatures with methyl alcohol, 0.2～0.5MPa, volume space velocity 1～2h during liquid
-1, 2～6 hours recovery times.
Compound concentration in the dipping solution is to calculate like this, and after this concentration should make dipping finish and impregnated carrier is converted into after the finished catalyst, the component that is deposited reaches in catalyst with carrier and calculates desirable content.
Desulfuration adsorbent activity after the regeneration can return to the fresh adsorbent desulfurization level, for guaranteeing that cracked C 5 fraction oil adsorption desulfurize process can continued operation, during the suggestion commercial Application, adopt two reactor adsorption operations, after one of them reactor absorption is saturated, switch to another reactor and continue absorption, meanwhile this reactor carries out regenerative operation.
Compared with prior art, our face has the following advantages:
(1) cracked C 5 fraction oil is after adsorption treatment, and sulfur content is lower than 1 μ g/g in the generation oil;
(2) adsorbent is to adsorptive selectivity and the adsorption capacity height of sulfide;
(3) adopt fixed-bed operation, the adsorbent free of losses, operating cost is low, basic non-environmental-pollution;
(4) adsorbent is renewable, and activity obtains fine recovery, is beneficial to the long period industrial operation.
The specific embodiment
Embodiment 1
Prepare adsorbent of the present invention
With 200g aluminium oxide and 4g methylcellulose mixing 30min, add the 3wt% dilute nitric acid solution of 170mL, mixes after 20 minutes roller forming 3mm ball in comminutor, 120 ℃ of dryings 12 hours, 500 ℃ of roastings 4 hours make aluminium oxide sphere carrier; Then 165g zinc nitrate, 65g copper nitrate, 7.5g potassium nitrate are added deionized water dissolving, be made into the 300mL settled solution, the oxide impregnation alumina supporter, flood after 4 hours, filter out unnecessary filtrate, filtrate for later use, dipping back carrier was 120 ℃ of dryings 12 hours, 450 ℃ of roastings 3 hours make the finished product adsorbent.
The catalyst of above-mentioned preparation is numbered A, and wherein ZnO quality percentage composition is 14.3wt%, and CuO quality percentage composition is 7.1wt%, K
2O quality percentage composition is 2.2%, surplus be aluminium oxide.
Embodiment 2～6
Method by embodiment 1 prepares other adsorbent B～F, and different is has changed concentration and IA family or the IIA family metallic element of slaine in the sintering temperature of carrier and the maceration extract.Adsorbent preparation condition and constituent content see Table 1.
Table 1
Embodiment 7
Cracked C 5 fraction oil with sulfur content 45.6 μ g/g, alkadienes quality percentage composition 41.5% is raw material, investigates the desulfurized effect of adsorbent, and adsorption process is carried out in fixed bed reactors.Adsorption conditions is: desulfuration adsorbent volume 300mL, adsorption temp are 30 ℃, and adsorptive pressure is 0.2MPa, and volume space velocity is 0.8 h during C5 fraction fluid
-1Before absorption, adsorbent is 280 ℃ of activation processing 3 hours under nitrogen atmosphere earlier, reduce temperature of reactor to 30 ℃ then, and beginning into, C5 fraction oil carries out adsorption treatment.Sulfur content adopts Antek 9000VLLS sulphur analysis-e/or determining in the sample, detects and is limited to 0.1 μ g/g.The diene content analysis is carried out on the gas chromatograph (Agilent 7890) that capillary column (PONA, 50 * 0.2mm, id * 0.5 μ m) is housed and fid detector in the cracked C 5 fraction oil.Absorption result is listed in the table 2.
Embodiment 8～14
Respectively adsorbent B～F is carried out the absorption property evaluation test in the 300mL fixed bed reactors, before absorption, adsorbent was handled certain hour under nitrogen atmosphere earlier, reduced temperature of reactor then to required adsorption temp.
The results are shown in Table 2 for the performance evaluation of each adsorbent.
Table 2
Evaluation result as can be seen from table, adopt desulfuration adsorbent provided by the invention, can effectively remove the sulfide in the cracked C 5 fraction oil, obtain the product that sulfur content is lower than 1 μ g/g, the realization ultra-deep desulfurization is handled, and guarantees that simultaneously diene content loses hardly.
Embodiment 15
The desulfuration adsorbent regeneration test
For adsorbent A, in the absorption evaluation procedure, it is 1.5 μ g/g that 350 hours afterproducts detect sulfur content, the processing that begins to regenerate, and the switching raw material is methyl alcohol, carries out desorption and handles.145 ℃ of regeneration temperatures, regeneration pressure 0.3MPa, volume space velocity 1.5h during liquid
-1, 4 hours recovery times.Adsorbent after the regeneration, 280 ℃ of activation processing are 3 hours under nitrogen atmosphere, advance cracked C 5 fraction oil again and carry out the adsorption desulfurize reaction, and adsorption temp is 30 ℃, and adsorptive pressure is 0.2MPa, and volume space velocity is 0.8 h during C5 fraction fluid
-1, the The product sulfur assay is 0.5 μ g/g, alkadienes quality percentage composition is 41.3%.
Claims (3)
1. the method for making of cracked C 5 fraction oil deep desulfurization absorbent is characterized in that:
Technical process comprises:
1) preparing carriers: get the boehmite powder, add a certain amount of binding agent, extrusion aid, extruded moulding or rotation granulation, 100～150 ℃ of dryings 6～12 hours, 450～600 ℃ of following roastings 2～6 hours, cool naturally then again, obtain bar shaped or spherical gamma-Al
2O
3Carrier;
2) dipping Zn, Cu, IA family or IIA family metal: adopt the co-impregnation loading metal-salt, nitrate with zinc nitrate, copper nitrate and IA family or IIA family metal under the normal temperature is made into the finite concentration dipping solution, will be through 1) carrier impregnation that obtains of step is in metal salt solution, at room temperature flooded 2～6 hours, filtering the back takes out, dry down more than 12 hours at 120～150 ℃, again 350～480 ℃ of following roastings 2～6 hours, cooling naturally then;
Wherein ZnO shared mass percent in adsorbent is that 5～15%, CuO shared mass percent in adsorbent is 2～8%, and IA family or IIA family metal oxide content are 1～5%, and all the other are alumina support;
Described at least a IA family or IIA family metal are the combinations of any one and/or they in potassium, sodium, the calcium.
2. according to the described method for making of claim 1, it is characterized in that; The fixed bed reactors operation is adopted in the application of prepared desulfuration adsorbent in the deep desulfuration reaction of cracked C 5 fraction oil, and the adsorption operations condition is as follows: 30～50 ℃ of adsorption temps, normal pressure～0.5MPa, volume space velocity 0.5～2h during liquid
-1, adsorbent activates 2～6 hours before using under 150～300 ℃ of nitrogen atmospheres.
3. according to method for making of the present invention, it is characterized in that, the renovation process of described cracked C 5 fraction oil deep desulfurization absorbent, when sulfur content is higher than 1 μ g/g in the reactor outlet cracked C 5 fraction oil, the desulfuration adsorbent processing of regenerating, the regenerative operation condition is as follows: be that solvent carries out desorption and handles 120～150 ℃ of regeneration temperatures with methyl alcohol, 0.2～0.5MPa, volume space velocity 1～2h during liquid
-1, 2～6 hours recovery times.
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| CN107175109A (en) * | 2017-06-28 | 2017-09-19 | 江苏晶晶新材料有限公司 | A kind of preparation method of heatproof desulfurizing industrial fume catalyst |
| CN110876924A (en) * | 2018-09-06 | 2020-03-13 | 中国石油化工股份有限公司 | Carbon five-raw material desulfurization adsorbent and preparation method and application thereof |
| CN111870999A (en) * | 2020-07-21 | 2020-11-03 | 辽宁石油化工大学 | Combined bed adsorption desulfurization method for ultra-deep removal of sulfur impurity in cracking carbon five |
| CN113083215A (en) * | 2021-04-08 | 2021-07-09 | 中国石油大学(北京) | Metal modified active alumina adsorbent and preparation method and application thereof |
| CN114106867A (en) * | 2021-10-27 | 2022-03-01 | 中国石油化工股份有限公司 | Method for reducing sulfur content in carbon five fraction |
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| CN104387220A (en) * | 2014-10-16 | 2015-03-04 | 吉林化工学院 | Adsorption desulphurization method for removing carbon disulfide from isoprene |
| CN104927906A (en) * | 2015-05-20 | 2015-09-23 | 宁波章甫能源科技有限公司 | Device for deeply removing sulfides in C5 fraction and desulfurization process utilizing device |
| CN107175109A (en) * | 2017-06-28 | 2017-09-19 | 江苏晶晶新材料有限公司 | A kind of preparation method of heatproof desulfurizing industrial fume catalyst |
| CN110876924A (en) * | 2018-09-06 | 2020-03-13 | 中国石油化工股份有限公司 | Carbon five-raw material desulfurization adsorbent and preparation method and application thereof |
| CN110876924B (en) * | 2018-09-06 | 2023-04-28 | 中国石油化工股份有限公司 | Carbon five-raw-material desulfurization adsorbent and preparation method and application thereof |
| CN111870999A (en) * | 2020-07-21 | 2020-11-03 | 辽宁石油化工大学 | Combined bed adsorption desulfurization method for ultra-deep removal of sulfur impurity in cracking carbon five |
| CN113083215A (en) * | 2021-04-08 | 2021-07-09 | 中国石油大学(北京) | Metal modified active alumina adsorbent and preparation method and application thereof |
| CN113083215B (en) * | 2021-04-08 | 2022-07-26 | 中国石油大学(北京) | Metal modified active alumina adsorbent and preparation method and application thereof |
| CN114106867A (en) * | 2021-10-27 | 2022-03-01 | 中国石油化工股份有限公司 | Method for reducing sulfur content in carbon five fraction |
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Address after: 100010 Chaoyangmen North Street, Dongcheng District, Dongcheng District, Beijing Co-patentee after: CNOOC Energy Development Co., Ltd. Patentee after: China Offshore Oil Group Co., Ltd. Co-patentee after: CNOOC TIANJIN CHEMICAL RESEARCH & DESIGN INSTITUTE CO., LTD. Address before: 100010 Chaoyangmen North Street, Dongcheng District, Dongcheng District, Beijing Co-patentee before: CNOOC Energy Development Co., Ltd. Patentee before: China National Offshore Oil Corporation Co-patentee before: CNOOC Tianjin Chemical Research & Design Institute |