CN103012036A - Aromatic hydrocarbon purifying method - Google Patents
Aromatic hydrocarbon purifying method Download PDFInfo
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- CN103012036A CN103012036A CN2012104989625A CN201210498962A CN103012036A CN 103012036 A CN103012036 A CN 103012036A CN 2012104989625 A CN2012104989625 A CN 2012104989625A CN 201210498962 A CN201210498962 A CN 201210498962A CN 103012036 A CN103012036 A CN 103012036A
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Abstract
The invention discloses an aromatic hydrocarbon purifying method which comprises the step of carrying out a contact reaction on aromatic hydrocarbon and a solid acid catalyst under the conditions that the temperature is 50-400 DEG C, the pressure is 0.1-12MPa and the feeding mass space velocity is 0.1-15h<-1> to obtain purified aromatic hydrocarbon. The aromatic hydrocarbon purifying method is simple in process without consuming hydrogen, low in device investment and operation cost, good in catalyst activity stability, long in device stable operation time and less in aromatic hydrocarbon loss; and reactor reaction and regeneration frequent switching operation can be avoided, the catalyst can be regenerated, a large quantity of waste catalysts can be prevented from being stacked and embedded, and environment influence is little.
Description
(1) technical field
The present invention relates to a kind of process for purification of aromatic hydrocarbons, especially a kind of method that adopts the nucleocapsid structure molecular sieve catalyst to carry out trace amounts of olefin in the acid catalyzed reaction Arene removal.
(2) background technology
Aromatic hydrocarbons is important Elementary Chemical Industry raw material, and petrochemical industry is produced aromatic hydrocarbons by techniques such as naphtha reforming and steam crackings.All have a certain amount of olefin impurity (less than 1%) in the aromatic hydrocarbon product of these techniques, this part olefin impurity affects the aromatic hydrocarbon product quality, and some follow-up chemical engineering processes are had detrimentally affect.Therefore, in order to obtain qualified aroamtic hydrocarbon raw material and to guarantee carrying out smoothly of subsequent technique, the olefin impurity in the aromatic hydrocarbons must be carried out deep removal.At present, both at home and abroad in the Arene removal product that extensively adopts of refinery the method for olefin impurity mainly contain hydrofining and clay-filtered two kinds.
Hydrofining mainly is to utilize alumina supporter Supported Pt Nanoparticles or palladium catalyst, carry out " back end hydrogenation " in the reforming reactor back thus process reaches the purpose that removes alkene to realize olefin saturated.The efficient of hydrofining deolefination impurity is high, thereby is widely used by domestic and international refinery.No matter for the benzene cut, be that its active component effect is all better with platinum or palladium, but for the aromatic hydrocarbons of benzene, toluene and dimethylbenzene etc. than wide fraction, the hydrogenation reaction degree of depth is difficult to take into account comprehensively, and causes aromatic hydrocarbons to lose more significantly.And its flow process is complicated, must be provided with many hydrogen high-tension apparatuses that face, and adds some noble metal catalyst, causes investment and process cost high.
Clay-filtered is to utilize acid-treated carclazyte, main by absorption or part alkene oligomerization and alkylated reaction, thereby reaches the purpose of alkene in the Arene removal.Although clay treatment process has obtained widely industrial application, the effect that removes alkene is relatively poor; In actual process, the carclazyte inactivation is fast, life cycle is short, consumption is large, and the carclazyte behind the inactivation can not be regenerated, just need to more renew carclazyte in about 1 month, frequent has increased aromatic hydrocarbons loss and workload, and a large amount of useless carclazytes needs heap buried to process, and causes environmental pollution.
Micro porous molecular sieve can be used as the catalyzer of trace amounts of olefin in the Arene removal owing to have stronger surface acidity and hydrothermal stability.For no other reason than that its aperture is too little, it is larger that the reaction such as alkene oligomerization generates more macromolecular inside diffusional resistance, causes catalyzer coking and deactivation speed larger, the catalyst activity less stable.And SBA-15 type mesopore molecular sieve has the meso-hole structure of high-sequential because of it, has improved the rate of diffusion of macromolecular reaction thing in its duct, obtains people's extensive concern.But because the hydrothermal stability of this mesopore molecular sieve and acid relatively poor has hindered its application in petrochemical complex.Have a realistic meaning with micro porous molecular sieve and mesopore molecular sieve are compound, can bring into play the stronger surface acidity of micro porous molecular sieve and hydrothermal stability, and the stronger diffusion of mesopore molecular sieve.Take micro porous molecular sieve as kernel, SBA-15 then is grown in the outside surface of micro porous molecular sieve kernel mutually, forms the composite molecular screen of hud typed hierarchical porous structure.Because the symbiosis of Jie's micropore two-phase causes the mesoporous wall thickening, so that the heat of mesopore molecular sieve and hydrothermal stability improve.Microporous-mesoporous composite molecular sieve was owing to both had the strongly-acid of micro porous molecular sieve hole wall structure, has again larger mesoporous aperture, strengthen the synergy between molecular sieve, overcome because the Catalysts Deactivation Problems that causes is limited in the micro porous molecular sieve duct, improve the activity stability of catalyzer.
(3) summary of the invention
The object of the invention provides the method for trace amounts of olefin in the long Arene removal of a kind of environmental friendliness, catalyst activity good stability, stable operation time.
The technical solution used in the present invention is:
A kind of process for purification of aromatic hydrocarbons, described method was: 50～400 ℃ of temperature, pressure 0.1～12MPa, charging mass space velocity 0.1～15 hour
-1Condition under, with aromatic hydrocarbons and solid acid catalyst contact reacts, make that trace amounts of olefin in the aromatic hydrocarbons adsorbs, superimposed and alkylated reaction, the trace amounts of olefin in the Arene removal, thereby aromatic hydrocarbons is made with extra care, obtain the aromatic hydrocarbons after refining; Described solid acid catalyst is that shell is wrapped in the hud typed composite molecular sieve catalyst of kernel or the composite solid acid catalyst that the loaded modified compound of hud typed composite molecular sieve catalyst obtains;
Described hud typed composite molecular sieve catalyst makes as follows: according to the preferred 1:10 of solid-liquid mass ratio 1:5～100(), kernel micro porous molecular sieve and water are mixed, form mixture A; With triblock polymer EO
20PO
70EO
20(P123) be template, according to EO
20PO
70EO
20: MO
N/2: SiO
2: mineral acid: H
2Preferred 1:1.3～the 25.8:62.5 of O=1:0.1～40:40～150:80～800:5000～18000(～125.3:100～500:8000～15000) amount of substance proportioning is with a certain amount of EO
20PO
70EO
20, H
2O, mineral acid mix, and add precursor and the silicon source of substituted element M, mix, and form mixture B; Described H
2O or water are distilled water or deionized water, mixture A is added among the mixture B, mix, crystallization is 0～72 hour under 10～200 ℃ of conditions, obtain crystallization product after filtration with after the washing, again crystallization product drying and 450～600 ℃ of roasting 2 ~ 30h are processed removed template method, obtain described hud typed composite molecular sieve catalyst; Described silicon source is silicon sol, tetraethoxy or methyl silicate; Described n is the valence electron number of substituted element M;
Described substituted element M is the mixture of following one or more arbitrary proportions: (1) beryllium, (2) magnesium, (3) calcium, (4) strontium, (5) boron, (6) aluminium, (7) gallium, (8) manganese, (9) iron, (10) cobalt, (11) nickel, (12) copper, (13) zinc, (14) titanium, (15) vanadium, (16) chromium, (17) germanium, (18) zirconium, (19) niobium, (20) molybdenum, (21) tin or (22) tungsten;
Described kernel micro porous molecular sieve is the mixture of following one or more arbitrary proportions: (1) HZSM-5 molecular sieve, (2) HY molecular sieve, (3) H beta-molecular sieve, (4) HUSY molecular sieve, (5) HMOR molecular sieve, (6) HMCM-22 molecular sieve; The massfraction that described kernel micro porous molecular sieve dosage accounts for hud typed composite molecular sieve catalyst is 0.1～50.0%; The silica alumina ratio of described all kinds kernel micro porous molecular sieve most preferably is its n (SiO of HZSM-5(
2)/n (Al
2O
3)=38), H β (its n (SiO
2)/n (Al
2O
3)=30), its n (SiO of HY(
2)/n (Al
2O
3)=9.6), its n (SiO of HUSY(
2)/n (Al
2O
3)=10), its n (SiO of HMOR(
2)/n (Al
2O
3)=23), its n (SiO of HMCM-22(
2)/n (Al
2O
3)=28.5).
Described modified compound is the mixture of following one or more arbitrary proportions: (1) phosphoric acid, (2) hydrofluoric acid, (3) Neutral ammonium fluoride, (4) phosphorus heteropoly tungstic acid, (5) silicotungstic heteropolyacid, (6) phosphato-molybdic heteropolyacid, (7) phosphorus heteropoly tungstic acid cesium salt, (8) silicotungstic heteropolyacid cesium salt, (9) phosphato-molybdic heteropolyacid cesium salt, (10) aluminum chloride, (11) zinc chloride, (12) iron(ic) chloride, (13) cupric chloride, (14) chromium chloride, (15) boric acid; The charge capacity of described modified compound is counted 0.01～60wt% with hud typed composite molecular screen quality.
It is one of following that described mineral acid is preferably: hydrochloric acid, nitric acid or sulfuric acid.
The precursor of described substituted element M is oxide compound, acid, oxyhydroxide or salt.
When described M was Al, the precursor of described M was: aluminum isopropylate, boehmite, pseudo-boehmite, monohydrate alumina, aluminum nitrate, aluminium colloidal sol, alumina gel or Tai-Ace S 150.
Described composite solid acid catalyst makes as follows: calculate the modified compound consumption according to the modified compound charge capacity, be dissolved in the solution that obtains in the solvent with modified compound hud typed composite molecular screen is carried out dip treating, then drying is or/and roasting, and namely obtaining the modified compound charge capacity is the composite solid acid catalyst of 0.01～60wt%; Described solvent is one of following: water, acetone, tetracol phenixin or dehydrated alcohol.
Further, 100～300 ℃ of preferred described temperature of reaction, pressure 0.2～4.0MPa, charging total mass air speed are 0.5～10.0 hour
-1, most preferably be 180～220 ℃ of temperature of reaction, pressure 1.0～2.5MPa, charging mass space velocity 0.5～2.0 hour
-1
Described aromatic hydrocarbons is the aromatic hydrocarbons of reformer generation, the aromatic hydrocarbons that steam cracking device generates.
Further, described aromatic hydrocarbons is benzene, toluene or the dimethylbenzene after the aromatic hydrocarbons of reformer or steam cracking device generation separates, and described separation method is method as well known to those skilled in the art, is generally distillation separation method.
Process for purification of the present invention also comprises the aromatic hydrocarbons pre-treatment, and described aromatic hydrocarbons pre-treatment is that aromatic hydrocarbons carries out the deolefination reaction through contacting with solid acid catalyst after the adsorbent bed absorption again; Described absorption pretreatment condition is: 0～200 ℃ of temperature, pressure 0.1～6.0MPa, mass space velocity 0.2～15 hour
-1, described sorbent material is following one or more arbitrary proportion mixtures: 13X molecular sieve, HY molecular sieve, atlapulgite, gac, HUSY molecular sieve or acidic ion exchange resin.
Reaction is to carry out in the reactor that two or more are in series or in parallel to form described in the described aromatic hydrocarbon refining method.
The optional fixed bed of reactor, expanded bed, fluidized-bed, stirred-tank reactor that reaction is adopted, and catalytic distillation reactor.Reaction unit can have a plurality of reactor parallel connections or serial operation.Fluid in the reactor can be taked upstriker, also can adopt downstriker.
Can adopt two reactors in series operations in the aromatic hydrocarbon refining process, first reactor is as the pretreatment reaction device, and second reactor is as the refining reaction device.In reaction, when the refining aromatic hydrocarbons olefin(e) centent of second reactor exceeds standard, greater than 100mgBr/100g, second reactor switched to first reactor such as its bromine index; The olefin(e) centent that flows out aromatic hydrocarbons when first reactor exceeds standard, and, just the catalyzer in first reactor is regenerated greater than 300mgBr/100g such as its bromine index.One of renovation process is to stop into aromatic hydrocarbons, with methyl alcohol, ethanol, acetone, methylene dichloride, tetracol phenixin, polyoxyethylene glycol, glycol ether, triglycol, tetrahydrofuran (THF), phenylformic acid, phenol isopolarity solvent decaying catalyst is carried out regenerated from washing; Two of renovation process is with oxygen-containing gas decaying catalyst to be carried out coke burning regeneration; Three of renovation process is to use first the polar solvent regenerated from washing, then with oxygen-containing gas decaying catalyst is carried out coke burning regeneration.
The beneficial effect of the method for trace amounts of olefin is mainly reflected in a kind of Arene removal of the present invention:
(1) technical process is simple, does not consume hydrogen, and plant investment and process cost are low;
(2) catalyst activity good stability, the device stable operation time is long, and the aromatic hydrocarbons loss is few, can avoid reactor reaction and the frequent blocked operation of regeneration;
(3) catalyzer is renewable, can avoid a large amount of spent catalyst heap burieds to process, and is little to environmental influence.
(4) embodiment
The present invention is described further below in conjunction with specific embodiment, but protection scope of the present invention is not limited in this:
Triblock polymer P123 used among the embodiment derives from Aldrich company, and monohydrate alumina derives from Shandong Aluminum Co., Ltd. group company; Its n (SiO of micro porous molecular sieve HZSM-5(
2)/n (Al
2O
3)=38), H β (its n (SiO
2)/n (Al
2O
3)=30) derive from Catalyst Factory, Nankai Univ, its n (SiO of HY(
2)/n (Al
2O
3)=9.6) and its n (SiO of HUSY(
2)/n (Al
2O
3)=10) derive from Wenzhou Hua Hua group company, its n (SiO of HMOR(
2)/n (Al
2O
3)=23) derive from Jiangsu AudioCodes petroleum chemistry technology company limited, its n (SiO of HMCM-22(
2)/n (Al
2O
3)=28.5) derive from Jiangyan City auxiliary chemicals factory.
The catalyst extruded forming process be M-SBA-15 that 30 grams are synthetic mesoporous/the mesoporous-microporous composite molecular sieve powder restrains the sesbania powder with 9 gram monohydrate aluminas, 0.75 and mixes, adding 36 gram distilled water and 55 gram mass content are 10% aqueous nitric acid, be kneaded into walk, extruded moulding dries rear temperature programming to 550 ℃ roasting 4 hours.
Comparative Examples
Synthesizing of Al-SBA-15 mesoporous molecular sieve catalyst
According to feed molar proportioning P123:Al
2O
3: SiO
2: HCl:H
2O is that 1:3.1:62.5:300:10000 calculates, and takes by weighing 20 gram P123, with distilled water and the mixed in hydrochloric acid of calculated amount, mixes 1.0 hours under 40 ℃ of temperature, adds 1.3 gram monohydrate aluminas and continues to mix 1.0 hours; Then, add 45.0 gram tetraethoxys and continue to mix 5.0 hours, obtain mixed slurry.This mixed slurry is placed plastic containers, and crystallization is 48 hours under 100 ℃ and autogenous pressure condition, after filtration, washing, drying treatment, at 5.0 hours removed template methods of 550 ℃ of roastings, obtains Al-SBA-15 mesoporous molecular sieve catalyst powder 13.8 grams.10 these catalyst fineses of gram and 3 gram monohydrate aluminas, 0.25 gram sesbania powder are mixed, adding 12 gram distilled water and 18.3 gram mass content are 10% aqueous nitric acid, be kneaded into walk, extruded moulding, dry rear temperature programming to 550 ℃ roasting 4 hours, through fragmentation, obtain 20～40 order granules of catalyst again, be designated as CAT-0.This catalyzer is used for aromatic hydrocarbons deolefination reaction experiment, and reaction experiment the results are shown in Table 3.
Embodiment 1:
Al-SBA-15 is mesoporous/H β mesoporous-microporous composite molecular sieve catalyzer synthetic
5 gram H β micro porous molecular sieve powder as kernel, are mixed 1.0 hours with 50 gram distilled water, obtain mixture A.According to feed molar proportioning P123:Al
2O
3: SiO
2: HCl:H
2O is that 1:3.1:62.5:300:10000 calculates, and takes by weighing 20 gram P123, with distilled water and the mixed in hydrochloric acid of calculated amount, mixes 1.0 hours under 40 ℃ of temperature, adds 1.3 gram monohydrate aluminas and continues to mix 1.0 hours; Under agitation condition, add 45.0 gram tetraethoxys, obtain mixture B.Then, mixture A is added among the mixture B, under 40 ℃ of temperature, continues to mix 5.0 hours, obtain mixed slurry.This mixed slurry is placed plastic containers, crystallization is 48 hours under 100 ℃ and autogenous pressure condition, after filtration, washing, drying treatment, at 5.0 hours removed template methods of 550 ℃ of roastings, obtain the kernel micro porous molecular sieve account for the Al-SBA-15 of catalyzer total mass 27.8% mesoporous/hud typed composite molecular sieve catalyst powder 18.7 grams of H β micropore, with broken, obtain 20～40 order granules of catalyst through extruded moulding, be designated as CAT-1.
Embodiment 2～6:
Adopt the synthetic method identical with embodiment 1, different is to use respectively HZSM-5 molecular sieve, HY molecular sieve, HUSY molecular sieve, HMOR molecular sieve, HMCM-22 molecular sieve as kernel, through Hydrothermal Synthesis, extruded moulding, obtain the kernel micro porous molecular sieve account for the Al-SBA-15 of catalyzer total mass 27.8% mesoporous/the hud typed composite molecular sieve catalyst of micropore, list in table 1.
Table 1
Embodiment 7～25:
Adopt the synthetic method identical with embodiment 1, different is as template take triblock polymer P123, use respectively butyl (tetra) titanate, Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES, zinc nitrate, gallium nitrate, manganous nitrate, strontium nitrate, zirconium nitrate, nitrocalcite, beryllium nitrate, iron nitrate, nickelous nitrate, nitric acid vanadium, chromium nitrate, nitric acid germanium, nitric acid tin, nitric acid molybdenum, niobic acid, cupric nitrate, wolframic acid as the precursor of substituted element M, according to P123:MO
N/2: SiO
2: HCl:H
2O is the synthetic M-SBA-15 molecular sieve powder that contains substituted element of the feed molar proportioning of 1:6.25:62.5:300:10000, with broken, obtains 20～40 order granules of catalyst through extruded moulding, lists in table 2.
Table 2
Embodiment 26:
B-Mg-SBA-15 is mesoporous/H β mesoporous-microporous composite molecular sieve catalyzer synthetic
5 gram H β micro porous molecular sieve powder and 50 gram distilled water are mixed 1.0 hours, obtain mixture A.According to feed molar proportioning P123:B
2O
3: MgO:SiO
2: HCl:H
2O is that 1:3.1:6.5:62.5:350:11000 calculates, and takes by weighing 20 gram P123, with distilled water and the mixed in hydrochloric acid of calculated amount, mixes 1.0 hours under 40 ℃ of temperature, adds the boric acid of calculated amount, continues to mix 1.0 hours; Under agitation condition, add magnesium acetate and the tetraethoxy of calculated amount, obtain mixture B.Then, mixture A is added among the mixture B, under 40 ℃ of temperature, continues to mix 5.0 hours, obtain mixed slurry.This mixed slurry is placed plastic containers, crystallization is 12 hours under 60 ℃ and autogenous pressure condition, through filtration, washing, drying treatment, at 5.0 hours removed template methods of 550 ℃ of roastings, obtain the kernel micro porous molecular sieve account for the B-Mg-SBA-15 of catalyzer total mass 26.3% mesoporous/the hud typed composite molecular sieve catalyst powder of H β micropore, with broken, obtain 20～40 order granules of catalyst through extruded moulding, be designated as CAT-26.
Embodiment 27～41:
Al-SBA-15 to embodiment 1 is mesoporous/and H β mesoporous-microporous composite molecular sieve catalyzer carries out loaded modified preparation composite solid acid catalyst
With embodiment 1 prepared 20～40 purpose Al-SBA-15 mesoporous/H β mesoporous-microporous composite molecular sieve particle is used for the operation of follow-up (1)～(14) preparation loaded catalyst:
(1) with 100 ml concns be 0.143mol/L phosphate aqueous solution to the Al-SBA-15 of 10 gram embodiment 1 gained mesoporous/H β mesoporous-microporous composite molecular sieve carried out the room temperature dip treating 24 hours, then carry out 110 ℃ of dryings 3 hours and 400 ℃ of calcination process 3 hours, obtain P
2O
5Charge capacity is the P/Al-SBA-15/H β composite solid acid catalyst of 10.0Wt%, is designated as CAT-27 catalyzer (embodiment 27).
(2) 5.0 gram boric acid are dissolved in the 30 gram acetone solvents, the Al-SBA-15 that adds 10 gram embodiment, 1 gained after the dissolving evenly is mesoporous/H β mesoporous-microporous composite molecular sieve, at room temperature stirred 15 minutes, heating evaporation falls acetone, 120 ℃ of dryings 3 hours, obtaining the boric acid charge capacity is the B/Al-SBA-15/H β composite solid acid catalyst of 50wt%, is designated as CAT-28 catalyzer (embodiment 28).
(3) with 100 ml concns be 0.167mol/L hydrofluoric acid aqueous solution to the Al-SBA-15 of 10 gram embodiment 1 gained mesoporous/H β mesoporous-microporous composite molecular sieve carried out the room temperature dip treating 24 hours, then carried out 110 ℃ of dryings 3 hours and 200 ℃ of calcination process 3 hours, obtaining the F charge capacity is the F/Al-SBA-15/H β composite solid acid catalyst of 3.0Wt%, is designated as CAT-29 catalyzer (embodiment 29).
(4) according to the method for embodiment 29, preparation Neutral ammonium fluoride charge capacity is the loaded modified NH of 3.0wt%
4F/Al-SBA-15/H β composite solid acid catalyst is designated as CAT-30(embodiment 30).
(5) with the loaded modified PW of phosphorus heteropoly tungstic acid (Solution on Chemical Reagents in Shanghai company) preparation phosphorus heteropoly tungstic acid
12/ Al-SBA-15/H β composite solid acid catalyst.With 100 ml concns be 0.008mol/L the phosphorus heteropoly tungstic acid aqueous solution to the Al-SBA-15 of 10 gram embodiment, 1 gained mesoporous/H β mesoporous-microporous composite molecular sieve carried out the room temperature dip treating 24 hours, then carry out 110 ℃ of dryings 3 hours and 200 ℃ of calcination process 3 hours, obtain PW
12Charge capacity is the PW of 20wt%
12/ Al-SBA-15/H β composite solid acid catalyst is designated as CAT-31(embodiment 31).
(6) with the loaded modified SiW of silicotungstic heteropolyacid (Shenyang becomes bright chemical reagent work) preparation silicotungstic heteropolyacid
12/ Al-SBA-15/H β composite solid acid catalyst.With 100 ml concns be 0.013mol/L the silicotungstic heteropolyacid aqueous solution to the Al-SBA-15 of 10 gram embodiment, 1 gained mesoporous/H β mesoporous-microporous composite molecular sieve carried out the room temperature dip treating 24 hours, then carry out 110 ℃ of dryings 3 hours and 200 ℃ of calcination process 3 hours, obtain SiW
12Charge capacity is the SiW of 30wt%
12/ Al-SBA-15/H β composite solid acid catalyst is designated as CAT-32(embodiment 32).
(7) with the loaded modified PMo of phosphato-molybdic heteropolyacid (the emerging chemical reagent work in Shenyang) preparation phosphato-molybdic heteropolyacid
12/ Al-SBA-15/H β composite solid acid catalyst.With 100 ml concns be 0.025mol/L the phosphato-molybdic heteropolyacid aqueous solution to the Al-SBA-15 of 10 gram embodiment, 1 gained mesoporous/H β mesoporous-microporous composite molecular sieve carried out the room temperature dip treating 24 hours, then carry out 110 ℃ of dryings 3 hours and 200 ℃ of calcination process 3 hours, obtain PMo
12Charge capacity is the PMo of 30wt%
12/ Al-SBA-15/H β composite solid acid catalyst is designated as CAT-33(embodiment 33).
(8) the loaded modified Cs of preparation phosphorus heteropoly tungstic acid cesium salt
2.5H
0.5PW
12/ Al-SBA-15/H β composite solid acid catalyst.
Respectively with 0.48 gram Cs
2CO
3With 3.49 gram H
3PW
12O
406H
2O is made into the aqueous solution of 0.1mol/L and 0.08mol/L.At first add 10 gram Al-SBA-15/H β composite molecular screens in the cesium carbonate aqueous solution, stirred 3 hours under the room temperature, evaporating water under 80 ℃ of temperature was in 500 ℃ of roasting temperatures 3 hours; Then the sample with roasting mixes with phosphotungstic acid aqueous solution, and stirring is 12 hours under the room temperature, evaporating water under 80 ℃ of temperature, and drying is 5 hours under 120 ℃ of temperature, in 200 ℃ of roasting temperatures 2 hours, obtains Cs
2.5H
0.5PW
12Charge capacity is the Cs of 30wt%
2.5H
0.5PW
12/ Al-SBA-15/H β composite solid acid catalyst is designated as CAT-34(embodiment 34).
(9) the loaded modified Cs of preparation silicotungstic heteropolyacid cesium salt
2.5H
0.5SiW
12/ Al-SBA-15/H β composite solid acid catalyst.
Respectively with 0.48 gram Cs
2CO
3With 3.49 gram H
3SiW
12O
406H
2O is made into the aqueous solution of 0.1mol/L and 0.08mol/L.At first add 10 gram Al-SBA-15/H β composite molecular screens in the cesium carbonate aqueous solution, stirred 3 hours under the room temperature, evaporating water under 80 ℃ of temperature was in 500 ℃ of roasting temperatures 3 hours; Then the sample with roasting mixes with silicon tungsten acid solution, and stirring is 12 hours under the room temperature, evaporating water under 80 ℃ of temperature, and drying is 5 hours under 120 ℃ of temperature, in 200 ℃ of roasting temperatures 2 hours, obtains Cs
2.5H
0.5SiW
12Charge capacity is the Cs of 30wt%
2.5H
0.5SiW
12/ Al-SBA-15/H β composite solid acid catalyst is designated as CAT-35(embodiment 35).
(10) the loaded modified Cs of preparation phosphato-molybdic heteropolyacid cesium salt
2.5H
0.5PMo
12/ Al-SBA-15/H β composite solid acid catalyst.
Respectively with 0.81 gram Cs
2CO
3With 3.83 gram H
3PMo
12O
406H
2O is made into the aqueous solution of 0.1mol/L and 0.08mol/L.At first add 10 gram Al-SBA-15/H β composite molecular screens in the cesium carbonate aqueous solution, stirred 3 hours under the room temperature, evaporating water under 80 ℃ of temperature was in 500 ℃ of roasting temperatures 3 hours; Then with sample and the phospho-molybdic acid aqueous solution of roasting, stirred 12 hours under the room temperature, evaporating water under 80 ℃ of temperature, drying is 5 hours under 120 ℃ of temperature, in 200 ℃ of roasting temperatures 2 hours, obtains Cs
2.5H
0.5PMo
12Charge capacity is the Cs of 30wt%
2.5H
0.5PMo
12/ Al-SBA-15/H β composite solid acid catalyst is designated as CAT-36(embodiment 36).
(11) the loaded modified AlCl of preparation aluminum chloride
3/ Al-SBA-15/H β composite solid acid catalyst.
With the Al-SBA-15/H β composite molecular screen of 10 gram embodiment, 1 gained and the CCl of 250 milliliters of dryings
4Be added in 500 milliliters the there-necked flask, then oil bath reflux 1.5 hours adds 2 gram aluminum chloride, continues reflux 3 hours; Filter, and use hot CCl
4Wash 2 times, the solid that obtains under 120 ℃ of temperature dry 5 hours obtains the AlCl that the aluminum chloride charge capacity is 20wt%
3/ Al-SBA-15/H β composite solid acid catalyst is designated as CAT-37(embodiment 37).
(12) according to the method for embodiment 37, preparation zinc chloride charge capacity is the loaded modified ZnCl of 20wt%
2/ Al-SBA-15/H β composite solid acid catalyst is designated as CAT-38(embodiment 38).
(13) according to the method for embodiment 37, preparation iron(ic) chloride charge capacity is the loaded modified FeCl of 20wt%
3/ Al-SBA-15/H β composite solid acid catalyst is designated as CAT-39(embodiment 39).
(14) according to the method for embodiment 37, preparation cupric chloride charge capacity is the loaded modified CuCl of 20wt%
2/ Al-SBA-15/H β composite solid acid catalyst is designated as CAT-40(embodiment 40).
(15) according to the method for embodiment 37, preparation chromium chloride charge capacity is the loaded modified CrCl of 20wt%
2/ Al-SBA-15/H β composite solid acid catalyst is designated as CAT-41(embodiment 41).
Embodiment 42:
With the synthetic Al-SBA-15 of nitric acid mesoporous/H β mesoporous-microporous composite molecular sieve catalyzer
0.4 gram H β micro porous molecular sieve powder as kernel, is mixed 1.0 hours with 50 gram distilled water, obtain mixture A.According to feed molar proportioning P123:Al
2O
3: SiO
2: HNO
3: H
2O is that 1:25.8:125.3:500:15000 calculates, and takes by weighing 20 gram P123, mixes with distilled water and the nitric acid of calculated amount, mixes 1.0 hours under 40 ℃ of temperature, and the aluminum nitrate that adds calculated amount continues to mix 1.0 hours; Under agitation condition, add the tetraethoxy of calculated amount, obtain mixture B.Then, mixture A is added among the mixture B, under 40 ℃ of temperature, continues to mix 5.0 hours, obtain mixed slurry.This mixed slurry is placed plastic containers, crystallization is 72 hours under 100 ℃ and autogenous pressure condition, through filtration, washing, drying treatment, at 5.0 hours removed template methods of 550 ℃ of roastings, obtain the kernel micro porous molecular sieve account for the Al-SBA-15 of catalyzer total mass 1.4% mesoporous/the hud typed composite molecular sieve catalyst powder of H β micropore, with broken, obtain 20～40 order granules of catalyst through extruded moulding, be designated as CAT-42.
Embodiment 43:
With the synthetic Al-SBA-15 of sulfuric acid mesoporous/H β mesoporous-microporous composite molecular sieve catalyzer
12.2 gram H β micro porous molecular sieve powder as kernel, are mixed 1.0 hours with 50 gram distilled water, obtain mixture A.According to feed molar proportioning P123:Al
2O
3: SiO
2: H
2SO
4: H
2O is that 1:1.3:76.5:100:8000 calculates, and takes by weighing 20 gram P123, mixes with distilled water and the sulfuric acid of calculated amount, mixes 1.0 hours under 40 ℃ of temperature, and the monohydrate alumina that adds calculated amount continues to mix 1.0 hours; Under agitation condition, add the tetraethoxy of calculated amount, obtain mixture B.Then, mixture A is added among the mixture B, under 40 ℃ of temperature, continues to mix 5.0 hours, obtain mixed slurry; Through filtration, washing, drying treatment, at 5.0 hours removed template methods of 550 ℃ of roastings, obtain the kernel micro porous molecular sieve account for the Al-SBA-15 of catalyzer total mass 42.1% mesoporous/the hud typed composite molecular sieve catalyst powder of H β micropore, through extruded moulding and fragmentation, obtain 20～40 order granules of catalyst, be designated as CAT-43.
Embodiment 44～86:
Carry out the arene engaging scraping olefine reaction with solid acid catalyst.
Adopt fixed-bed reactor, reactor is the stainless steel tube of long 100cm, internal diameter 1.0cm, and at the reactor middle part, quartz sand is filled up at the reactor two ends with 5.0 gram catalyst loadings.At pressure 1.0MPa, 180 ℃ of temperature, mass space velocity 2.0h
-1Under the condition, reformed arene to certain petrochemical enterprise continues to remove the olefine reaction experiment, with the RPA-100Br type bromine index determinator assaying reaction raw material of Jiangsu Jianghuan Analyser Co., Ltd.'s production and the bromine index of refined products, the measurement result of aroamtic hydrocarbon raw material bromine index is 865.5mgBr/100g, and the experimental result of refined products bromine index is listed in table 3.
Comparison sheet 3 data as can be known because Comparative Examples prepared catalyst CAT-0 is without the kernel micro porous molecular sieve, its catalytic activity is lower, causes aromatic hydrocarbon refining product bromine index larger.
Table 3
Embodiment 87:
Investigate temperature of reaction to the impact of arene engaging scraping alkene.
Adopt fixed-bed reactor, reactor be the stainless steel tube of long 100cm, internal diameter 1.0cm, restrains the prepared CAT-1 catalyst loading of embodiment 1 in the middle part of reactor with 5.0, and quartz sand is filled up at the reactor two ends.At pressure 3.0MPa, mass space velocity 2.0h
-1Under the condition, reformed arene to certain petrochemical enterprise removes the olefine reaction experiment, bromine index with RPA-100Br type bromine index determinator assaying reaction raw material and refined products, the measurement result of aroamtic hydrocarbon raw material bromine index is 865.5mgBr/100g, and the refined products bromine index measurement result of differing temps is listed in table 4.From table 4 data as can be known, take off the alkene rate and improve and increase along with temperature of reaction, this explanation suitably improves temperature of reaction and is conducive to the aromatic hydrocarbons deolefination.
Table 4
Embodiment 88:
Investigate mass space velocity to the impact of arene engaging scraping alkene.
Adopt fixed-bed reactor, reactor be the stainless steel tube of long 100cm, internal diameter 1.0cm, restrains the prepared CAT-1 catalyst loading of embodiment 1 in the middle part of reactor with 5.0, and quartz sand is filled up at the reactor two ends.Under the condition of 180 ℃ of pressure 1.5MPa, temperature, reformed arene to certain petrochemical enterprise removes the olefine reaction experiment, bromine index with RPA-100Br type bromine index determinator assaying reaction raw material and refined products, the measurement result of aroamtic hydrocarbon raw material bromine index is 865.5mgBr/100g, and the refined products bromine index measurement result of different mass air speed is listed in table 5.As can be seen from Table 5, take off the alkene rate and reduce and increase along with mass space velocity, the suitable reduction of this explanation mass space velocity is conducive to improve aromatic hydrocarbons and takes off the alkene rate.
Table 5
Embodiment 89:
Aromatic hydrocarbons is through the serial operation of absorption pre-treatment and the reaction of catalysis deolefination.
Adopt respectively the 13X molecular sieve of atlapulgite that Fushun Petrochemical Company produces, HY molecular sieve that Hua Hua group company in Wenzhou produces, Shanghai Chemical Reagent Co., Ltd., Sinopharm Group and D005 type acidic ion exchange resin that gac, Dandong Mingzhu Special Type Resin Co., Ltd. produce as sorbent material.With two fixed-bed reactor series connection, first reactor is as the adsorption treatment bed, and second reactor is as beds.Respectively 10.0 gram sorbent materials and 5.0 gram catalyzer CAT-1 are seated in first and second reactor, quartz sand is all filled up at the two ends of two reactors.Under the condition of pressure 1.0MPa, 180 ℃ of 50 ℃, second temperature of reactor of first temperature of reactor, reformed arene inlet amount 5.0g/h, continue the reaction experiment of arene engaging scraping alkene, the measurement result of aroamtic hydrocarbon raw material bromine index is 865.5mgBr/100g, and the refined products bromine index measurement result of different sustained reaction time is listed in table 6.
Table 6
From table 6 data as can be known, through 100 days lasting aromatic hydrocarbons deolefination reaction, refining aromatic hydrocarbons bromine index took off the alkene rate all the time more than 95.0% less than 40 mgBr/100g, shows that catalyzer has good activity stability under this operational condition.
Embodiment 90:
Aromatic hydrocarbons is through the serial operation of absorption pre-treatment and the reaction of catalysis deolefination of different condition.
Adopt the 13X molecular sieve of Shanghai Chemical Reagent Co., Ltd., Sinopharm Group as sorbent material, with two fixed-bed reactor series connection, first reactor is as the adsorption treatment bed, second reactor is as beds, respectively sorbent material and catalyzer CAT-1 are seated in first and second reactor, quartz sand is all filled up at the two ends of two reactors.Pressure 6.0MPa, 10～200 ℃ of first temperature of reactor and mass space velocity 0.2～15 hour
-1, second 180 ℃ of temperature of reactor and mass space velocity 1.0 hours
-1Condition under carry out the reaction experiment that reformed arene removes alkene, the measurement result of aroamtic hydrocarbon raw material bromine index is 865.5mgBr/100g, the refined products bromine index measurement result of different condition being adsorbed the reaction of pre-treatment and definite condition catalysis deolefination is listed in table 7.
Table 7
As can be seen from Table 7, react serial operation about aromatic hydrocarbons through the absorption pre-treatment of different condition and the catalysis deolefination of definite condition, along with adsorption temp improves or the reduction of quality of adsorption air speed, the bromine index of refining aromatic hydrocarbons reduces gradually, the deolefination effect improves gradually, shows suitable raising adsorption temp or reduce the quality of adsorption air speed to be conducive to improve the aromatic hydrocarbon refining effect.
Embodiment 91:
Adopt the arene engaging scraping olefine reaction of two reactors in series reaction units.
Respectively 5.0 gram catalyzer CAT-1 and 5.0 gram catalyzer CAT-4 are seated in first reactor and second reactor middle part, quartz sand is all filled up at the two ends of two reactors.Under the condition of pressure 1.0MPa, 180 ℃ of 100 ℃, second temperature of reactor of first temperature of reactor, reformed arene inlet amount 10.0g/h, continue the reaction experiment of arene engaging scraping alkene, the measurement result of aroamtic hydrocarbon raw material bromine index is 865.5mgBr/100g, and the refined products bromine index measurement result of different sustained reaction time is listed in table 8.The 1790 type gas chromatographs with 50 meters OV-101 capillary columns, fid detector of producing with Agilent science and technology Shanghai Analytical Instrument Co., Ltd carry out compositional analysis to aroamtic hydrocarbon raw material and refined products, the results are shown in Table 9.
Table 8
From table 8 data as can be known, through 100 days lasting aromatic hydrocarbons deolefination reaction, take off the alkene rate all the time more than 96.0%, show that catalyzer has good activity stability under this operational condition, the device stable operation time is long.
Table 9
As can be seen from Table 9, the aromatic hydrocarbon product of process catalyst treatment keeps identical substantially with raw material on product forms, and aromatic hydrocarbon product does not have the variation of generation substantially on forming, illustrate that this catalyzer can satisfy industrial production to the requirement of quality product.
Embodiment 92:
Carry out benzene and remove the reaction experiment of alkene.
Adopt fixed-bed reactor, the CAT-1 catalyst loading that 5.0 gram embodiment 1 are prepared is at the reactor middle part, and quartz sand is filled up at the reactor two ends.At pressure 2.5MPa, 200 ℃ of temperature, mass space velocity 2.0h
-1Condition under, the benzene that certain petrochemical enterprise reformation BTX aromatics is obtained through fractionation by distillation removes the olefine reaction experiment, bromine index with RPA-100Br type bromine index determinator assaying reaction raw material and refined products, the measurement result of benzene feedstock bromine index is 348.6mgBr/100g, through the reaction that continues 90 days, the measurement result of commercial benzene bromine index is less than 38.0mgBr/100g.
Embodiment 93:
Carry out the reaction experiment of steam cracking arene engaging scraping alkene.
Adopt fixed-bed reactor, the CAT-1 catalyst loading that 5.0 gram embodiment 1 are prepared is at the reactor middle part, and quartz sand is filled up at the reactor two ends.At pressure 2.0MPa, 220 ℃ of temperature, mass space velocity 2.0h
-1Condition under, steam cracking aromatic hydrocarbons to certain petrochemical enterprise removes the olefine reaction experiment, bromine index with RPA-100Br type bromine index determinator assaying reaction raw material and refined products, the measurement result of raw material aromatic hydrocarbons bromine index is 1127.5mgBr/100g, through the reaction that continues 90 days, the measurement result of refining steam cracking aromatic hydrocarbons bromine index is less than 81.0mgBr/100g.
Above-mentioned showing, catalyzer provided by the invention has very high catalytic activity, reaction preference and activity stability, and the method for trace amounts of olefin has good application prospect in the Arene removal provided by the invention.
Claims (10)
1. the process for purification of an aromatic hydrocarbons is characterized in that described method is: 50～400 ℃ of temperature, pressure 0.1～12MPa, charging mass space velocity 0.1～15 hour
-1Condition under, with aromatic hydrocarbons and solid acid catalyst contact reacts, obtain the aromatic hydrocarbons after refining; Described solid acid catalyst is that shell is wrapped in the hud typed composite molecular sieve catalyst of kernel or the composite solid acid catalyst that the loaded modified compound of hud typed composite molecular sieve catalyst obtains, described shell is the M-SBA-15 mesopore molecular sieve that contains substituted element M, and described kernel is micro porous molecular sieve;
Described hud typed composite molecular sieve catalyst makes as follows: according to solid-liquid mass ratio 1:5～100, kernel micro porous molecular sieve and water are mixed, form mixture A; With triblock polymer EO
20PO
70EO
20Be template, according to EO
20PO
70EO
20: MO
N/2: SiO
2: mineral acid: H
2The amount of substance proportioning of O=1:0.1～40:40～150:80～800:5000～18000 is with a certain amount of EO
20PO
70EO
20, H
2O, mineral acid mix, and add precursor and the silicon source of substituted element M, mix, and form mixture B; Described H
2O or water are distilled water or deionized water, mixture A is added among the mixture B, mix, crystallization is 0～72 hour under 10～200 ℃ of conditions, obtain crystallization product after filtration with after the washing, with crystallization product drying and calcination process removed template method, obtain described hud typed composite molecular sieve catalyst again; Described silicon source is silicon sol, tetraethoxy or methyl silicate; Described n is the valence electron number of substituted element M;
Described substituted element M is the mixture of following one or more arbitrary proportions: (1) beryllium, (2) magnesium, (3) calcium, (4) strontium, (5) boron, (6) aluminium, (7) gallium, (8) manganese, (9) iron, (10) cobalt, (11) nickel, (12) copper, (13) zinc, (14) titanium, (15) vanadium, (16) chromium, (17) germanium, (18) zirconium, (19) niobium, (20) molybdenum, (21) tin or (22) tungsten;
Described kernel micro porous molecular sieve is the mixture of following one or more arbitrary proportions: (1) HZSM-5 molecular sieve, (2) HY molecular sieve, (3) H beta-molecular sieve, (4) HUSY molecular sieve, (5) HMOR molecular sieve or (6) HMCM-22 molecular sieve; The massfraction that described kernel micro porous molecular sieve dosage accounts for hud typed composite molecular sieve catalyst is 0.1～50.0%;
Described modified compound is the mixture of following one or more arbitrary proportions: (1) phosphoric acid, (2) hydrofluoric acid, (3) Neutral ammonium fluoride, (4) phosphorus heteropoly tungstic acid, (5) silicotungstic heteropolyacid, (6) phosphato-molybdic heteropolyacid, (7) phosphorus heteropoly tungstic acid cesium salt, (8) silicotungstic heteropolyacid cesium salt, (9) phosphato-molybdic heteropolyacid cesium salt, (10) aluminum chloride, (11) zinc chloride, (12) iron(ic) chloride, (13) cupric chloride, (14) chromium chloride or (15) boric acid; The charge capacity of described modified compound is counted 0.01～60wt% with hud typed composite molecular screen quality.
2. aromatic hydrocarbon refining method as claimed in claim 1 is characterized in that described mineral acid is one of following: hydrochloric acid, nitric acid or sulfuric acid.
3. aromatic hydrocarbon refining method as claimed in claim 1, the precursor that it is characterized in that described substituted element M is oxide compound, acid, oxyhydroxide or salt.
4. aromatic hydrocarbon refining method as claimed in claim 3, when it is characterized in that described M is Al, the precursor of described M is: aluminum isopropylate, boehmite, pseudo-boehmite, monohydrate alumina, aluminum nitrate, aluminium colloidal sol, alumina gel or Tai-Ace S 150.
5. aromatic hydrocarbon refining method as claimed in claim 1, it is characterized in that described composite solid acid catalyst makes as follows: calculate the modified compound consumption according to the modified compound charge capacity, be dissolved in the solution that obtains in the solvent with modified compound hud typed composite molecular screen is carried out dip treating, then drying is or/and roasting, and namely obtaining the modified compound charge capacity is the composite solid acid catalyst of 0.01～60wt%; Described solvent is one of following: water, acetone, tetracol phenixin or dehydrated alcohol.
6. aromatic hydrocarbon refining method as claimed in claim 1 is characterized in that 100～300 ℃ of described temperature of reaction, pressure 0.2～4.0MPa, charging total mass air speed 0.5～10.0 hour
-1
7. aromatic hydrocarbon refining method as claimed in claim 1 is characterized in that described aromatic hydrocarbons is the aromatic hydrocarbons of reformer generation or the aromatic hydrocarbons that steam cracking device generates.
8. aromatic hydrocarbon refining method as claimed in claim 1 is characterized in that described aromatic hydrocarbons is benzene, toluene or the dimethylbenzene after aromatic hydrocarbons that reformer or steam cracking device generate separates.
9. aromatic hydrocarbon refining method as claimed in claim 1 is characterized in that described process for purification also comprises the aromatic hydrocarbons pre-treatment, and described aromatic hydrocarbons pre-treatment is that aromatic hydrocarbons reacts through contacting with solid acid catalyst after the adsorbent bed absorption again; Described absorption pretreatment condition is: 0～200 ℃ of temperature, pressure 0.1～6.0MPa, mass space velocity 0.2～15 hour
-1, described sorbent material is following one or more arbitrary proportion mixtures: 13X molecular sieve, HY molecular sieve, atlapulgite, gac, HUSY molecular sieve or acidic ion exchange resin.
10. aromatic hydrocarbon refining method as claimed in claim 1 is characterized in that described reaction is to carry out in the reactor that two or more are in series or in parallel to form.
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| CN110813370B (en) * | 2019-10-29 | 2022-05-24 | 浙江工业大学 | Method for refining aromatic hydrocarbon by utilizing microporous mesoporous core-shell structure composite molecular sieve |
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