CN103894146A - Potassium ion-containing molecular sieve desulfurizing agent, and preparation method thereof - Google Patents
Potassium ion-containing molecular sieve desulfurizing agent, and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a potassium ion-containing molecular sieve desulfurizing agent, and a preparation method thereof. According to the preparation method, metal cation K+ is used for modifying a molecular sieve, and potassium ion exchange degree is controlled to be 5 to 25%, so that electrostatic field intensity of local positions in hole passages of the molecular sieve is increased, and when the molecular sieve is used for desulphurization of hydrocarbon flow via physical adsorption, neutral sulfide and disulphide molecules in the hydrocarbon flow are polarized, and are absorbed easily, absorption capacity and absorption efficiency of the molecular sieve on the sulfides are increased. The potassium ion-containing molecular sieve desulfurizing agent with an ion exchange degree of 5 to 25% is excellent in absorption effect, is high in absorption capacity, and is capable of reducing generation times of the potassium ion-containing molecular sieve desulfurizing agent effectively.
Description
Technical field
The present invention relates to a kind ofly for removing molecular sieve type desulfurizing agent of liquid hydrocarbon or light-end products disulphide and preparation method thereof, belong to desulfurizing agent technical field.
Background technology
In petrochemicals, conventionally contain a certain amount of sulfide, these sulfide exist with the form of organic sulfur compound and inorganic sulphide.Wherein, inorganic sulphide is mainly hydrogen sulfide, and removing of hydrogen sulfide can be by adopting different desulfurizing agents and corresponding sulfur removal technology to carry out; Organic sulfur compound comprises mercaptan, thioether, thiophenol, sulphur oxygen carbon, carbon disulfide, thiophene etc., because often needing that organic sulfur compound is converted into inorganic sulphide effectively, removing of organic sulfur compound just can remove later, and cannot directly remove by direct employing desulfurizing agent and corresponding sulfur removal technology, thereby increase the difficulty that removes of organic sulfur compound.
At present, the method for conventional organic sulfide removal compound has hydro desulfurization and catalytic oxidation.Hydro desulfurization is to remove after the above-mentioned organic sulfur compound in hydrocarbon ils (comprising liquefied petroleum gas, naphtha, catalytic gasoline, aviation kerosine, lam-oil, diesel oil) is hydroconverted into inorganic sulphide (being hydrogen sulfide) again, catalytic oxidation is thioether or the disulfide etc. that mercaptan is changed into odorless, removes with solvent extraction; The precision of above-mentioned its desulfurization of doctor treatment for organic sulfide removal compound is lower, and complex disposal process is simultaneously also very high to the requirement of equipment.
Along with the development of modern petrochemical technology, in Chemical Manufacture, for guarantee effective catalyst in follow-up Chemical Manufacture technique stability, avoid its sulfur poisoning, so more and more harsher to the requirement of the sulfur content in raw material, simultaneously also more and more stricter to the environmental protection standard of sulphur emissions, thereby the total sulfur content in petrochemicals is proposed to stricter requirement, so that adopted above-mentioned doctor treatment can not meet the requirement to raw material organic sulfur removal effect.
Molecular sieve is to adopt the artificial synthetic silicon aluminate crystal of hydro-thermal method, reach absorption or repel different material molecule effect according to crystals hole size, determine the order of absorption simultaneously according to the difference of material molecule polarity or polarizable degree, thereby realize the object separating.Can be divided into various dissimilar according to the difference of silicon-aluminum containing ratio in molecular sieve, as A type, X-type and Y zeolite etc., the molecular sieve of same type is through exchanging with different metal cation and becoming different classes of molecular sieve of the same type, thereby can change physics, the chemical property of molecular sieve by exchange different ions, thereby expand its application in petrochemistry field.In addition, very homogeneous of the pore-size distribution of molecular sieve, thereby molecular sieve has unique absorption and separating property than the adsorbent of other types.For these reasons, the molecular sieve after the modification of exchange different ions, is used for the desulfurization of industrial chemicals or chemical products widely by physical absorption and two kinds of modes of chemisorbed.Wherein, when the mode of employing chemisorbed is carried out desulfurization, because sulfide with molecular sieve, chemical reaction has occurred, so molecular sieve can only use once, can not regenerate; And while adopting the mode of physical absorption to carry out desulfurization, the just combination by suction-operated between sulfide and molecular sieve, chemical reaction does not occur, the recycling so molecular sieve can repeatedly be regenerated, greatly reduces chemical industry production cost.
Although molecular sieve has stronger desulphurizing activated for desulfurization, but for removing of the disulphide containing in oil gas, it still has certain limitation, this is because disulphide belongs to neutral organic sulfur compound, while adopting this organic sulfur compound of physical absorption, the conventional molecular sieve using is because center electric-field intensity is lower, and centering organic sulfur compound adsorption capacity is low, thereby is difficult to the neutral sulfide containing in oil gas to remove.
In order to address the above problem, Chinese patent literature CN1329937 discloses a kind of molecular sieve desulfurizer, the Main Ingredients and Appearance of this desulfurizing agent is the modified molecular screen after high valence state (being generally 3 valencys) rare earth metal cation (as lanthanum, cerium or mixed light rare earth metal) exchange, and its exchange degree is up to 70%-95%.This molecular sieve desulfurizer utilizes the rare earth metal cation of high valence state to carry out modification to molecular sieve, by after sodium ion exchange less inner molecular sieve most radiuses, the electric stress of local location in molecular sieve pore passage is improved, thereby make neutral organic sulfur compound molecule polarized and be more easily adsorbed, and then make the Sulfur capacity that once penetrates of this molecular sieve desulfurizer improve 2% left and right than molecular screen primary powder.In this technology, in order to improve the polarization absorption of modified molecular screen to organic sulfur compound molecule, need to improve as much as possible the exchange degree of modified molecular screen middle rare earth metal cation, meanwhile, this is also technological means conventional in prior art.But, even if in this technology still there is the problem that desulfuration efficiency is low in the modified molecular screen of high exchange degree when for organic sulfur compound Molecular Adsorption desulphurization reaction.So any reason is caused to the problems referred to above, up to the present also there is no result of study.
From the desulfurization absorption property of molecular sieve desulfurizer, effectively desulfurizing agent should have good absorption property and desorption performance simultaneously, and for above-mentioned through the cation-modified molecular sieve desulfurizer of the rare earth metal such as lanthanum, cerium, because the rare earth metal such as lanthanum, cerium cation valence is high, polarity is strong, to the adsorption capacity of organic sulfur compound molecule compared with strong, adsorption capacity is large, once just be difficult to desorption after its absorption organic sulfur compound molecule, and then affected the regeneration use of molecular sieve.
Summary of the invention
First technical problem that the present invention will solve is that in prior art, exchange degree exchanges modified molecular screen up to 70%～95% lanthanum, cerium ion, in the time organic sulfur compound molecule being carried out to desulfurization processing, still there is the problem that desulfuration efficiency is low, and then the molecular sieve of the potassium ion exchange modification that a kind of exchange degree is 5%～25%, centering disulphide adsorption capacity is large is provided.
Second technical problem that the present invention will solve is that lanthanum, cerium ion that available technology adopting polarity is stronger exchange modification to molecular sieve, make to be just difficult to desorption after described lanthanum, cerium ion molecular sieve adsorption organic sulfur compound molecule, so provide a kind of easy desorption and regeneration containing potassium ion molecular sieve.
In order to solve the problems of the technologies described above, the invention provides a kind of molecular sieve desulfurizer, described desulfurizing agent is the molecular sieve after potassium ion exchange modification, the exchange degree of described potassium ion is 5%～25%.
The exchange degree of described potassium ion is 10%～20%.
The exchange degree of described potassium ion is 10%～15%.
Described molecular sieve is 13X type molecular sieve.
Described molecular sieve is spherical, cylindrical, sheet shape or cloverleaf pattern mesopore molecular sieve.
The preparation method of molecular sieve desulfurizer of the present invention, comprises the steps:
(1) prepare K
+concentration is the in return liquid of the aqueous solution of 0.05～1mol/L;
(2) in exchange liquid, add molecular sieve to carry out ion-exchanged, be at least 2 hours swap time;
(3) filter, separate obtain through exchange after molecular sieve, to described molecular sieve dry, roasting, obtain the molecular sieve desulfurizer after modification.
Described in described step (2), exchanging the volume of liquid and the mass ratio of described molecular sieve is 10:1～2:1mL/g.
The temperature of drying described in described step (3) is 70～100 ℃, and drying time is 3～12 hours, and described sintering temperature is 350～500 ℃, and roasting time is 2～4 hours.
Described K
+concentration is 0.05～0.2mol/L.
Described K
+concentration is 0.08～0.15mol/L.
The present invention has following beneficial effect compared to prior art:
(1) molecular sieve desulfurizer of the present invention, adopts metal cation K
+molecular sieve is carried out to modification, and the exchange degree that limits described potassium ion is 5%～25%, make local location in molecular sieve pore passage improve electrostatic field intensity, in the time that described molecular sieve carries out desulfurization by physical absorption to hydrocarbon material flow, can make that thereby neutral sulfide disulphide molecule in hydrocarbon material flow is polarized to be easily adsorbed, and then improve adsorption capacity and the adsorption efficiency of molecular sieve to sulfide.Show after tested, the molecular sieve that exchange degree is 5%～25% after potassium ion modification, it once penetrates Sulfur capacity and has improved 3%-5.1% than molecular screen primary powder, and exchange degree exchanges modified molecular screen up to 70%～95% lanthanum, cerium ion in prior art, it once penetrates Sulfur capacity only than the maximum raisings of molecular screen primary powder 2% left and right, therefore, and the advantages of good adsorption effect containing potassium ion molecular sieve desulfurizer that exchange degree of the present invention is 5%～25%, adsorption capacity is large, thereby effectively reduces the regeneration times of desulfurizing agent.
Moreover, in molecular sieve desulfurizer of the present invention, the exchange degree of potassium ion is 5%～25%, middle compared to prior art lanthanum, cerium ion modified molecular screen are up to 70%～95% exchange degree, potassium ion modified molecular screen desulfurizing agent of the present invention has reduced cationic exchange degree when raising penetrates Sulfur capacity, thereby significantly reduces the experimental cost consuming while carrying out ion-exchange.
In addition, molecular sieve desulfurizer of the present invention, its potassium ion containing compare with 3 valency rare-earth cation lanthanums, cerium etc. its polarity a little less than, in the time disulphide being carried out to physical absorption processing, be adsorbed onto disulphide molecule on described molecular sieve also than being easier to desorption and desulfurization degree is high, thereby molecular sieve is easily regenerated, long service life, and then significantly reduced production cost and operating cost.
(2) molecular sieve desulfurizer of the present invention uses 13X type molecular sieve as molecular screen primary powder, and it is a kind of preferably that described 13X type molecular sieve belongs to X-type molecular sieve performance, and compared with Y zeolite, the desulfuration efficiency of 13X type molecular sieve is higher simultaneously.
The specific embodiment
Below in conjunction with specific embodiment and desulfurized effect test, object of the present invention, principle and effect are described further.
Embodiment 1
The in return liquid of the aqueous solution that configuration 150mL potassium nitrate concentration is 0.08mol/L, take the 13X type molecular screen primary powder of 40g and join in above-mentioned exchange liquid, normal temperature ion-exchange 4 hours, to the molecular sieve after exchange filter, separate, wash, 70 ℃ dry 12 hours, 490 ℃ of roastings 2 hours, make sample A.By analysis, the exchange degree that records potassium is 10%.
Embodiment 2
The in return liquid of the aqueous solution that configuration 400mL potassium nitrate concentration is 0.1mol/L, take the 13X type molecular screen primary powder of 40g and join in above-mentioned exchange liquid, normal temperature ion-exchange 36 hours, to the molecular sieve after exchange filter, separate, wash, 80 ℃ dry 8 hours, 350 ℃ of roastings 4 hours, make sample B.By analysis, the exchange degree that records potassium is 15%.
Embodiment 3
The in return liquid of the aqueous solution that configuration 80mL potassium nitrate concentration is 0.05mol/L, take the 13X type molecular screen primary powder of 40g and join in above-mentioned exchange liquid, normal temperature ion-exchange 24 hours, to the molecular sieve after exchange filter, separate, wash, 90 ℃ dry 6 hours, 350 ℃ of roastings 4 hours, make sample C.By analysis, the exchange degree that records potassium is 5%.
Embodiment 4
The in return liquid of the aqueous solution that configuration 200mL potassium sulfate concentration is 0.2mol/L, take the 13X type molecular screen primary powder of 40g and join in above-mentioned exchange liquid, normal temperature ion-exchange 10 hours, to the molecular sieve after exchange filter, separate, wash, 70 ℃ dry 12 hours, 500 ℃ of roastings 4 hours, make sample D.By analysis, the exchange degree that records potassium is 20%.
Embodiment 5
The in return liquid of the aqueous solution that configuration 300mL potassium nitrate concentration is 1mol/L, take the 13X type molecular screen primary powder of 40g and join in above-mentioned exchange liquid, normal temperature ion-exchange 12 hours, to the molecular sieve after exchange filter, separate, wash, 100 ℃ dry 3 hours, 400 ℃ of roastings 4 hours, make sample E.By analysis, the exchange degree that records potassium is 25%.
Embodiment 6
The in return liquid of the aqueous solution that configuration 150mL potassium nitrate concentration is 0.15mol/L, take the 13X type molecular screen primary powder of 40g and join in above-mentioned exchange liquid, normal temperature ion-exchange 2 hours, to the molecular sieve after exchange filter, separate, wash, 80 ℃ dry 10 hours, 400 ℃ of roastings 4 hours, make sample F.By analysis, the exchange degree that records potassium is 7%.
Embodiment 7
The in return liquid of the aqueous solution that configuration 400mL potassium chloride concentration is 0.15mol/L, the former powder of Y zeolite that the commercially available silica alumina ratio that takes 40g is 3.0-5.0 also joins in above-mentioned exchange liquid, normal temperature ion-exchange 10 hours, to the molecular sieve after exchange filter, separate, wash, 90 ℃ dry 6 hours, 500 ℃ of roastings 4 hours, make sample G.By analysis, the exchange degree that records potassium is 6%.
Embodiment 8
The in return liquid of the aqueous solution that configuration 400mL potassium nitrate concentration is 0.1mol/L, the X-type molecular screen primary powder that the commercially available silica alumina ratio that takes 40g is 2.2-3.0 also joins in above-mentioned exchange liquid, normal temperature ion-exchange 24 hours, to the molecular sieve after exchange filter, separate, wash, 90 ℃ dry 8 hours, 350 ℃ of roastings 4 hours, make sample H.By analysis, the exchange degree that records potassium is 13%.
Comparative example 1
The in return liquid of the aqueous solution that configuration 250mL lanthanum nitrate concentration is 0.11mol/L, the X-type molecular screen primary powder that the commercially available silica alumina ratio that takes 40g is 2.2-3.0 also joins in above-mentioned exchange liquid, adopts reverse-flow type normal pressure ion-exchange to carry out swap operation: in electric furnace, to add hot reflux 4 hours.Cooled and filtered, separation, washing, 70 ℃ are dried 12 hours, 480 ℃ of roastings 2 hours, make sample I.By analysis, the exchange degree that records lanthanum is 88%.
Comparative example 2
The in return liquid of the aqueous solution that configuration 250mL cerous nitrate concentration is 0.11mol/L, the X-type molecular screen primary powder that the commercially available silica alumina ratio that takes 40g is 2.2-3.0 also joins in above-mentioned exchange liquid, adopts reverse-flow type normal pressure ion-exchange to carry out swap operation: in electric furnace, to add hot reflux 4 hours.Cooled and filtered, separation, washing, 70 ℃ are dried 12 hours, 480 ℃ of roastings 2 hours, make sample J.By analysis, the exchange degree that records cerium is 80%.
Comparative example 3
The in return liquid of the aqueous solution that configuration 400mL potassium nitrate concentration is 1mol/L, take the 13X type molecular screen primary powder of 40g and join in above-mentioned exchange liquid, normal temperature ion-exchange 24 hours, to the molecular sieve after exchange filter, separate, wash, 100 ℃ dry 3 hours, 400 ℃ of roastings 4 hours, make sample K.By analysis, the exchange degree that records potassium is 30%.
Comparative example 4
The in return liquid of the aqueous solution that configuration 200mL potassium nitrate concentration is 0.05mol/L, take the 13X type molecular screen primary powder of 40g and join in above-mentioned exchange liquid, normal temperature ion-exchange 2 hours, to the molecular sieve after exchange filter, separate, wash, 100 ℃ dry 3 hours, 400 ℃ of roastings 4 hours, make sample L.By analysis, the exchange degree that records potassium is 3%.
Test case
For the desulfurized effect of molecular sieve desulfurizer of the present invention is described better, the present invention is carried out to following desulfurized effect evaluation containing potassium ion desulfurizing agent molecular sieve:
Evaluation test is carried out in normal pressure evaluating apparatus, the reaction tube diameter 13mm of normal pressure evaluating apparatus, and desulfurizing agent is respectively above-mentioned sample A～L, and granularity is 40 orders, and charge weight is 10mL.Experimental condition: air speed is 2h
-1, temperature is 20～25 ℃, pressure is normal pressure; Experimental raw gas: use the isopentane that picks up from certain refinery, allocate dimethyl disulphide (C into
2h
6s
2).Allow the experimental raw gas that contains disulphide by the reaction tube of normal pressure evaluating apparatus, to the content of the experimental raw of import and export Microcoulomb instrument (detection limit >=0.2ppm) detection sulphur for gas.
Different samples and unmodified X-type molecular sieve, 13X type molecular sieve, the comparison of Y zeolite desulfurized effect and the impact of regenerating on desulfurizing agent desulfurized effect after modification mainly investigated in evaluation test.In process of the test, think that desulfurizing agent penetrates in the time that outlet has detected that sulphur exists, Sulfur capacity is now for penetrating Sulfur capacity.
Result of the test is in table 1.
Table 1
As shown in Table 1, comparative example I, J are respectively the molecular sieve after lanthanum in prior art, cerium ion exchange modification, the exchange degree of lanthanum, cerium is respectively 88%, 80%, adopt above-mentioned evaluation test to evaluate the desulfurized effect of this lanthanum, cerium ion modified molecular screen, record it and once penetrate Sulfur capacity and improved respectively 2%, 1.5% than the X-type molecular screen primary powder of commercially available silica alumina ratio 2.2-3.0; Sample A-H is that the present invention adopts the molecular sieve desulfurizer after potassium ion exchange modification, the exchange degree control of its potassium ion is 5%～25%, adopt above-mentioned evaluation test to evaluate the desulfurized effect of described potassium ion modified molecular screen, recording it once penetrates Sulfur capacity and has improved 3%-5.1% than molecular screen primary powder, in actual industrial production, with sulphur concentration in the material of molecular sieve adsorption desulfurization generally at 20ppm, can improve 1% if penetrate Sulfur capacity, the desulfurization cycle can extend 15～30 days, thereby the regeneration times that reduces desulfurizing agent, has reduced industrial production desulphurization cost.In addition, in comparative example 3,4, in sample K, L, potassium ion exchange degree is respectively 30%, 3%, carry out the evaluation of desulfurized effect, recording it once penetrates Sulfur capacity and has improved respectively 1.4%, 1.7% than molecular screen primary powder, further illustrate, in the time that the exchange degree control of potassium ion is 5%～25%, desulfurized effect is best.
Regeneration tests: the sample A-H of sulfur-bearing is purged and regenerated by 300 ℃ of high temperature nitrogen respectively, and regeneration air speed is 500h
-1the desulfuration efficiency after 80 times of regenerating is still the more than 98% of original state, lanthanum compared to prior art, cerium exchange modified molecular screen, its desulfuration efficiency after 10 times of regenerating reduces to below 80% of original state, potassium ion modified molecular screen of the present invention is easily regenerated, long service life, thus cost further reduced.
Obviously, above-described embodiment is only for example is clearly described, and the not restriction to embodiment.For those of ordinary skill in the field, can also make other changes in different forms on the basis of the above description.Here without also giving exhaustive to all embodiments.And the apparent variation of being extended out thus or variation are still among the protection domain in the invention.
Claims (10)
1. a molecular sieve desulfurizer, is characterized in that: described desulfurizing agent is the molecular sieve after potassium ion exchange modification, and the exchange degree of described potassium ion is 5%～25%.
2. molecular sieve desulfurizer according to claim 1, is characterized in that: the exchange degree of described potassium ion is 10%～20%.
3. molecular sieve desulfurizer according to claim 1, is characterized in that: the exchange degree of described potassium ion is 10%～15%.
4. according to the arbitrary described molecular sieve desulfurizer of claim 1-3, it is characterized in that: described molecular sieve is 13X type molecular sieve.
5. according to the arbitrary described molecular sieve desulfurizer of claim 1-4, it is characterized in that: described molecular sieve is spherical, cylindrical, sheet shape or cloverleaf pattern mesopore molecular sieve.
6. the preparation method of the arbitrary described molecular sieve desulfurizer of claim 1-5, comprises the steps:
(1) prepare K
+concentration is the in return liquid of the aqueous solution of 0.05～1mol/L;
(2) in exchange liquid, add molecular sieve to carry out ion-exchanged, be at least 2 hours swap time;
(3) filter, separate obtain through exchange after molecular sieve, to described molecular sieve dry, roasting, obtain the molecular sieve desulfurizer after modification.
7. preparation method according to claim 6, is characterized in that: described in described step (2), exchanging the volume of liquid and the mass ratio of described molecular sieve is 10:1～2:1mL/g.
8. according to the preparation method described in claim 6 or 7, it is characterized in that: the temperature of drying described in described step (3) is 70～100 ℃, and drying time is 3～12 hours, and described sintering temperature is 350～500 ℃, and roasting time is 2～4 hours.
9. according to the arbitrary described preparation method of claim 6-8, it is characterized in that described K
+concentration is 0.05～0.2mol/L.
10. preparation method according to claim 9, is characterized in that: described K
+concentration is 0.08～0.15mol/L.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104383874A (en) * | 2014-12-05 | 2015-03-04 | 上海绿强新材料有限公司 | Purification adsorbent based on mesoporous molecular sieve material and preparation method and application of purification adsorbent based on mesoporous molecular sieve material |
| CN107413293A (en) * | 2017-08-09 | 2017-12-01 | 沈阳三聚凯特催化剂有限公司 | A kind of desulfurizing agent and preparation method and application |
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| CN107413293B (en) * | 2017-08-09 | 2021-01-01 | 沈阳三聚凯特催化剂有限公司 | Desulfurizing agent and preparation method and application thereof |
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Application publication date: 20140702 |