CN103012035B - Method for removing trace hydrocarbon out of aromatic hydrocarbon by utilizing HMCM-41 type mesoporous molecular sieve - Google Patents
Method for removing trace hydrocarbon out of aromatic hydrocarbon by utilizing HMCM-41 type mesoporous molecular sieve Download PDFInfo
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Abstract
The invention discloses a method for removing hydrocarbon out of aromatic hydrocarbon by utilizing an HMCM-41 type mesoporous molecular sieve. The method comprises the following steps of allowing aromatic hydrocarbon to contact and react with solid acid catalyst under conditions that the temperature is between 30 and 350 DEG C, the pressure is between 0.1 and 12MPa and the feeding mass space velocity is between 0.1 and 15 hour<-1> to obtain hydrocarbon removed aromatic hydrocarbon, wherein the hydrocarbon is reformed oil, reformed hydrocarbon or aromatic hydrocarbon generated by a steam cracking device. The method is simple in process flow, does not consume hydrogen, and is low in device investment and operation cost; the catalyst is good in activity stability, the device is stable and long in operation time, less hydrocarbon is lost, and operation of frequent switching between reaction and regeneration of the reactor can be avoided; and the catalyst is reproducible to avoid massive waste catalyst accumulation and bury, and has small influence on the environment.
Description
(1) technical field
The present invention relates to a kind of method utilizing alkene in HMCM-41 type mesopore molecular sieve Arene removal, especially a kind of method adopting solid acid catalyst to carry out reacting trace amounts of olefin in Arene removal.
(2) background technology
Aromatic hydrocarbons is important foundation raw material, and petrochemical industry mainly adopts Naphtha reformation/arene extracting process to produce aromatic hydrocarbons.Naphtha fraction is converted into reformed oil through catalytic reforming, and reformed oil is rich in aromatic hydrocarbons and spirit fraction, also containing a small amount of alkene.This part alkene character is enlivened, and easily forming colloid affects aromatic hydrocarbon product quality, and has detrimentally affect to some follow-up chemical engineering processes, affects further processing and the utilization of aromatic hydrocarbons.Therefore, in order to obtain qualified industrial chemicals and ensure carrying out smoothly of subsequent technique, the olefin impurity in aromatic hydrocarbons must be carried out deep removal.At present, hydrofining and clay-filtered two kinds are mainly contained by the method removing olefin impurity that domestic and international refinery extensively adopts.
Hydrofining mainly utilizes platinum or palladium to plant on alumina as catalyzer, 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 life cycle is short, consumption large, and the carclazyte after inactivation can not regenerate, and within about 1 month, just needs more to renew carclazyte, and frequent replacing adds aromatic hydrocarbons loss and workload, a large amount of spent bleaching clays need heap buried process, causes environmental pollution.
From 1992, since the scientist of Mobil company of the U.S. has successfully synthesized MCM-41 meso-porous molecular sieve material first, because of its have that specific surface area is large, duct is regular, aperture and the feature such as acidity is adjustable, in catalytic field research, cause extensive concern.But there is the more weak shortcoming of acidity in this type of mesopore molecular sieve, its application prospect is limited by very large.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 HMCM-41 type mesopore molecular sieve Arene removal, described method is: in temperature 30 ~ 350 DEG C, pressure 0.1 ~ 12MPa, 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, obtains the aromatic hydrocarbons removing alkene; Described aromatic hydrocarbons is the aromatic hydrocarbons that reformed oil, reformed arene or steam cracking device generate;
Described solid acid catalyst is the composite solid acid catalyst that the HMCM-41 type mesoporous molecular sieve catalyst containing substituted element M or the loaded modified compound of HMCM-41 mesoporous molecular sieve catalyst containing substituted element M obtain; In described M and molecular sieve, Si atomic ratio is 0.01 ~ 1:1;
Described substituted element M is one or more mixture 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;
Described modified compound is one or more mixture following: phosphoric acid, hydrofluoric acid, Neutral ammonium fluoride, phosphorus heteropoly tungstic acid, silicotungstic heteropolyacid, phosphato-molybdic heteropolyacid, phosphorus heteropoly tungstic acid cesium salt, silicotungstic heteropolyacid cesium salt, phosphato-molybdic heteropolyacid cesium salt, aluminum chloride, zinc chloride, iron(ic) chloride, cupric chloride or boric acid; The charge capacity of described modified compound is 0.01 ~ 60wt%, preferably 3.0 ~ 50.0wt%.
Further, the described HMCM-41 mesoporous molecular sieve catalyst preparation method containing substituted element M is: according to MO
n/2: SiO
2: CTMAB:NaOH:ETHA: H
2the preferred MO of amount proportioning 1:1 ~ 100:0.5 ~ 3:0.5 ~ 5:0 ~ 30:50 ~ 300(of the raw material of O
n/2: SiO
2: CTMAB:NaOH:ETHA: H
2feed molar proportioning 1:5.0 ~ 50.0:1.0 ~ 2.5:1.5 ~ 4.0:0 ~ 20.0:100.0 ~ 240.0 of O), by the precursor of the substituted element M of respective amount, silicon source, cetyl trimethylammonium bromide template, sodium hydroxide, dehydrated alcohol and H
2o mixes, 1 ~ 10 hour is uniformly mixed (preferably 60 ~ 90 DEG C at stir 3 ~ 8 hours) under 50 ~ 100 DEG C of temperature condition, crystallization 2 hours ~ 5 days (preferably 120 ~ 180 DEG C crystallization 12 ~ 48 hours) under 100 ~ 200 DEG C of conditions, after filtration, washing, obtains crystallization product; Then, crystallization product is at 50 ~ 150 DEG C of dryings 1 ~ 8 hour, 300 ~ 600 DEG C of roastings, 2 ~ 10 hours removed template methods; Be that the aqueous ammonium nitrate solution of 0.5 ~ 1.5mol/L stirs and carries out ion-exchange in 1 ~ 10 hour at 60 ~ 100 DEG C of temperature again by concentration, again through 50 ~ 150 DEG C of dryings 1 ~ 8 hour, 300 ~ 600 DEG C of roastings 2 ~ 10 hours, obtain Jie's HMCM-41 scintilla sieve catalyst containing substituted element M, MO
n/2middle M is substituted metal element, and n is the valence electron number of substituted element M.
Further, the precursor of described substituted element M is the salt of the oxide compound of M, the acid of M, the oxyhydroxide of M or M.
Further, when described substituted element M is Al, the precursor of described substituted element M is: aluminum isopropylate, boehmite, pseudo-boehmite, monohydrate alumina, aluminum nitrate, Alumina gel, alumina gel or Tai-Ace S 150.
Further, described silicon source is silicon sol, tetraethoxy or methyl silicate.
Further, described composite solid acid catalyst obtains as follows: require to calculate modified compound consumption according to the modified compound charge capacity relative to carrier, be dissolved in the solution obtained in solvent with modified compound and dip treating is carried out to the HMCM-41 mesopore molecular sieve containing substituted element M, then through super-dry or/and roasting, namely obtain 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 ethanol.
Further, described temperature of reaction 100 ~ 300 DEG C, pressure 0.2 ~ 4.0MPa, mass space velocity 0.5 ~ 10.0 hour
-1, most preferably temperature of reaction 220 ~ 260 DEG C, pressure 1.0 ~ 4.0MPa, mass space velocity 1.0 ~ 3.0 hours
-1.
Further, described aromatic hydrocarbons can also be benzene, toluene or dimethylbenzene after reformed arene or steam cracking aromatics seperation, and the method that described separation method is known to the skilled person, is generally distillation separation method.
Further, also through adsorbent bed absorption pre-treatment before described aromatic hydrocarbons contacts with solid acid catalyst, 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 mixture following: 13X molecular sieve, HY molecular sieve, atlapulgite, gac, HUSY molecular sieve or acidic ion exchange resin (preferred D005 type acidic ion exchange resin).
Further, described reaction carries out in the reactor of two or more serial or parallel connections, the catalyzer that in each reactor, filling is identical or different.
Catalyzer of the present invention shaping adopts the beaded catalyst that conventional forming technique (as added binding agent) is shaping by it, make certain particle size.
The present invention reacts 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.Material 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, in the refining aromatic hydrocarbons of second reactor, olefin(e) centent exceeds standard, and 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 HMCM-41 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:
Monohydrate alumina used in embodiment derives from Shandong Aluminum Co., Ltd. group company.
The 769YP-15A type powder compressing machine adopting Tianjin Keqi High Technology Corp. to produce carries out compression molding to molecular sieve catalyst powder, and compression molding pressure is 15MPa.
Embodiment 1:
The synthesis of Al-HMCM-41 mesoporous molecular sieve catalyst
According to Al
2o
3: SiO
2: CTMAB:NaOH:ETHA: H
2the feed molar proportioning 1:10.0:1.4:2.4:8.67:140.0 of O, take 4.86 grams of monohydrate aluminas, and the silicon sol of calculated amount, cetyl trimethylammonium bromide (CTMAB), sodium hydroxide, ethanol (ETHA) and deionized water, they are uniformly mixed 5.0 hours at 70 DEG C of temperature, under 150 DEG C and autogenous pressure condition, crystallization 24 hours, then filters, washes, 110 DEG C of dryings 3 hours, 550 DEG C of roastings 5 hours, obtain the molecular sieve of removed template method; Then solid-liquid mass ratio 1:20 is pressed, with aqueous ammonium nitrate solution (NH
4nO
3, 1.0mol/L) and ion-exchange was carried out in 5 hours in the stirring of 85 DEG C of temperature to gained molecular sieve, then through 110 DEG C of dryings 3 hours and 550 DEG C of roastings 3 hours, obtain Al-HMCM-41 mesoporous molecular sieve catalyst powder; It is through compression molding, after grinding, gets 20 ~ 40 mesh sieve divided catalysts, is designated as CAT-1.
Embodiment 2:
The synthesis of Cu-HMCM-41 mesoporous molecular sieve catalyst
According to Cu (NO
3)
2: SiO
2: CTMAB:NaOH:ETHA: H
2the feed molar proportioning 1:5.0:1.0:1.5:20.0:100.0 of O, take 12.1 grams of cupric nitrates, and the silicon sol of calculated amount, cetyl trimethylammonium bromide (CTMAB), sodium hydroxide, ethanol (ETHA) and distilled water, they are uniformly mixed 8.0 hours at 60 DEG C of temperature, under 180 DEG C and autogenous pressure condition, crystallization 12 hours, then filters, washes, 100 DEG C of dryings 5 hours, 500 DEG C of roastings 8 hours, obtain the molecular sieve of removed template method; Then solid-liquid mass ratio 1:30 is pressed, with aqueous ammonium nitrate solution (NH
4nO
3, 0.7mol/L) gained molecular sieve stirred at 90 DEG C of temperature and within 8 hours, carries out ion-exchange, then through 100 DEG C of dryings 3 hours and 500 DEG C of roastings 3 hours, obtain Cu-HMCM-41 mesoporous molecular sieve catalyst powder; It is through compression molding, after grinding, gets 20 ~ 40 mesh sieve divided catalysts, is designated as CAT-2.
Embodiment 3:
The synthesis of B-HMCM-41 mesoporous molecular sieve catalyst
According to H
3bO
3: SiO
2: CTMAB:NaOH:H
2the feed molar proportioning 1:50.0:2.5:4.0:240.0 of O, take 3.1 grams of boric acid, and the silicon sol of calculated amount, cetyl trimethylammonium bromide (CTMAB), sodium hydroxide and deionized water, they are uniformly mixed 3.0 hours at 90 DEG C of temperature, under 120 DEG C and autogenous pressure condition, crystallization 48 hours, then filters, washes, 120 DEG C of dryings 5 hours, 600 DEG C of roastings 3 hours, obtain the molecular sieve of removed template method; Then solid-liquid mass ratio 1:20 is pressed, with aqueous ammonium nitrate solution (NH
4nO
3, 1.2mol/L) gained molecular sieve stirred at 85 DEG C of temperature and within 8 hours, carries out ion-exchange, then through 120 DEG C of dryings 3 hours and 600 DEG C of roastings 3 hours, obtain B-HMCM-41 mesoporous molecular sieve catalyst powder; It is through compression molding, after grinding, gets 20 ~ 40 mesh sieve divided catalysts, is designated as CAT-3.
Embodiment 4 ~ 21:
Adopt the synthetic method identical with embodiment 1, unlike the precursor using butyl (tetra) titanate, Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES, zinc nitrate, gallium nitrate, manganous nitrate, strontium nitrate, zirconium nitrate, nitrocalcite, magnesium 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, boric acid alternatively element M respectively, synthesis, containing the M-HMCM-41 mesoporous molecular sieve catalyst of substituted element, lists in table 1.
Table 1
Embodiment 22 ~ 35:
Carry out loaded modifiedly preparing composite solid acid catalyst to the Al-HMCM-41 mesoporous molecular sieve catalyst of embodiment 1.
20 ~ 40 object Al-HMCM-41 mesopore molecular sieve particles prepared by embodiment 1 are used for the operation preparing loaded catalyst in follow-up (1) ~ (14):
(1) be that the Al-HMCM-41 mesopore molecular sieve of phosphate aqueous solution to 10 grams of embodiment 1 gained of 0.143mol/L carries out room temperature (25 DEG C) dip treating 5 hours with 100 ml concns, then carry out 110 DEG C of dryings 8 hours and 400 DEG C of calcination process 3 hours, obtain P
2o
5charge capacity is the P/Al-HMCM-41 composite solid acid catalyst of 10.0Wt%, is designated as CAT-22 catalyzer (embodiment 22).
(2) 5 grams of boric acid are dissolved in 30 grams of acetone solvents, the Al-HMCM-41 mesopore molecular sieve of 10 grams of embodiment 1 gained is added after being uniformly dissolved, at room temperature stir 20 minutes, heating evaporation falls acetone, 120 DEG C of dryings 3 hours, obtain the B/Al-HMCM-41 composite solid acid catalyst that boric acid charge capacity is 50wt%, be designated as CAT-23 catalyzer (embodiment 23).
(3) be that the Al-HMCM-41 mesopore 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 5 hours and 200 DEG C of roastings process in 3 hours, obtain the F/Al-HMCM-41 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-HMCM-41 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-HMCM-41 composite solid acid catalyst.Be that the Al-HMCM-41 mesopore 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 300 DEG C of calcination process 3 hours, obtain PW
12charge capacity is the PW of 20wt%
12/ Al-HMCM-41 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-HMCM-41 composite solid acid catalyst.Be that the Al-HMCM-41 mesopore 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 300 DEG C of calcination process 3 hours, obtain SiW
12charge capacity is the SiW of 30wt%
12/ Al-HMCM-41 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-HMCM-41 composite solid acid catalyst.Be that the Al-HMCM-41 mesopore 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 300 DEG C of calcination process 3 hours, obtain PMo
12charge capacity is the PMo of 30wt%
12/ Al-HMCM-41 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-HMCM-41 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, the Al-HMCM-41 molecular sieve of 10 grams of embodiment 1 gained is 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-HMCM-41 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-HMCM-41 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, the Al-HMCM-41 molecular sieve of 10 grams of embodiment 1 gained is 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-HMCM-41 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-HMCM-41 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, the Al-HMCM-41 molecular sieve of 10 grams of embodiment 1 gained is 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-HMCM-41 composite solid acid catalyst, is designated as CAT-31(embodiment 31).
(11) AlCl that aluminum chloride is loaded modified is prepared
3/ Al-HMCM-41 composite solid acid catalyst.
By the Al-HMCM-41 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-HMCM-41 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-HMCM-41 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-HMCM-41 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-HMCM-41 composite solid acid catalyst, is designated as CAT-35(embodiment 35).
Embodiment 36 ~ 70:
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 be seated in the middle part of reactor by 5.0 grams of catalyzer (see table 2), quartz sand is filled up at reactor two ends.At pressure 1.0MPa, 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 65 mgBr/100g, and de-alkene rate is greater than 92%, 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 71:
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 deolefination.
Table 3
Embodiment 72:
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 catalytic reforming 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 de-alkene rate.
Table 4
Embodiment 73:
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 1.0MPa, first temperature of reactor, 50 DEG C, second temperature of reactor 220 DEG C, catalytic reforming, 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 42 mgBr/100g, and de-alkene rate is all the time more than 95%, and under showing this operational condition, catalyzer has good activity stability.
Embodiment 74:
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 4.0MPa, 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, BTX aromatics through different condition absorption pre-treatment with determine that the catalysis deolefination of condition reacts, 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 75:
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 of lasting arene engaging scraping alkene is carried out under the condition of the reformation BTX aromatics inlet amount 5.0g/h of pressure 1.5MPa, 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 aromatic hydrocarbons deolefination reaction of 100 days, de-alkene rate was all the time more than 94%, 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 purified product through catalyst treatment substantially keeps identical with raw material on composition, and BTX aromatics does not substantially change on composition, illustrates that this catalyzer can meet the requirement of industrial production to quality product.
Embodiment 76:
Carry out the reaction experiment that benzene 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.At pressure 3.0MPa, temperature 250 DEG C, mass space velocity 3.0h
-1condition under, through the benzene that fractionation by distillation obtains, olefine reaction experiment is removed to certain petrochemical enterprise reformation BTX aromatics, 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 38.8mgBr/100g.
Embodiment 77:
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 4.0MPa, temperature 260 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 80.0mgBr/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 HMCM-41 type mesopore molecular sieve Arene removal, it is characterized in that described method is: in temperature 100 ~ 250 DEG C, pressure 0.2 ~ 4MPa, feedstock quality air speed 0.5 ~ 10 hour
-1condition under, by aromatic hydrocarbons and solid acid catalyst contact reacts, obtain the aromatic hydrocarbons removing alkene; Described aromatic hydrocarbons is the aromatic hydrocarbons that reformed oil, reformed arene or steam cracking device generate;
Described solid acid catalyst is the composite solid acid catalyst that the HMCM-41 type mesoporous molecular sieve catalyst containing substituted element M or the loaded modified compound of HMCM-41 mesoporous molecular sieve catalyst containing substituted element M obtain; In described M and molecular sieve, Si atomic ratio is 0.01 ~ 1:1;
Described substituted element M is one or more mixture 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;
Described modified compound is one or more mixture following: phosphoric acid, hydrofluoric acid, Neutral ammonium fluoride, phosphorus heteropoly tungstic acid, silicotungstic heteropolyacid, phosphato-molybdic heteropolyacid, phosphorus heteropoly tungstic acid cesium salt, silicotungstic heteropolyacid cesium salt, phosphato-molybdic heteropolyacid cesium salt, aluminum chloride, zinc chloride, iron(ic) chloride, cupric chloride or boric acid; The charge capacity of described modified compound is 0.01 ~ 60wt%.
2. utilize the method for alkene in HMCM-41 type mesopore molecular sieve Arene removal as claimed in claim 1, it is characterized in that the described HMCM-41 mesoporous molecular sieve catalyst preparation method containing substituted element M is: according to MO
n/2: SiO
2: cetyl trimethylammonium bromide: NaOH: dehydrated alcohol: H
2amount proportioning 1:1 ~ 100:0.5 ~ 3:0.5 ~ 5:0 ~ 30:50 ~ 300 of the raw material of O, by the precursor of the substituted element M of respective amount, silicon source, cetyl trimethylammonium bromide template, sodium hydroxide, dehydrated alcohol and H
2o mixes, and is uniformly mixed 1 ~ 10 hour under 50 ~ 100 DEG C of temperature condition, crystallization 2 hours ~ 5 days under 100 ~ 200 DEG C of conditions, after filtration, washs, obtains crystallization product; Then, crystallization product is at 50 ~ 150 DEG C of dryings 1 ~ 8 hour, 300 ~ 600 DEG C of roastings, 2 ~ 10 hours removed template methods; Be that the aqueous ammonium nitrate solution of 0.5 ~ 1.5mol/L stirs and carries out ion-exchange in 1 ~ 10 hour at 60 ~ 100 DEG C of temperature again by concentration, again through 50 ~ 150 DEG C of dryings 1 ~ 8 hour, 300 ~ 600 DEG C of roastings 2 ~ 10 hours, obtain Jie's HMCM-41 scintilla sieve catalyst containing substituted element M, MO
n/2middle M is substituted metal element, and n is the valence electron number of substituted element M.
3. utilize the method for alkene in HMCM-41 type mesopore molecular sieve Arene removal as claimed in claim 2, it is characterized in that the precursor of described substituted element M is the salt of the oxide compound of M, the acid of M, the oxyhydroxide of M or M.
4. utilize the method for alkene in HMCM-41 type mesopore molecular sieve Arene removal as claimed in claim 2, when it is characterized in that described substituted element M is Al, the precursor of described substituted element 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 HMCM-41 type mesopore molecular sieve Arene removal as claimed in claim 2, it is characterized in that described silicon source is silicon sol, tetraethoxy or methyl silicate.
6. utilize the method for alkene in HMCM-41 type mesopore molecular sieve Arene removal as claimed in claim 1, it is characterized in that described composite solid acid catalyst obtains as follows: require to calculate modified compound consumption according to the modified compound charge capacity relative to carrier, be dissolved in the solution obtained in solvent with modified compound and dip treating is carried out to the HMCM-41 mesopore molecular sieve containing substituted element M, then through super-dry or/and roasting, namely obtain 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 ethanol.
7. utilize the method for alkene in HMCM-41 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 HMCM-41 type mesopore molecular sieve Arene removal as claimed in claim 1, it is characterized in that described aromatic hydrocarbons also through adsorbent bed absorption pre-treatment before contacting with solid acid catalyst, 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 mixture following: 13X molecular sieve, HY molecular sieve, atlapulgite, gac, HUSY molecular sieve or acidic ion exchange resin.
9. utilize the method for alkene in HMCM-41 type mesopore molecular sieve Arene removal as claimed in claim 1, it is characterized in that described reaction carries out in the reactor of two or more serial or parallel connections.
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| CN106345499B (en) * | 2016-08-04 | 2019-10-11 | 盱眙恒信粘土科技有限公司 | It is a kind of load P elements Attapulgite Catalyst preparation method and its reformed oil removing trace amounts of olefin in application |
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| CN108864041A (en) * | 2018-06-12 | 2018-11-23 | 北京京大律业知识产权代理有限公司 | A kind of preparation method of medicine intermediate tetrazole compound |
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| CN112391195B (en) * | 2019-08-16 | 2022-04-05 | 中国石油化工股份有限公司 | Method for removing olefin from aromatic hydrocarbon raw material |
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