CN102992932B - Method for removing olefin in aromatic hydrocarbon by M-SBA-15 type mesoporous molecular sieve - Google Patents
Method for removing olefin in aromatic hydrocarbon by M-SBA-15 type mesoporous molecular sieve Download PDFInfo
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Abstract
The invention discloses a method for removing olefin in aromatic hydrocarbon by an M-SBA-15 type mesoporous molecular sieve. The method comprises the step of carrying out contact reaction of aromatic hydrocarbon with a solid acid catalyst to obtain aromatic hydrocarbon without olefin at 30-350 DEGC, at a pressure of 0.1-10MPa, and at an air speed of 0.1-15/h for feed quality, wherein the aromatic hydrocarbon is aromatic hydrocarbon generated by reforming generated oil, reforming aromatic hydrocarbon or steam cracking. The method is simple in process flow, free of hydrogen consumption and low in device investment and operating cost. The catalyst activity is good in stability, the stable operation of the device is long and the aromatic hydrocarbon loss is small, so that the frequency switching operation between reaction and regeneration of a reactor is avoided. The catalyst is reproducible, so that a great amount of dead catalysts is not buried, therefore, the environmental influence is small.
Description
(1) technical field
The present invention relates to a kind of process for purification of aromatic hydrocarbons, the especially a kind of M-SBA-15 of employing type mesoporous molecular sieve catalyst carries out the method for trace amounts of olefin in acid catalyzed reaction Arene removal.
(2) background technology
Catalytic reforming and Aromatics Extractive Project machinery are that petrochemical enterprise produces one of main processing unit (plant) of the aromatic hydrocarbons such as benzene,toluene,xylene, and naphtha fraction is converted into reformed oil by it.Reformed oil is rich in aromatic hydrocarbons and spirit fraction, also containing a small amount of alkene.This part olefin impurity affects Aromatics Extractive Project operation and aromatic hydrocarbon product quality, also affects some follow-up chemical engineering processes.Therefore, in order to obtain qualified aroamtic hydrocarbon raw material and ensure carrying out smoothly of subsequent technique, the olefin impurity in reformed oil or aromatic hydrocarbons must be carried out deep removal.At present, the method removing olefin impurity that domestic and international refinery extensively adopts mainly contains hydrofining and clay-filtered two kinds.
Hydrofining mainly utilizes alumina supporter Supported Pt Nanoparticles or palladium catalyst, and " back end hydrogenation " process of carrying out after reforming reactor is to realize olefin saturated thus to reach the object removing alkene.The efficiency of hydrofining deolefination impurity is high, thus widely use by domestic and international refinery.No matter for being that its active component effect is all better with platinum or palladium benzene cut, but for the aromatic hydrocarbons comparatively wide fraction of benzene, toluene and dimethylbenzene etc., 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 more complicated, must be provided with and manyly faces hydrogen high-tension apparatus, add some noble metal catalyst, cause investment and process cost high.
Clay-filtered is utilize acid-treated carclazyte, mainly through absorption or some olefin is superimposed and alkylated reaction, thus reaches the object removing alkene.Although clay treatment process has obtained industrial application widely, the effect removing alkene is poor; In actual process, carclazyte inactivation is fast, life cycle is short, consumption is large, and the carclazyte after inactivation can not regenerate, within about 1 month, just need more to renew carclazyte, frequent replacing adds aromatic hydrocarbons loss and workload, and a large amount of spent bleaching clays needs heap buried process, causes environmental pollution.
The meso-hole structure that SBA-15 type mesopore molecular sieve has high-sequential because of it, improves the rate of diffusion of macromolecular reaction thing in its duct, obtains the extensive concern of people.But because the surface acidity of this mesopore molecular sieve is more weak, hinder its application in petrochemical complex.Add isomorphous substitution element when this kind of zeolite-water thermal synthesis, or it is loaded modified to carry out acidic substance to molecular sieve, can improve molecular sieve catalyst surface acidity, improve the activity stability of catalyzer.
(3) summary of the invention
The object of the invention is to provide the method for trace amounts of olefin in the Arene removal of a kind of environmental friendliness, catalyst activity good stability, stable operation time length.
The technical solution used in the present invention is:
Utilize a method for alkene in M-SBA-15 type mesopore molecular sieve Arene removal, described method is: in temperature 30 ~ 350 DEG C, pressure 0.1 ~ 10MPa, feedstock quality air speed 0.1 ~ 15 hour
-1condition under, by aromatic hydrocarbons and solid acid catalyst contact reacts, the trace amounts of olefin in aromatic hydrocarbons is adsorbed, superimposed and alkylated reaction, the trace amounts of olefin in Arene removal, thus aromatic hydrocarbons is refined, obtain the aromatic hydrocarbons removing alkene; Described solid acid catalyst is the composite solid acid catalyst obtained containing the M-SBA-15 mesoporous molecular sieve catalyst of substituted element M or the loaded modified compound of M-SBA-15 mesoporous molecular sieve catalyst; Described aromatic hydrocarbons is the aromatic hydrocarbons that reformed oil, reformed arene or steam cracking produce;
Described substituted element M is the mixture of one or more arbitrary proportions following: (1) magnesium, (2) calcium, (3) strontium, (4) boron, (5) aluminium, (6) gallium, (7) manganese, (8) iron, (9) cobalt, (10) nickel, (11) copper, (12) zinc, (13) titanium, (14) vanadium, (15) chromium, (16) germanium, (17) zirconium, (18) niobium, (19) molybdenum, (20) tin, (21) tungsten; In described M and molecular sieve, Si atomic ratio is 0.001 ~ 1:1;
Described modified compound is the mixture of one or more arbitrary proportions following: (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 counts 0.01 ~ 70wt% with M-SBA-15 mesoporous molecular sieve catalyst quality.
Described M-SBA-15 type mesoporous molecular sieve catalyst obtains as follows: with triblock polymer EO
20pO
70eO
20(P123) be template, according to EO
20pO
70eO
20: MO
n/2: SiO
2: mineral acid: H
2o=1:0.1 ~ 40:40 ~ 150:80 ~ 800:5000 ~ 18000(preferred 1:1.3 ~ 25.8:62.5 ~ 125.3:100 ~ 500:8000 ~ 15000) amount of substance proportioning, by a certain amount of EO
20pO
70eO
20, H
2o, mineral acid mix, and add precursor and the silicon source of substituted element M, are uniformly mixed, described H
2o or water are distilled water or deionized water, crystallization 0 ~ 72 hour under 10 ~ 200 DEG C of conditions, obtain crystallization product after filtration with after washing, then by crystallization product drying and 450 ~ 600 DEG C of roasting 2 ~ 30h process removed template methods, obtain described M-SBA-15 type mesoporous molecular sieve catalyst; Described silicon source is silicon sol, tetraethoxy or methyl silicate; Described n is the valence electron number of substituted element M, and described mineral acid is one of following: hydrochloric acid, nitric acid or sulfuric acid.
The precursor of described substituted element M is oxide compound, acid, oxyhydroxide or salt.
Further, when described M is Al, the precursor of described M is: aluminum isopropylate, boehmite, pseudo-boehmite, monohydrate alumina, aluminum nitrate, Alumina gel, alumina gel or Tai-Ace S 150.
Described composite solid acid catalyst obtains as follows: calculate modified compound consumption according to modified compound charge capacity, be dissolved in the solution obtained in solvent with modified compound and dip treating is carried out to M-SBA-15 type mesopore molecular sieve, then drying is or/and roasting, and namely obtaining modified compound charge capacity is 0.01 ~ 60wt%(preferably 3 ~ 50 wt %) composite solid acid catalyst; Described solvent is one of following: water, acetone, tetracol phenixin or dehydrated alcohol.
Further, preferably described temperature of reaction 100 ~ 300 DEG C, pressure 0.2 ~ 4.0MPa, charging total mass air speed 0.5 ~ 10.0 hour
-1.
Further, described aromatic hydrocarbons can also be benzene, toluene or dimethylbenzene after reformed arene or steam cracking aromatics seperation, and the technology that described separation method is known to the skilled person, is generally distillation separation method.
Process for purification of the present invention also comprises aromatic hydrocarbons pre-treatment, and described aromatic hydrocarbons pre-treatment is that aromatic hydrocarbons contacts with solid acid catalyst and carries out deolefination reaction after adsorbent bed absorption; Described absorption pretreatment condition is: temperature 0 ~ 200 DEG C, pressure 0.1 ~ 6.0MPa, mass space velocity 0.2 ~ 15 hour
-1, described sorbent material is one or more arbitrary proportion mixtures following: 13X molecular sieve, HY molecular sieve, atlapulgite, gac, HUSY molecular sieve or acidic ion exchange resin (preferred D005 type acidic ion exchange resin).
Described in described aromatic hydrocarbon refining method, reaction carries out in the reactor that two or more are in series or in parallel to form.
React the optional fixed bed of reactor, expanded bed, fluidized-bed, the stirred-tank reactor that adopt, and catalytic distillation reactor.Reaction unit can have the parallel connection of multiple reactor or serial operation.Fluid in reactor can take upstriker, also can adopt downstriker.
Can adopt two reactors in series operations in aromatic hydrocarbon refining process, first reactor is as preatreating reactors, and second reactor is as refining reaction device.In the reaction, when the refining aromatic hydrocarbons olefin(e) centent of second reactor exceeds standard, as its bromine index is greater than 100mgBr/100g, second reactor is switched to first reactor; The olefin(e) centent flowing out aromatic hydrocarbons when first reactor exceeds standard, and as its bromine index is greater than 300mgBr/100g, just regenerates the catalyzer in first reactor.One of renovation process stops into aromatic hydrocarbons, carries out regenerated from washing with methyl alcohol, ethanol, acetone, methylene dichloride, tetracol phenixin, polyoxyethylene glycol, glycol ether, triglycol, tetrahydrofuran (THF), phenylformic acid, phenol polar solvent to decaying catalyst; Two of renovation process carries out coke burning regeneration with oxygen-containing gas to decaying catalyst; Three of renovation process first uses polar solvent regenerated from washing, then carries out coke burning regeneration with oxygen-containing gas to decaying catalyst.
In a kind of M-SBA-15 of utilization type mesopore molecular sieve Arene removal of the present invention, the beneficial effect of the method for alkene is mainly reflected in:
(1) technical process is simple, does not consume hydrogen, plant investment and process cost low;
(2) catalyst activity good stability, the device stable operation time is long, and aromatic hydrocarbons loss is few, can avoid reactor reaction and the frequent blocked operation of regeneration;
(3) catalyzer is renewable, can avoid the process of a large amount of spent catalyst heap buried, little to environmental influence.
(4) embodiment
Below in conjunction with specific embodiment, the present invention is described further, but protection scope of the present invention is not limited in this:
Triblock polymer P123 used in embodiment derives from Aldrich company, and monohydrate alumina derives from Shandong Aluminum Co., Ltd. group company.
Catalyst extruded forming process is mixed with 9 grams of monohydrate aluminas, 0.75 gram of field mountain valley with clumps of trees and bamboo powder by mesoporous for the M-SBA-15 of 30 grams of synthesis/mesoporous-microporous composite molecular sieve powder, add 36 grams of distilled water and 55 gram mass content are the aqueous nitric acid of 10%, be kneaded into walk, extruded moulding, dries rear temperature programming to 550 DEG C of roastings 4 hours.
Embodiment 1:
The synthesis of Al-SBA-15 type 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 take 20 grams of P123, distilled water and mixed in hydrochloric acid with calculated amount, be uniformly mixed 1.0 hours at 40 DEG C of temperature, adds 1.3 grams of monohydrate aluminas and continue to be uniformly mixed 1.0 hours; Then, add 45.0 grams of tetraethoxys to continue to be uniformly mixed 5.0 hours; Crystallization 48 hours under 100 DEG C and autogenous pressure condition, through filtering, washing, 120 DEG C of drying treatment 5 hours, at 550 DEG C of roastings, 5.0 hours removed template methods, obtain 13.5 grams, Al-SBA-15 type molecular sieve catalyst powder, through extruded moulding with broken, obtain 20 ~ 40 order granules of catalyst, be designated as CAT-1.
Embodiment 2 ~ 21:
Adopt the synthetic method identical with embodiment 1, unlike with triblock polymer P123 for template, use the precursor of butyl (tetra) titanate, Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES, zinc nitrate, gallium nitrate, manganous nitrate, strontium nitrate, zirconium nitrate, nitrocalcite, magnesium acetate, iron nitrate, nickelous nitrate, nitric acid vanadium, chromium nitrate, nitric acid germanium, nitric acid tin, nitric acid molybdenum, niobic acid, cupric nitrate, wolframic acid, boric acid alternatively element M respectively, according to P123:MO
n/2: SiO
2: HCl:H
2o is the M-SBA-15 molecular sieve powder of feed molar proportioning synthesis containing substituted element of 1:6.25:62.5:300:10000, through extruded moulding with broken, obtains 20 ~ 40 order granules of catalyst, lists in table 1.
Table 1
Embodiment 22 ~ 36:
Carry out loaded modifiedly preparing composite solid acid catalyst to the Al-SBA-15 type molecular sieve catalyst of embodiment 1
20 ~ 40 object Al-SBA-15 type sieve particles prepared by embodiment 1 are used for the operation preparing loaded catalyst in follow-up (1) ~ (14):
(1) be that the Al-SBA-15 type molecular sieve of phosphate aqueous solution to 10 grams of embodiment 1 gained of 0.143mol/L carries out room temperature immersion process 24 hours with 100 ml concns, then carry out 110 DEG C of dryings 3 hours and 400 DEG C of calcination process 3 hours, obtain P
2o
5charge capacity is the P/Al-SBA-15 composite solid acid catalyst of 10.0Wt%, is designated as CAT-22 catalyzer (embodiment 22).
(2) 5.0 grams of boric acid are dissolved in 30 grams of acetone solvents, above-mentioned Al-SBA-15 type molecular sieve is added after being uniformly dissolved, at room temperature stir 15 minutes, heating evaporation falls acetone, 120 DEG C of dryings 3 hours, obtain the B/Al-SBA-15 composite solid acid catalyst that boric acid charge capacity is 50wt%, be designated as CAT-23 catalyzer (embodiment 23).
(3) be that the Al-SBA-15 type molecular sieve of hydrofluoric acid aqueous solution to 10 grams of embodiment 1 gained of 0.167mol/L carries out room temperature immersion process 24 hours with 100 ml concns, then 110 DEG C of dryings are carried out 3 hours and 200 DEG C of calcination process 3 hours, obtain the F/Al-SBA-15 composite solid acid catalyst that F charge capacity is 3.0Wt%, be designated as CAT-24 catalyzer (embodiment 24).
(4) according to the method for embodiment 24, the loaded modified NH that Neutral ammonium fluoride charge capacity is 3.0wt% is prepared
4f/Al-SBA-15 composite solid acid catalyst, is designated as CAT-25(embodiment 25).
(5) the loaded modified PW of phosphorus heteropoly tungstic acid is prepared with phosphorus heteropoly tungstic acid (Solution on Chemical Reagents in Shanghai company)
12/ Al-SBA-15 composite solid acid catalyst.Be that the Al-SBA-15 type molecular sieve of the phosphorus heteropoly tungstic acid aqueous solution to 10 grams of embodiment 1 gained of 0.008mol/L carries out room temperature immersion process 24 hours with 100 ml concns, then carry out 110 DEG C of dryings 3 hours and 200 DEG C of calcination process 3 hours, obtain PW
12charge capacity is the PW of 20wt%
12/ Al-SBA-15 composite solid acid catalyst, is designated as CAT-26(embodiment 26).
(6) the loaded modified SiW of silicotungstic heteropolyacid is prepared with silicotungstic heteropolyacid (Shenyang Cheng Sheng chemical reagent work)
12/ Al-SBA-15 composite solid acid catalyst.Be that the Al-SBA-15 type molecular sieve of the silicotungstic heteropolyacid aqueous solution to 10 grams of embodiment 1 gained of 0.013mol/L carries out room temperature immersion process 24 hours with 100 ml concns, then carry out 110 DEG C of dryings 3 hours and 200 DEG C of calcination process 3 hours, obtain SiW
12charge capacity is the SiW of 30wt%
12/ Al-SBA-15 composite solid acid catalyst, is designated as CAT-27(embodiment 27).
(7) the loaded modified PMo of phosphato-molybdic heteropolyacid is prepared with phosphato-molybdic heteropolyacid (the emerging chemical reagent work in Shenyang)
12/ Al-SBA-15 composite solid acid catalyst.Be that the Al-SBA-15 type molecular sieve of the phosphato-molybdic heteropolyacid aqueous solution to 10 grams of embodiment 1 gained of 0.025mol/L carries out room temperature immersion process 24 hours with 100 ml concns, then carry out 110 DEG C of dryings 3 hours and 200 DEG C of calcination process 3 hours, obtain PMo
12charge capacity is the PMo of 30wt%
12/ Al-SBA-15 composite solid acid catalyst, is designated as CAT-28(embodiment 28).
(8) Cs that phosphorus heteropoly tungstic acid cesium salt is loaded modified is prepared
2.5h
0.5pW
12/ Al-SBA-15 composite solid acid catalyst.
Respectively by 0.48 gram of Cs
2cO
3with 3.49 grams of H
3pW
12o
406H
2o is made into the aqueous solution of 0.1mol/L and 0.08mol/L.First in cesium carbonate aqueous solution, 10 grams of Al-SBA-15 type molecular sieves are added, stirred at ambient temperature 3 hours, evaporating water at 80 DEG C of temperature, in 500 DEG C of roasting temperatures 3 hours; Then the sample of roasting is mixed with phosphotungstic acid aqueous solution, stirred at ambient temperature 12 hours, evaporating water at 80 DEG C of temperature, at 120 DEG C of temperature dry 5 hours, in 200 DEG C of roasting temperatures 2 hours, obtain Cs
2.5h
0.5pW
12charge capacity is the Cs of 30wt%
2.5h
0.5pW
12/ Al-SBA-15 composite solid acid catalyst, is designated as CAT-29(embodiment 29).
(9) Cs that silicotungstic heteropolyacid cesium salt is loaded modified is prepared
2.5h
0.5siW
12/ Al-SBA-15 composite solid acid catalyst.
Respectively by 0.48 gram of Cs
2cO
3with 3.49 grams of H
3siW
12o
406H
2o is made into the aqueous solution of 0.1mol/L and 0.08mol/L.First in cesium carbonate aqueous solution, 10 grams of Al-SBA-15 type molecular sieves are added, stirred at ambient temperature 3 hours, evaporating water at 80 DEG C of temperature, in 500 DEG C of roasting temperatures 3 hours; Then the sample of roasting is mixed with silicon tungsten acid solution, stirred at ambient temperature 12 hours, evaporating water at 80 DEG C of temperature, at 120 DEG C of temperature dry 5 hours, in 200 DEG C of roasting temperatures 2 hours, obtain Cs
2.5h
0.5siW
12charge capacity is the Cs of 30wt%
2.5h
0.5siW
12/ Al-SBA-15 composite solid acid catalyst, is designated as CAT-30(embodiment 30).
(10) Cs that phosphato-molybdic heteropolyacid cesium salt is loaded modified is prepared
2.5h
0.5pMo
12/ Al-SBA-15 composite solid acid catalyst.
Respectively by 0.81 gram of Cs
2cO
3with 3.83 grams of H
3pMo
12o
406H
2o is made into the aqueous solution of 0.1mol/L and 0.08mol/L.First in cesium carbonate aqueous solution, 10 grams of Al-SBA-15 type molecular sieves are added, stirred at ambient temperature 3 hours, evaporating water at 80 DEG C of temperature, in 500 DEG C of roasting temperatures 3 hours; Then by the sample of roasting and phospho-molybdic acid aqueous solution, stirred at ambient temperature 12 hours, evaporating water at 80 DEG C of temperature, at 120 DEG C of temperature dry 5 hours, in 200 DEG C 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 composite solid acid catalyst, is designated as CAT-31(embodiment 31).
(11) AlCl that aluminum chloride is loaded modified is prepared
3/ Al-SBA-15 composite solid acid catalyst.
By the Al-SBA-15 type molecular sieve of 10 grams of embodiment 1 gained and 250 milliliters of dry CCl
4be added in the there-necked flask of 500 milliliters, oil bath reflux 1.5 hours, then add 2 grams of aluminum chloride, continue reflux 3 hours; Filter, and use hot CCl
4wash 2 times, the solid obtained at 120 DEG C of temperature dry 5 hours, obtains the AlCl that aluminum chloride charge capacity is 20wt%
3/ Al-SBA-15 composite solid acid catalyst, is designated as CAT-32(embodiment 32).
(12) according to the method for embodiment 32, the loaded modified ZnCl that zinc chloride charge capacity is 20wt% is prepared
2/ Al-SBA-15 composite solid acid catalyst, is designated as CAT-33(embodiment 33).
(13) according to the method for embodiment 32, the loaded modified FeCl that iron(ic) chloride charge capacity is 20wt% is prepared
3/ Al-SBA-15 composite solid acid catalyst, is designated as CAT-34(embodiment 34).
(14) according to the method for embodiment 32, the loaded modified CuCl that cupric chloride charge capacity is 20wt% is prepared
2/ Al-SBA-15 composite solid acid catalyst, is designated as CAT-35(embodiment 35).
(15) according to the method for embodiment 32, the loaded modified CrCl that chromium chloride charge capacity is 20wt% is prepared
2/ Al-SBA-15 composite solid acid catalyst, is designated as CAT-36(embodiment 36).
Embodiment 37:
With nitric acid synthesis Al-SBA-15 type molecular sieve catalyst
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 take 20 grams of P123, mix with the distilled water of calculated amount and nitric acid, at 40 DEG C of temperature, be uniformly mixed 1.0 hours, the aluminum nitrate adding calculated amount continues to be uniformly mixed 1.0 hours; Then, the tetraethoxy adding calculated amount continues to be uniformly mixed 5.0 hours; Crystallization 12 hours under 70 DEG C and autogenous pressure condition, through filtering, washing, 120 DEG C of drying treatment 4 hours, at 550 DEG C of roastings, 5.0 hours removed template methods, obtain Al-SBA-15 type molecular sieve catalyst powder, through extruded moulding with broken, obtain 20 ~ 40 order granules of catalyst, be designated as CAT-37.
Embodiment 38:
With sulfuric acid synthesis Al-SBA-15 type molecular sieve catalyst
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 take 20 grams of P123, mix with the distilled water of calculated amount and sulfuric acid, at 40 DEG C of temperature, be uniformly mixed 1.0 hours, the monohydrate alumina adding calculated amount continues to be uniformly mixed 1.0 hours; Then, the tetraethoxy adding calculated amount continues to be uniformly mixed 5.0 hours; After filtration, washing, 100 DEG C of drying treatment 6 hours, at 550 DEG C of roastings, 5.0 hours removed template methods, obtain Al-SBA-15 type molecular sieve catalyst powder, through extruded moulding with broken, obtain 20 ~ 40 order granules of catalyst, be designated as CAT-38.
Embodiment 39 ~ 76:
Carry out catalytic reforming generation oil with solid acid catalyst and remove olefine reaction.
Adopt fixed-bed reactor, reactor is the stainless steel tube of long 100cm, internal diameter 1.0cm, and by 5.0 grams of catalyst loading portions in the reactor, quartz sand is filled up at reactor two ends.At pressure 1.5MPa, temperature 220 DEG C, mass space velocity 1.0h
-1under condition, generate oil to the catalytic reforming of certain petrochemical enterprise naphtha fraction to continue to remove olefine reaction experiment, the RPA-100Br type bromine index determinator assaying reaction raw material produced with Jiangsu Jianghuan Analyser Co., Ltd. and the bromine index of refined products, the measurement result of raw material bromine index is 835.6mgBr/100g, and the experimental result of refined products bromine index lists in table 2.
As can be seen from table 2 data, prepared catalyst refined products bromine index is at reaction conditions less than 70 mgBr/100g, and de-alkene rate is greater than 91%, and the sustained reaction operating time is longer than 90 days, illustrate that prepared catalyst has higher deolefination catalytic activity, there is good activity stability.
Table 2
Embodiment 77:
Investigate temperature of reaction and the impact that oil removes alkene is generated on catalytic reforming.
Adopt fixed-bed reactor, reactor is the stainless steel tube of long 100cm, internal diameter 1.0cm, and by the CAT-1 catalyst loading portion in the reactor prepared by 5.0 grams of embodiments 1, quartz sand is filled up at reactor two ends.At pressure 2.0MPa, mass space velocity 1.0h
-1under condition, oil is generated to the catalytic reforming of certain petrochemical enterprise and removes olefine reaction experiment, with the bromine index of RPA-100Br type bromine index determinator assaying reaction raw material and refined products, the measurement result of raw material bromine index is 835.6mgBr/100g, and the refined products bromine index measurement result of differing temps is listed in table 3.From table 3 data, de-alkene rate improves along with temperature of reaction and increases, and this illustrates that suitably improving temperature of reaction is conducive to reforming and generating oil-off olefin.
Table 3
Embodiment 78:
Investigation quality air speed generates on catalytic reforming the impact that oil removes alkene.
Adopt fixed-bed reactor, reactor is the stainless steel tube of long 100cm, internal diameter 1.0cm, and by the CAT-1 catalyst loading portion in the reactor prepared by 5.0 grams of embodiments 1, quartz sand is filled up at reactor two ends.Under the condition of pressure 1.5MPa, temperature 220 DEG C, oil is generated to the catalytic reforming of certain petrochemical enterprise and removes olefine reaction experiment, with the bromine index of RPA-100Br type bromine index determinator assaying reaction raw material and refined products, the measurement result of raw material bromine index is 835.6mgBr/100g, and the refined products bromine index measurement result of different mass air speed is listed in table 4.As can be seen from Table 4, de-alkene rate reduces along with mass space velocity and increases, and this illustrates that suitably reducing mass space velocity is conducive to improving reforming and generating oil-off alkene rate.
Table 4
Embodiment 79:
Catalytic reforming generates the serial operation that oil reacts through absorption pre-treatment and catalysis deolefination.
The D005 type acidic ion exchange resin that the atlapulgite adopting Fushun Petrochemical Company to produce respectively, the HY molecular sieve of Wenzhou Hua Hua group company production, the 13X molecular sieve of Shanghai Chemical Reagent Co., Ltd., Sinopharm Group and gac, Dandong Mingzhu Special Type Resin Co., Ltd. produce is as sorbent material.By two fixed-bed reactor series connection, first reactor is as adsorption treatment bed, and second reactor is as beds.10.0 grams of sorbent materials and 5.0 grams of catalyzer CAT-1 are seated in first and second reactor respectively, quartz sand is all filled up in the two ends of two reactors.The reaction experiment continuing to remove alkene is carried out under generating the condition of oily inlet amount 5.0g/h in pressure 2.0MPa, first temperature of reactor, 60 DEG C, second temperature of reactor 220 DEG C, catalytic reforming, with the bromine index of RPA-100Br type bromine index determinator assaying reaction raw material and refined products, the measurement result of raw material bromine index is 835.6mgBr/100g, and the refined products bromine index measurement result of different sustained reaction time is listed in table 5.
Table 5
From table 5 data, through the lasting catalytic reformate deolefination reaction of 100 days, refined products bromine index was less than 45 mgBr/100g, and de-alkene rate is all the time more than 94.6%, and under showing this operational condition, catalyzer has good activity stability.
Embodiment 80:
The serial operation that BTX aromatics is reacted through absorption pre-treatment and the catalysis deolefination of different condition.
Adopt the 13X molecular sieve of Shanghai Chemical Reagent Co., Ltd., Sinopharm Group as sorbent material, by two fixed-bed reactor series connection, first reactor is as adsorption treatment bed, second reactor is as beds, sorbent material and catalyzer CAT-1 are seated in first and second reactor respectively, quartz sand is all filled up in the two ends of two reactors.Pressure 6.0MPa, first temperature of reactor 10 ~ 200 DEG C and mass space velocity 0.2 ~ 15 hour
-1, second temperature of reactor 220 DEG C and mass space velocity 1.0 hours
-1condition under carry out the reaction experiment that reformation BTX aromatics removes alkene, with the bromine index of RPA-100Br type bromine index determinator assaying reaction raw material and refined products, the measurement result of BTX aromatics raw material bromine index is 865.5mgBr/100g, different condition is adsorbed pre-treatment and determines that the refined products bromine index measurement result that condition catalysis deolefination reacts lists in table 6.
Table 6
As can be seen from Table 6, aromatic hydrocarbons through different condition absorption pre-treatment with determine that the catalysis deolefination of condition reacts serial operation, along with adsorption temp improves or the reduction of quality of adsorption air speed, the bromine index of refining aromatic hydrocarbons reduces gradually, deolefination effect improves gradually, shows suitably to improve adsorption temp or reduce quality of adsorption air speed to be conducive to improving aromatic hydrocarbon refining effect.
Embodiment 81:
The BTX aromatics of two reactors in series reaction units is adopted to remove olefine reaction.
Adopt the fixed-bed reactor of two reactors in series to react, two reactors are the stainless steel tube of long 100cm, internal diameter 1.0cm.Be seated in the middle part of first reactor and second reactor by 5.0 grams of catalyzer CAT-1 and 5.0 gram catalyzer CAT-4 respectively, quartz sand is all filled up in the two ends of two reactors.The reaction experiment that lasting BTX aromatics removes alkene is carried out under the condition of the reformation BTX aromatics inlet amount 5.0g/h of pressure 1.0MPa, first temperature of reactor, 100 DEG C, second temperature of reactor 220 DEG C, catalytic reforming/aromatic extraction unit production, the measurement result of BTX aromatics 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 7.With Agilent Technologies Shanghai Analytical Instrument Co., Ltd produce there are long 50 meters of OV-101 capillary columns, 1790 type gas chromatographs of fid detector carry out compositional analysis to BTX aromatics raw material and refined products, the results are shown in Table 8.
Table 7
From table 7 data, through the lasting BTX aromatics deolefination reaction of 100 days, de-alkene rate was all the time more than 95%, and under showing this operational condition, catalyzer has good activity stability, and the device stable operation time is long.
Table 8
As can be seen from Table 8, the BTX aromatics product through catalyst treatment substantially keeps identical with raw material, the change that BTX aromatics product does not substantially occur on composition on product composition, illustrates that this catalyzer can meet the requirement of industrial production to quality product.
Embodiment 82:
Carry out the reaction experiment that benzene removes alkene.
Adopt fixed-bed reactor, by the CAT-1 catalyst loading portion in the reactor prepared by 5.0 grams of embodiments 1, quartz sand is filled up at reactor two ends.At pressure 3.0MPa, temperature 240 DEG C, mass space velocity 2.0h
-1condition under, through the benzene that fractionation by distillation obtains, olefine reaction experiment is removed to certain petrochemical enterprise reformed arene, with the bromine index of 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 continuing the reaction of 90 days, the measurement result of commercial benzene bromine index is less than 41.2mgBr/100g.
Embodiment 83:
Carry out the reaction experiment of steam cracking arene engaging scraping alkene.
Adopt fixed-bed reactor, by the CAT-1 catalyst loading portion in the reactor prepared by 5.0 grams of embodiments 1, quartz sand is filled up at reactor two ends.At pressure 3.0MPa, temperature 250 DEG C, mass space velocity 2.0h
-1condition under, olefine reaction experiment is removed to the steam cracking aromatic hydrocarbons of certain petrochemical enterprise, with the bromine index of 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 continuing the reaction of 90 days, the measurement result of refining steam cracking aromatic hydrocarbons bromine index is less than 83.0mgBr/100g.
Above-mentionedly show, catalyzer provided by the invention has very high catalytic activity, reaction preference and activity stability, and in Arene removal provided by the invention, the method for trace amounts of olefin has good application prospect.
Claims (9)
1. utilize a method for alkene in M-SBA-15 type mesopore molecular sieve Arene removal, it is characterized in that described method is: in temperature 30 ~ 350 DEG C, pressure 0.1 ~ 10MPa, feedstock quality air speed 0.1 ~ 15 hour
-1condition under, by aromatic hydrocarbons and solid acid catalyst contact reacts, obtain the aromatic hydrocarbons removed after alkene; Described solid acid catalyst is the composite solid acid catalyst obtained containing the M-SBA-15 mesoporous molecular sieve catalyst of substituted element M or the loaded modified compound of M-SBA-15 mesoporous molecular sieve catalyst; Described aromatic hydrocarbons is the aromatic hydrocarbons that reformed oil, reformed arene or steam cracking produce;
Described substituted element M is the mixture of one or more arbitrary proportions following: (1) magnesium, (2) calcium, (3) strontium, (4) boron, (5) aluminium, (6) gallium, (7) manganese, (8) iron, (9) cobalt, (10) nickel, (11) copper, (12) zinc, (13) titanium, (14) vanadium, (15) chromium, (16) germanium, (17) zirconium, (18) niobium, (19) molybdenum, (20) tin, (21) tungsten; In described M and molecular sieve, Si atomic ratio is 0.001 ~ 1:1;
Described modified compound is the mixture of one or more arbitrary proportions following: (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 counts 0.01 ~ 70wt% with M-SBA-15 mesoporous molecular sieve catalyst quality.
2. utilize the method for alkene in M-SBA-15 type mesopore molecular sieve Arene removal as claimed in claim 1, it is characterized in that described M-SBA-15 type mesoporous molecular sieve catalyst obtains as follows: with triblock polymer EO
20pO
70eO
20for 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, by a certain amount of EO
20pO
70eO
20, H
2o, mineral acid mix, and add precursor and the silicon source of substituted element M, are uniformly mixed, described H
2o is distilled water, crystallization 0 ~ 72 hour under 10 ~ 200 DEG C of conditions, obtains crystallization product after filtration with after washing, then by crystallization product drying and calcination process removed template method, obtains described M-SBA-15 type mesoporous molecular sieve catalyst; Described silicon source is silicon sol, tetraethoxy or methyl silicate; Described n is the valence electron number of substituted element M, and described mineral acid is one of following: hydrochloric acid, nitric acid or sulfuric acid.
3. utilize the method for alkene in M-SBA-15 type mesopore molecular sieve Arene removal as claimed in claim 2, it is characterized in that the precursor of described substituted element M is oxide compound, acid, oxyhydroxide or salt.
4. utilize the method for alkene in M-SBA-15 type mesopore molecular sieve Arene removal as claimed in claim 2, 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, Alumina gel, alumina gel or Tai-Ace S 150.
5. utilize the method for alkene in M-SBA-15 type mesopore molecular sieve Arene removal as claimed in claim 1, it is characterized in that described composite solid acid catalyst obtains as follows: calculate modified compound consumption according to modified compound charge capacity, be dissolved in the solution obtained in solvent with modified compound and dip treating is carried out to M-SBA-15 type mesopore molecular sieve, then drying is or/and roasting, namely obtains the composite solid acid catalyst that modified compound charge capacity is 0.01 ~ 60wt%; Described solvent is one of following: water, acetone, tetracol phenixin or dehydrated alcohol.
6. utilize the method for alkene in M-SBA-15 type mesopore molecular sieve Arene removal as claimed in claim 1, it is characterized in that described temperature of reaction 100 ~ 300 DEG C, pressure 0.2 ~ 4.0MPa, charging total mass air speed 0.5 ~ 10.0 hour
-1.
7. utilize the method for alkene in M-SBA-15 type mesopore molecular sieve Arene removal as claimed in claim 1, it is characterized in that described aromatic hydrocarbons is benzene, toluene or dimethylbenzene after reformed arene or steam cracking aromatics seperation.
8. utilize the method for alkene in M-SBA-15 type mesopore molecular sieve Arene removal as claimed in claim 1, it is characterized in that the method for alkene in described Arene removal also comprises aromatic hydrocarbons pre-treatment, described aromatic hydrocarbons pre-treatment is that aromatic hydrocarbons contacts with solid acid catalyst again and reacts after adsorbent bed absorption; Described absorption pretreatment condition is: temperature 0 ~ 200 DEG C, pressure 0.1 ~ 6.0MPa, mass space velocity 0.2 ~ 15 hour
-1, described sorbent material is one or more arbitrary proportion mixtures following: 13X molecular sieve, HY molecular sieve, atlapulgite, gac, HUSY molecular sieve or acidic ion exchange resin.
9. utilize the method for alkene in M-SBA-15 type mesopore molecular sieve Arene removal as claimed in claim 1, it is characterized in that described reaction carries out in the reactor that two or more are in series or in parallel to form.
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| CN103272629A (en) * | 2013-04-25 | 2013-09-04 | 安徽生力农化有限公司 | Alcoholysis catalyst comprising palladium and metal oxides loaded by mesoporous molecular sieve and preparation method thereof |
| CN103272628A (en) * | 2013-04-25 | 2013-09-04 | 安徽生力农化有限公司 | Alcoholysis catalyst comprising metal oxides loaded by mesoporous molecular sieve and preparation method thereof |
| CN103285907A (en) * | 2013-04-25 | 2013-09-11 | 安徽生力农化有限公司 | Mesoporous molecular sieve supported composite metal oxide alcoholysis catalyst, and preparation method of alcoholysis catalyst |
| CN104449823B (en) * | 2013-09-23 | 2017-01-25 | 中国石油化工股份有限公司 | Method for removing olefin from mixed aromatics |
| CN106582776B (en) * | 2016-11-18 | 2019-08-16 | 湘潭大学 | A kind of Sn-Zr/SBA-15 mesoporous molecular sieve catalyst and the preparation method and application thereof |
| CN109485060B (en) * | 2017-09-13 | 2020-12-18 | 中国石油化工股份有限公司 | SBA-16 molecular sieve modified by nano iron and preparation method and application thereof |
| CN109046438B (en) * | 2018-08-21 | 2021-06-29 | 海南大学 | Double-activity Ni2P/Zr-SBA-15 catalyst and preparation method and application thereof |
| CN109603893A (en) * | 2018-12-10 | 2019-04-12 | 合肥学院 | A kind of preparation method of Cu, Sr doping SBA-16 mesopore molecular sieve |
| CN112521243B (en) * | 2019-09-19 | 2023-07-04 | 中国石油化工股份有限公司 | Method and system for long-period running toluene methanol methylation reaction |
| CN111151291A (en) * | 2020-01-21 | 2020-05-15 | 山东玉皇化工有限公司 | Preparation method and application of mesoporous molecular sieve catalyst |
| CN111760584A (en) * | 2020-07-10 | 2020-10-13 | 安徽国星生物化学有限公司 | Preparation method of novel picoline catalyst |
| CN115007201A (en) * | 2022-06-01 | 2022-09-06 | 浙江工业大学 | Microporous/mesoporous composite SAPO-5 molecular sieve solid acid catalyst, and preparation method and application thereof |
| CN115010569A (en) * | 2022-06-01 | 2022-09-06 | 浙江工业大学 | Method for synthesizing linear alkyl aromatic hydrocarbon |
| CN116477586A (en) * | 2023-01-03 | 2023-07-25 | 万华化学集团股份有限公司 | Impurity removing method for dichloro sulfonyl imide |
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