CN104190352B - A kind of adsorbent for removing sulfur-bearing, oxygen impurities in light hydrocarbon materials stream and preparation thereof, renovation process - Google Patents
A kind of adsorbent for removing sulfur-bearing, oxygen impurities in light hydrocarbon materials stream and preparation thereof, renovation process Download PDFInfo
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Abstract
The present invention relates to a kind of adsorbent for removing light hydrocarbon materials stream Semi-polarity molecule and preparation thereof, renovation process, this adsorbent is raw material by molecular screen primary powder, activated alumina, through organic amine reaming, metal ion-modified after in addition binding agent carry out roller forming, carry out high-temperature roasting activation after low temperature drying obtained, obtained adsorbent is by Al
2o
3, SiO
2, alkali metal oxide and trace rare-earth metal oxide composition, obtained adsorbent particle diameter is 1.0 ~ 4.2mm, and specific area is 260 ~ 320 ㎡/g, pore volume 0.3 ~ 0.35ml/g.The present invention carries out modification by introducing rare earth metal complex alkali metal to adsorbent, and introduce waterglass further as binding agent, substantially increase adsorbent to the selective of polar molecule and adsorption capacity, reduce heat of adsorption on the whole, this adsorbent can reach 99.2% to the removal efficiency of methyl alcohol, and adsorption capacity can reach 6.7%, and this present invention is simple, the adsorbent prepared has the features such as renewablely recycle, renovation process is simple, improves resource utilization.
Description
Technical field
The present invention relates to a kind of adsorbent and preparation thereof, renovation process, particularly relating to a kind of for removing in light hydrocarbon materials stream sulfur-bearing, oxygen impurities as COS, CS
2, H
2s, CO
2with the adsorbent of water etc. and preparation thereof, renovation process.
Background technology
In Chemical Manufacture, along with the appearance of new technology and the update of catalyst, require more and more higher to impurity in raw material.In recent years along with the situation of crude oil heaviness and in poor quality is serious all the more, the continuous renewal of Coal Chemical Industry product, impurity content in hydrocarbon material constantly raises, particularly the impurity such as sulfur-bearing, oxygen compounds cries out content constantly to raise, and these materials are very high to the toxicity of catalyst in hydro carbons deep-processing process.In these sulfur-bearings, oxygen compounds to catalyst toxicity larger be COS, CS
2, H
2s, CO
2with water etc., particularly in polyolefin device to these impurity contents require higher, General Requirements refine after raw material in COS content be less than 0.02ppm, CO
2be less than 5ppm, water is less than 1ppm, and total sulfur is less than 1ppm.
In these impurity removal techniques, H
2the removing process of S and water and catalyst are all very ripe, and traditional COS removing process is then utilize hydrolyst that COS is hydrolyzed into H
2s and CO
2again by H
2s and CO
2remove, CO
2remove, be utilize distillation or MDEA absorbing and removing.In these subtractive processes, the hydrolysis of COS removes particularly crucial, and precision prescribed is the highest.And removing in COS process application, application publication number is the process for purification that patent discloses a kind of liquefied petroleum gas of CN101993750A, raw liquefied petroleum gas to be refined mixes with hydramine liquid by the method, enter cos hydrolysis reactor, under the acting in conjunction of hydrolytic catalyst of carbonyl sulfur and hydramine liquid, by the cos in liquefied petroleum gas and hydrogen sulfide removing, remove the liquefied petroleum gas after cos and hydrogen sulfide and enter removal of mercaptans operation again.Application publication number be CN101143286B patent discloses a kind of method removing COS from acid gas stream, adopt a kind of serotonin aqueous solution to make absorbent, add appropriate activator, from air-flow, H can be removed completely
2s, and at CO
2when removal rate is not high, remove most COS.Although these methods above-mentioned effectively can remove COS, but the method being still utilization hydrolysis most widely used is at present to remove COS, patent CN101590392A, CN102463107A, CN101239319A etc. all mention the preparation of COS hydrolyst, these catalyst all adopt alumina load metal oxide to obtain, the main distinction is that the metal oxide of load is different, and the H produced after hydrolysis
2s then needs the desulfurizing agents such as zinc oxide to be removed, and technological process is longer.Patent CN101912774B---a kind of Catalysts and its preparation method of hydrolyzing carbonyl sulfide under low temperature condition provides a kind of catalyst of hydrolyzing carbonyl sulfide under low temperature condition, but as can be seen from the principle of COS hydrolysis, if COS thoroughly will be removed, must ensure that the water content in material is higher than COS, otherwise COS hydrolysis may not be thorough, impact removes the degree of depth, in addition, the CO produced after how removing hydrolysis
2these patents utilizing the method for hydrolysis to remove COS all in not mentioned.In addition, adsorption refining, as popular technique in recent years, removes at COS and also applies to some extent, application publication number be CN1180870C patent discloses a kind of one-step desulfurizing agent of sulfur carbonyl, utilize active carbon for carrier, add a certain amount of metal oxide, modulating agent and mass transfer promoter obtaining; Application publication number be CN103506071A patent discloses a kind of purificant for hydrogen sulfide and cos in absorbed natural gas tail gas and preparation method thereof, this purificant is carrier by active carbon, the zinc salt of solubility and soluble copper salt are active component, be carried on absorbent charcoal carrier to obtain, be applicable in factory and use for laboratory natural gas tail gas containing ppm level hydrogen sulfide and cos gas cleaning; Application publication number be CN102600850A patent discloses a kind of preparation method simultaneously removing the catalyst of cos and carbon disulfide, take microwave activated carbon as carrier, alkaline matter and metal oxide are that active component obtains, and this catalyst can by COS and CS in gas under lower temperature (30 ~ 90 DEG C)
2remove simultaneously; Above-mentioned patent utilization is inhaled refining mode and is proposed feasible thinking, but it is low with active carbon to be that the adsorbent of carrier exists adsorption capacity, adsorbs the problem of saturated rear difficult life, and to CO
2, H
2the impurity absorption removal effects such as S are limited.Application publication number be CN103816864A patent discloses a kind of adsorbent for removing disulphide in liquid hydrocarbon and preparation method thereof, but the method adopts multiple high temp sintering processes, unavoidably cause the destruction to molecular sieve structure, greatly reduce the serviceability of this adsorbent.Therefore, develop a kind of low heat of adsorption, high-adsorption-capacity and preparation technology simple, can to COS, CO
2, H
2s, CS
2realize deep removal and the renewable adsorbent recycled Deng impurity, there are good realistic meaning and market prospects.
Summary of the invention
In view of the deficiencies in the prior art, the object of the present invention is to provide a kind of adsorbent for removing sulfur-bearing, oxygen impurities in light hydrocarbon materials stream and preparation thereof, renovation process.
In order to realize first object of the present invention, provide a kind of adsorbent for removing sulfur-bearing, oxygen impurities in light hydrocarbon materials stream, inventor is studied by lot of experiments, obtains following technical scheme:
For removing an adsorbent for sulfur-bearing, oxygen impurities in light hydrocarbon materials stream, it is characterized in that, being prepared from by each component of following weight portion:
Kaolin 15 ~ 35 parts
Activated alumina 60 ~ 75 parts,
Organic amine 2 ~ 4 parts
Rare earth metal salt 0.5 ~ 3 part
Alkali metal salt 1 ~ 10 part
Binding agent 1 ~ 2 part
The present invention with activated alumina and kaolin for raw material, through organic amine reaming, add alkali metal salt soln containing a small amount of rare earth metal blended after in addition binding agent carry out roller forming, carry out high-temperature roasting activation after low temperature drying obtained, obtained adsorbent is by Al
2o
3, SiO
2, alkali metal oxide and trace rare-earth metal oxide composition, by weight percentage, wherein Al
2o
3content be 78 ~ 82%, SiO
2content be 15 ~ 18%, the content of alkali metal oxide is 2% ~ 6%, and the content of rare-earth oxide is 0.4 ~ 0.8%.And obtained adsorbent particle diameter is 2.5 ~ 5.5mm, specific area is 260 ~ 320 ㎡/g, and pore volume is 0.3 ~ 0.35ml/g.
As above for removing the adsorbent of sulfur-bearing in hydrocarbon material, oxygen impurities, it is characterized in that, described kaolin is soft or sandy kaoline, and granularity is 200 order ~ 400 orders, is preferably 250 ~ 320 orders.
Preferably, the particle diameter of described activated alumina is 1 ~ 5 μm, and further preferably, the particle diameter of described activated alumina is 2 ~ 4 μm.
Preferably, the crystal structure of described activated alumina is γ-Al
2o
3, δ-Al
2o
3or η-Al
2o
3in one or more.
Preferably, described organic amine expanding agent is one or more in ethylenediamine, triethylamine, diethylenetriamine, triethylene tetramine.
Preferably, described binding agent is waterglass.
Described alkali metal soln is the salting liquid containing Na+, K+ ion, as NaHCO
3, Na
2cO
3, KNO
3deng solution, the mass percent concentration 10% ~ 15% of described alkali metal soln.
Described rare earth metal salt comprises and containing
lanthanum(La),
cerium(Ce),
praseodymium(Pr),
neodymiumetc. (Nd) salt of one or more elements in, be preferably the mixture of two kinds of rare earth metal salt solutions, the mass percent concentration of described rare earth metal salt solutions is 2% ~ 4%.
Further preferably, described rare earth metal salt solutions is the composite mixed solution of lanthanum nitrate that mass percent concentration is identical and neodymium nitrate, because the synergy of different thulium makes adsorbent surface distribution of charges more reasonable, therefore the degree of depth is removed and adsorption capacity has obvious lifting compared with the adsorbent of single-element, through the composite modified obtained adsorbent capacity of lanthanum+neodymium with remove the degree of depth and improve a lot.
Second object of the present invention is the preparation method providing a kind of adsorbent corresponding with the present invention's first object, it is characterized in that, comprises the steps:
Step 1: by a certain amount of Al
2o
3be placed in container with kaolin, in container, drip a certain amount of organic amine expanding agent reaming modification, reaction temperature 20 ~ 40 DEG C, after 2 ~ 3 hours reaming reaction time, filtering drying is for subsequent use;
Step 2: by the Al after reaming described in step 1
2o
3be placed in container with kaolin, the alkali metal salt prepared described in adding in container and rare earth metal mixed salt solution, be uniformly mixed rear still aging 1 ~ 3h;
Step 3: to the Al handled well described in step 2
2o
3with add a small amount of adhesive in kaolin, be placed in bowling machine and carry out spin granulation, the adsorbent after shaping is dried, bake out temperature 120 ~ 180 DEG C, drying time 0.5 ~ 1h;
Step 4: adsorbent step 3 handled well carries out high-temperature roasting, sintering temperature 400 ~ 650 DEG C, cooling encapsulation after roasting time 3 ~ 4h.
Adsorbent involved in the present invention is as follows for the evaluation method of the adsorbent removing sulfur-bearing, oxygen impurities in light hydrocarbon materials stream: in distribution bottle, prepare the simulation sulfur-bearing needed for test, oxygen impurities gas, refine filled with adsorbent in bed in the simulation of diameter 25mm and be placed in water bath with thermostatic control, distribution bottle pipeline is connected to the refining bed of simulation by flow control system.In refining bed, pass into the Simulated gas prepared, process of the test can control gas space velocity by flow control system.Gas after refining bed adsorption refining enters tail gas absorbing system, and timing is analyzed the impurity in refining tail gas, measures wherein impurity content and composition.
In the evaluation method of adsorbent as above, preferred test temperature is 20 ~ 50 DEG C, adsorbent inventory 20 ~ 50ml, test simulation gas space velocity 1000 ~ 3000h
-1, test tail gas impurity is analyzed by special color spectrometer.
3rd object of the present invention is to provide the renewable method of the adsorbent corresponding with first, second goal of the invention of the present invention, and the technical scheme of employing is as follows:
The saturated adsorbent of absorption is placed in tubular type regeneration reactor, to the adsorbent bed N passing into heating
2, control N
2flow, regulates heating-up temperature, controls regeneration reactor outlet N
2temperature, more than 240 DEG C, keeps purging 4 hours, and after purging, stopping is heating and continuous passes into N
2, be down to room temperature and obtain the adsorbent after regenerating.
Preferably, described regeneration N
2air speed controls at 100 ~ 1000h
-1.
Compared with prior art, one involved in the present invention is used for removing sulfur-bearing in light hydrocarbon materials stream, the adsorbent of oxygen impurities and preparation thereof, renovation process tool has the following advantages and improves: (1) the present invention introduces rare earth metal complex alkali metal and carries out modification to adsorbent, both the acid centre distribution of adsorbent had been improved, improve selective to polar molecule of adsorbent, reduce heat of adsorption on the whole, in addition, by introducing different types of thulium, its synergy makes adsorbent surface distribution of charges more reasonable, substantially increase adsorbent to sulfur-bearing, oxygen impurities remove precision and adsorption capacity, (2) the present invention introduces waterglass as binding agent, in high-temperature calcination process, improve the intensity of adsorbent, ensure that adsorbent is not broken in repeated regeneration process, more firmly, decrease the structural damage of adsorbent duct, ensure that the service life of adsorbent, (3) adsorbent prepared of the inventive method removes to the sulfur-bearing in hydrocarbon material, oxygen impurities that precision is high, adsorption capacity large, and this adsorbent is to H
2the removal efficiency of S can reach 99.6%, and adsorption capacity reaches 6.1%, (4) the present invention prepares the technique of adsorbent simply, and the multiple high temp avoiding conventional treatment method sinters the destruction of causing sorbent structure, greatly reduces energy consumption, (5) adsorbent in the present invention has the features such as renewablely recycle, renovation process is simple, improves resource utilization, can avoid again the pollution to environment, have good market prospects and economic benefit.
Accompanying drawing explanation
Fig. 1 is simulated test evaluation rubric figure.
Detailed description of the invention
In order to understand the present invention better, illustrate content of the present invention further below in conjunction with embodiment, but content of the present invention is not only confined to the following examples.Those skilled in the art can make various changes or modifications the present invention, and these equivalent form of values are equally within claims limited range listed by the application.Described in embodiment, concentration is mass percent concentration, enumerates specific embodiment below and is described invention:
Embodiment 1
(1) activated alumina (γ-Al that 60g particle diameter is 1 μm is taken
2o
3) and 15g granularity be that 200 object kaolin are placed in beaker, in beaker, slowly add ethylenediamine expanding agent 2.5g, beaker is placed in band stir water bath with thermostatic control, adjust the temperature to 30 DEG C, stirring reaction 2h post-drying is for subsequent use, and obtained adsorbent masterbatch, the specific area of this adsorbent masterbatch is 280m
2/ g;
(2) adsorbent masterbatch obtained in 50g step 1 is placed in beaker, in beaker, adding 15g containing concentration is 12%Na
2cO
3be 3% lanthanum nitrate mixed solution with concentration, be uniformly mixed rear still aging 2h; Ageing completes in backward adsorbent masterbatch that to add concentration be 0.4% water glass solution, be placed in bowling machine and carry out spin granulation, the adsorbent after shaping is dried, bake out temperature 150 DEG C, be warmed up to 550 DEG C after drying 0.5h and carry out high-temperature roasting 3h, finally obtained adsorbent A.
Refining bed apparatus carries out the adsorption cleaning performance evaluation of low concentration COS in propylene gas.Experiment condition is: be seated in refining bed by above-mentioned for 50ml obtained adsorbent A, will prepare the simulation propylene gas containing COS500ppm in distribution bottle, and distribution bottle pipeline is connected to the refining bed of simulation by flow control system.In refining bed, pass into the simulation propylene gas prepared, control gas space velocity is 3000h
-1.Gas after refining bed enters tail gas absorbing system, utilizes special chromatographic determination wherein COS content.When exporting COS content overproof, cut out the sample introduction of refining bed, record logistics flows through the time of adsorbent and calculates adsorption capacity.Appraisal result is in table 1.
Embodiment 2
(1) activated alumina (δ-Al that 60g particle diameter is 5 μm is taken
2o
3) and 35g granularity be that 400 object kaolin are placed in beaker, in beaker, slowly add triethylamine expanding agent 2g, beaker is placed in band stir water bath with thermostatic control, adjust the temperature to 30 DEG C, stirring reaction 2h post-drying is for subsequent use, and obtained adsorbent masterbatch, the specific area of this adsorbent masterbatch is 235m
2/ g;
(2) adsorbent masterbatch obtained in 50g step 1 is placed in beaker, in beaker, adding 15g containing concentration is 12%KNO
3be 3% nitric acid with concentration
neodymiummixed solution, is uniformly mixed rear still aging 2h; Ageing completes in backward adsorbent masterbatch that to add concentration be 0.4% water glass solution, be placed in bowling machine and carry out spin granulation, the adsorbent after shaping is dried, bake out temperature 150 DEG C, be warmed up to 550 DEG C after drying 0.5h and carry out high-temperature roasting 4h, finally obtained adsorbent B.
Evaluated by the solid absorbent B prepared according to each step of embodiment 1 and condition, appraisal result lists in table 1.
Embodiment 3
(1) activated alumina (δ-Al that 75g particle diameter is 2 μm is taken
2o
3) and 15g granularity be that 320 object kaolin are placed in beaker, diethylenetriamine expanding agent 4g is slowly added in beaker, beaker is placed in the water bath with thermostatic control that band stirs, adjust the temperature to 30 DEG C, stirring reaction 3h post-drying is for subsequent use, obtained adsorbent masterbatch, the specific area of this adsorbent masterbatch is 224m
2/ g;
(2) adsorbent masterbatch obtained in 50g step 1 is placed in beaker, in beaker, adding 15g containing concentration is 10%NaHCO
3be 4% nitric acid with concentration
praseodymiummixed solution, is uniformly mixed rear still aging 2h; Ageing completes in backward adsorbent masterbatch that to add concentration be 0.4% water glass solution, be placed in bowling machine and carry out spin granulation, the adsorbent after shaping is dried, bake out temperature 150 DEG C, be warmed up to 400 DEG C after drying 0.5h and carry out high-temperature roasting 3h, finally obtained adsorbent C.
Evaluated by the solid absorbent C prepared according to each step of embodiment 1 and condition, appraisal result lists in table 1.
Embodiment 4
(1) activated alumina (η-Al that 60g particle diameter is 4 μm is taken
2o
3) and 15g granularity be that 250 object kaolin are placed in beaker, triethylene tetramine expanding agent 2g is slowly added in beaker, beaker is placed in the water bath with thermostatic control that band stirs, adjust the temperature to 30 DEG C, stirring reaction 2h post-drying is for subsequent use, obtained adsorbent masterbatch, the specific area of this adsorbent masterbatch is 220m
2/ g;
(2) adsorbent masterbatch obtained in 50g step 1 is placed in beaker, in beaker, adding 15g containing concentration is 12%Na
2cO
3be 3% cerous nitrate mixed solution with concentration, be uniformly mixed rear still aging 2h; Ageing completes in backward adsorbent masterbatch that to add concentration be 0.4% water glass solution, be placed in bowling machine and carry out spin granulation, the adsorbent after shaping is dried, bake out temperature 150 DEG C, be warmed up to 550 DEG C after drying 0.5h and carry out high-temperature roasting 3h, finally obtained adsorbent D.
Evaluated by the solid absorbent D prepared according to each step of embodiment 1 and condition, appraisal result lists in table 1.
Embodiment 5
By the Na in embodiment 4
2cO
3change K into
2cO
3, lanthanum nitrate concentration is constant, obtained adsorbent E.
Evaluated by the solid absorbent E prepared according to each step of embodiment 1 and condition, appraisal result lists in table 1.
Embodiment 6
Lanthanum nitrate hexahydrate in embodiment 1 to be changed into concentration be 1.5% lanthanum nitrate concentration is the combination solution of 1.5% neodymium nitrate, Na
2cO
3concentration is constant, obtained adsorbent F.
Evaluated by the solid absorbent F prepared according to each step of embodiment 1 and condition, appraisal result lists in table 1.
Embodiment 7
Adsorbent F obtained in embodiment 6 is carried out evaluation test, prepares containing CO in distribution bottle
2concentration is the simulation propylene gas of 500ppm, and fixed bed device carries out low concentration CO in propylene gas
2adsorption cleaning performance evaluation, in the same manner as in Example 1, appraisal result is in table 1 for other experimental conditions.
Embodiment 8
Adsorbent F obtained in embodiment 6 is carried out evaluation test, prepares containing CS in distribution bottle
2concentration is the simulation propylene gas of 500ppm, and fixed bed device carries out low concentration CS in propylene gas
2adsorption cleaning performance evaluation, in the same manner as in Example 1, appraisal result is in table 1 for other experimental conditions.
Embodiment 9
Adsorbent F in embodiment 6 is carried out evaluation test, prepares containing H in distribution bottle
2the simulation propylene gas of the 500ppm of S, fixed bed device carries out low concentration H in propylene gas
2the adsorption cleaning performance evaluation of S, in the same manner as in Example 1, appraisal result is in table 1 for other experimental conditions.
Embodiment 10
Adsorbent F in embodiment 6 is carried out evaluation test, prepares containing 500ppmCOS, 500ppmCO in distribution bottle
2, 500ppmCS
2,500ppmH
2the simulation propylene gas of S, fixed bed device carries out the adsorption cleaning performance evaluation of the above-mentioned foreign gas of low concentration in propylene gas, and in the same manner as in Example 1, appraisal result is in table 1 for other experimental conditions.
Comparative example 1
Take the activated alumina (γ-Al that 60g particle diameter is 1 μm
2o
3) and 15g granularity be that 200 object kaolin are placed in beaker, be uniformly mixed, obtain non-reaming adsorbent masterbatch, the specific area of this adsorbent masterbatch is 210m
2/ g, in the adsorbent masterbatch after drying, add 0.4% water glass solution, be placed in bowling machine and carry out spin granulation, the adsorbent after shaping is dried, bake out temperature 150 DEG C, carries out the obtained non-reaming adsorbent of high-temperature roasting 3h after drying time 1h at 550 DEG C.
Evaluated by the non-reaming adsorbent prepared according to each step of embodiment 1 and condition, appraisal result lists in table 1.
Embodiment 11
Adsorbent F after saturated for 50ml CO absorption S is placed in tubular type regeneration reactor, adds through chuck heating N to adsorbent bed passing into
2, control N
2flow 15000ml/h, regulates chuck heating-up temperature, controls regeneration reactor outlet N
2temperature, more than 250 DEG C, keeps purging 5h.Continue after purging to pass into N
2, the heating of closedown chuck is down to room temperature and is obtained the adsorbent G after regenerating.After regenerating 100 times, adsorbent is 92.9% to the removal efficiency of COS, and adsorption capacity is 4.6%.
Embodiment 12
Certain poly-200,000 tons/year of polypropylene plant propylene takes off COS tower, and design liquid propylene flow 26000kg/h, operating pressure 2.6MPa, drying bed adopts two towers one to open one and runs for mode, single tower filled with adsorbent F15m3.In propylene, impurity content is: COS≤2ppm, water content≤5ppm; CO
2≤ 2ppm refines target: COS≤0.02ppm, water content≤1ppm, CO
2≤ 0.5ppm.Device operates steadily after feeding intake and running, 3 months regeneration periods.Export targets equality circuit refines requirement.Concrete analysis form is in table 2.
Table 1
Table 2
The content be not described in detail in this description belongs to the known prior art of professional and technical personnel in the field.
Claims (10)
1. for removing an adsorbent for sulfur-bearing, oxygen impurities in light hydrocarbon materials stream, it is characterized in that: described adsorbent is by Al
2o
3, SiO
2, alkali metal oxide and trace rare-earth metal oxide composition, by weight percentage, wherein Al
2o
3content be 78 ~ 82%, SiO
2content be 15 ~ 18%, the content of alkali metal oxide is 2% ~ 6%, and the content of rare-earth oxide is 0.4 ~ 0.8%.
2. a kind of adsorbent for removing sulfur-bearing, oxygen impurities in light hydrocarbon materials stream according to claim 1, it is characterized in that: described adsorbent particle diameter is 2.5 ~ 5.5mm, specific area is 260 ~ 320 ㎡/g, and pore volume is 0.3 ~ 0.35ml/g.
3. a kind of adsorbent for removing sulfur-bearing, oxygen impurities in light hydrocarbon materials stream according to claim 1 and 2, is characterized in that: described adsorbent is prepared from by each component raw material of following weight portion:
Kaolin 15 ~ 35 parts
Activated alumina 60 ~ 75 parts,
Organic amine 2 ~ 4 parts
Rare earth metal salt 0.5 ~ 3 part
Alkali metal salt 1 ~ 10 part
Binding agent 1 ~ 2 part.
4. prepare a method for the adsorbent for removing sulfur-bearing, oxygen impurities in light hydrocarbon materials stream described in claim 1 or 2, it is characterized in that, described method comprises following steps:
Step 1: by a certain amount of Al
2o
3be placed in container with kaolin, in container, drip a certain amount of organic amine expanding agent reaming modification, reaction temperature 20 ~ 40 DEG C, after 2 ~ 3 hours reaming reaction time, filtering drying is for subsequent use;
Step 2: by the Al after reaming described in step 1
2o
3be placed in container with kaolin, in container, add the alkali metal salt prepared and rare earth metal mixed salt solution, be uniformly mixed rear still aging 1 ~ 3h;
Step 3: the Al handled well to step 2
2o
3with add a small amount of binding agent in kaolin, be placed in bowling machine and carry out spin granulation, the adsorbent after shaping is dried, bake out temperature 120 ~ 180 DEG C, drying time 0.5 ~ 1h;
Step 4: adsorbent step 3 handled well carries out high-temperature roasting, sintering temperature 400 ~ 650 DEG C, cooling encapsulation after roasting time 3 ~ 4h.
5. according to claim 4 a kind of for the preparation of remove sulfur-bearing in light hydrocarbon materials stream, oxygen impurities the method for adsorbent, it is characterized in that, described binding agent is water glass solution.
6. according to claim 5 a kind of for the preparation of remove sulfur-bearing in light hydrocarbon materials stream, oxygen impurities the method for adsorbent, it is characterized in that, described adsorbent is reproducible, and its regeneration step is as follows:
The saturated adsorbent of absorption is placed in tubular type regeneration reactor, to the adsorbent bed N passing into heating
2, control N
2flow, regulates heating-up temperature, controls regeneration reactor outlet N
2temperature, more than 240 DEG C, keeps purging 4 hours, and after purging, stopping is heating and continuous passes into N
2, be down to room temperature and obtain the adsorbent after regenerating.
7. according to claim 5 a kind of for the preparation of remove sulfur-bearing in light hydrocarbon materials stream, oxygen impurities the method for adsorbent, it is characterized in that, described kaolin is soft or sandy kaoline, and granularity is 200 order ~ 400 orders.
8. according to claim 5 a kind of for the preparation of remove sulfur-bearing in light hydrocarbon materials stream, oxygen impurities the method for adsorbent, it is characterized in that, the crystal structure of described activated alumina is γ-Al
2o
3, δ-Al
2o
3or η-Al
2o
3in one or more, the particle diameter of described activated alumina is 1 ~ 5 μm.
9. according to claim 5 a kind of for the preparation of remove sulfur-bearing in light hydrocarbon materials stream, oxygen impurities the method for adsorbent, it is characterized in that, described organic amine expanding agent is one or more in ethylenediamine, triethylamine, diethylenetriamine, triethylene tetramine.
10. according to claim 4 a kind of for the preparation of remove sulfur-bearing in light hydrocarbon materials stream, oxygen impurities the method for adsorbent, it is characterized in that, described alkali metal soln is for containing Na
+, K
+the salting liquid of ion, the mass percent concentration 10% ~ 15% of described alkali metal soln, described rare earth metal salt is the mixture of two kinds of rare earth metal salt solutions, and the mass percent concentration of described rare earth metal salt solutions is 2% ~ 4%.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107970877A (en) * | 2017-10-24 | 2018-05-01 | 武汉纺织大学 | A kind of preparation method of modified porous aluminium oxide decarburizer |
| CN107970877B (en) * | 2017-10-24 | 2020-07-31 | 武汉纺织大学 | Preparation method of modified porous alumina decarbonizer |
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