CN103012035A - 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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- CN103012035A CN103012035A CN2012104989377A CN201210498937A CN103012035A CN 103012035 A CN103012035 A CN 103012035A CN 2012104989377 A CN2012104989377 A CN 2012104989377A CN 201210498937 A CN201210498937 A CN 201210498937A CN 103012035 A CN103012035 A CN 103012035A
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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 the method for alkene in a kind of HMCM-41 of utilization type mesopore molecular sieve Arene removal, especially a kind of method that adopts solid acid catalyst to react trace amounts of olefin in the Arene removal.
(2) background technology
Aromatic hydrocarbons is the important foundation raw material, and petrochemical industry mainly adopts petroleum naphtha catalytic reforming/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 solvent oil cut, also contains a small amount of alkene.This part alkene character is active, and easily forming colloid affects the aromatic hydrocarbon product quality, and some follow-up chemical engineering processes are had detrimentally affect, affects further processing and the utilization of aromatic hydrocarbons.Therefore, in order to obtain qualified industrial chemicals and to guarantee carrying out smoothly of subsequent technique, the olefin impurity in the aromatic hydrocarbons must be carried out deep removal.At present, the method that removes olefin impurity that is extensively adopted by domestic and international refinery mainly contains hydrofining and clay-filtered two kinds.
Hydrofining mainly is to utilize platinum or palladium to be planted on the aluminum oxide as catalyzer, carry out " back end hydrogenation " in the reforming reactor back process is to realize that thus olefin saturated reaches the purpose that removes alkene.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 that removes alkene.Although clay treatment process has obtained widely industrial application, the effect that removes alkene is relatively poor; In actual process, the carclazyte life cycle is short, consumption is large, and the carclazyte behind the inactivation can not be regenerated, and just need to more renew carclazyte in about 1 month, and frequent has increased the aromatic hydrocarbons loss and workload, a large amount of useless carclazytes need heap buried to process, and causes environmental pollution.
From 1992, the scientist of U.S. Mobil company successfully synthesized since the MCM-41 meso-porous molecular sieve material first, because it has that specific surface area is large, the duct is regular, aperture and the acid characteristics such as adjustable, had caused extensive concern in catalytic field research.But there is the weak shortcoming of acidity in this type of mesopore molecular sieve, and its application prospect is limited by very large.When this molecular sieve analog Hydrothermal Synthesis, add the isomorphous substitution element, or it is loaded modified that molecular sieve is carried out acidic substance, can improve the molecular sieve catalyst surface acidity, improves 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 method of utilizing alkene in the HMCM-41 type mesopore molecular sieve Arene removal, described method was: 30～350 ℃ 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 obtains to remove the aromatic hydrocarbons of alkene; Described aromatic hydrocarbons is the aromatic hydrocarbons that reformed oil, reformed arene or steam cracking device generate;
Described solid acid catalyst is to contain the HMCM-41 type mesoporous molecular sieve catalyst of substituted element M or contain the composite solid acid catalyst that the loaded modified compound of HMCM-41 mesoporous molecular sieve catalyst of substituted element M obtains; The Si atomic ratio is 0.01～1:1 in described M and the molecular sieve;
Described substituted element M is following one or more mixture: (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 following one or more mixture: 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%, preferred 3.0 ~ 50.0wt%.
Further, the described HMCM-41 mesoporous molecular sieve catalyst preparation method who contains substituted element M is: according to MO
N/2: SiO
2: CTMAB:NaOH:ETHA: H
2The amount proportioning 1:1～100:0.5 of the raw material of the O～preferred MO of 3:0.5～5:0～30:50～300(
N/2: SiO
2: CTMAB:NaOH:ETHA: H
2Feed molar proportioning 1:5.0～50.0:1.0 of O～2.5:1.5～4.0:0～20.0:100.0～240.0), with precursor, silicon source, cetyl trimethylammonium bromide template, sodium hydroxide, dehydrated alcohol and the H of the substituted element M of respective amount
2O mixes, under 50～100 ℃ of temperature condition, mix 1～10 hour (preferred 60～90 ℃ of lower stirrings 3～8 hours), crystallization 2 hours～5 days (preferred 120～180 ℃ of crystallization 12～48 hours) under 100～200 ℃ of conditions, after filtration, the washing, obtain crystallization product; Then, crystallization product is at 2～10 hours removed template methods of 1～8 hour, 300～600 ℃ roastings of 50～150 ℃ of dryings; Be that the aqueous ammonium nitrate solution of 0.5～1.5mol/L stirs under 60～100 ℃ of temperature and carried out ion-exchange in 1～10 hour with concentration again, again through 50～150 ℃ of dryings 1～8 hour, 300～600 ℃ of roastings 2～10 hours obtain containing Jie's HMCM-41 scintilla sieve catalyst of substituted element M, MO
N/2Middle M is the substituted metal element, and n is the valence electron number of substituted element M.
Further, the precursor of described substituted element M is the oxide compound of M, the acid of M, the oxyhydroxide of M or the salt of M.
Further, when described substituted element M was Al, the precursor of described substituted element M was: aluminum isopropylate, boehmite, pseudo-boehmite, monohydrate alumina, aluminum nitrate, aluminium colloidal sol, alumina gel or Tai-Ace S 150.
Further, described silicon source is silicon sol, tetraethoxy or methyl silicate.
Further, described composite solid acid catalyst makes as follows: require to calculate the modified compound consumption according to the modified compound charge capacity with respect to carrier, be dissolved in the solution that obtains in the solvent with modified compound the HMCM-41 mesopore molecular sieve that contains substituted element M is carried out dip treating, then through super-dry or/and roasting, 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 ethanol.
Further, 100～300 ℃ of described temperature of reaction, pressure 0.2～4.0MPa, mass space velocity are 0.5～10.0 hour
-1, most preferably 220～260 ℃ of temperature of reaction, pressure 1.0～4.0MPa, mass space velocity are 1.0～3.0 hours
-1
Further, described aromatic hydrocarbons can also be benzene, toluene or the dimethylbenzene after reformed arene or the separation of steam cracking aromatic hydrocarbons, and described separation method is generally distillation separation method for well known to a person skilled in the art method.
Further, described aromatic hydrocarbons with also pass through adsorbent bed absorption pre-treatment before solid acid catalyst contacts, 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 mixture: 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 is to carry out in the reactor of two or more serial or parallel connections, the identical or different catalyzer of filling in each reactor.
The moulding of catalyzer of the present invention adopt conventional forming technique (as adding binding agent) with its moulding, make the beaded catalyst of certain particle size.
The optional fixed bed of reactor, expanded bed, fluidized-bed, stirred-tank reactor that the present invention's reaction is adopted, and catalytic distillation reactor.Reaction unit can have a plurality of reactor parallel connections or serial operation.Material 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, olefin(e) centent exceeds standard in the refining aromatic hydrocarbons of second reactor, greater than 100mgBr/100g, second reactor is 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 alkene is mainly reflected in a kind of HMCM-41 of utilization type mesopore molecular sieve 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:
Used monohydrate alumina derives from Shandong Aluminum Co., Ltd. group company among the embodiment.
The 769YP-15A type powder compressing machine that adopts Tianjin Keqi High Technology Corp. to produce carries out compression molding to the molecular sieve catalyst powder, and compression molding pressure is 15MPa.
Embodiment 1:
Synthesizing 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 by weighing 4.86 gram monohydrate aluminas, and the silicon sol of calculated amount, cetyl trimethylammonium bromide (CTMAB), sodium hydroxide, ethanol (ETHA) and deionized water, they are mixed 5.0 hours under 70 ℃ of temperature, crystallization is 24 hours under 150 ℃ and autogenous pressure condition, then filters, washes, 110 ℃ of dryings 3 hours, 550 ℃ of roastings 5 hours obtain the molecular sieve of removed template method; Then press solid-liquid mass ratio 1:20, with aqueous ammonium nitrate solution (NH
4NO
3, 1.0mol/L) the gained molecular sieve was carried out ion-exchange in 5 hours in the stirring of 85 ℃ of temperature, through 110 ℃ of dryings 3 hours and 550 ℃ of roastings 3 hours, obtain Al-HMCM-41 mesoporous molecular sieve catalyst powder again; It after grinding, gets 20～40 mesh sieve divided catalysts through compression molding, is designated as CAT-1.
Embodiment 2:
Synthesizing 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 by weighing 12.1 gram cupric nitrates, and the silicon sol of calculated amount, cetyl trimethylammonium bromide (CTMAB), sodium hydroxide, ethanol (ETHA) and distilled water, they are mixed 8.0 hours under 60 ℃ of temperature, crystallization is 12 hours under 180 ℃ and autogenous pressure condition, then filters, washes, 100 ℃ of dryings 5 hours, 500 ℃ of roastings 8 hours obtain the molecular sieve of removed template method; Then press solid-liquid mass ratio 1:30, with aqueous ammonium nitrate solution (NH
4NO
3, 0.7mol/L) the gained molecular sieve is stirred under 90 ℃ of temperature carried out ion-exchange in 8 hours, through 100 ℃ of dryings 3 hours and 500 ℃ of roastings 3 hours, obtain Cu-HMCM-41 mesoporous molecular sieve catalyst powder again; It after grinding, gets 20～40 mesh sieve divided catalysts through compression molding, is designated as CAT-2.
Embodiment 3:
Synthesizing 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 by weighing 3.1 gram boric acid, and the silicon sol of calculated amount, cetyl trimethylammonium bromide (CTMAB), sodium hydroxide and deionized water, they are mixed 3.0 hours under 90 ℃ of temperature, crystallization is 48 hours under 120 ℃ and autogenous pressure condition, then filters, washes, 120 ℃ of dryings 5 hours, 600 ℃ of roastings 3 hours obtain the molecular sieve of removed template method; Then press solid-liquid mass ratio 1:20, with aqueous ammonium nitrate solution (NH
4NO
3, 1.2mol/L) the gained molecular sieve is stirred under 85 ℃ of temperature carried out ion-exchange in 8 hours, through 120 ℃ of dryings 3 hours and 600 ℃ of roastings 3 hours, obtain B-HMCM-41 mesoporous molecular sieve catalyst powder again; It after grinding, gets 20～40 mesh sieve divided catalysts through compression molding, is designated as CAT-3.
Embodiment 4～21:
Adopt the synthetic method identical with embodiment 1, different is uses respectively 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 as the precursor of substituted element M, the synthetic M-HMCM-41 mesoporous molecular sieve catalyst that contains substituted element is listed in table 1.
Table 1
Embodiment 22～35:
Al-HMCM-41 mesoporous molecular sieve catalyst to embodiment 1 carries out loaded modified preparation composite solid acid catalyst.
Embodiment 1 prepared 20～40 purpose Al-HMCM-41 mesopore molecular sieve particles are used for the operation of follow-up (1)～(14) preparation loaded catalyst:
(1) is that the phosphate aqueous solution of 0.143mol/L carried out room temperature (25 ℃) dip treating 5 hours to the Al-HMCM-41 mesopore molecular sieves of 10 gram embodiment 1 gained with 100 ml concns, then carried out 110 ℃ of dryings 8 hours and 400 ℃ 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 gram boric acid are dissolved in the 30 gram acetone solvents, the Al-HMCM-41 mesopore molecular sieve that adds 10 gram embodiment, 1 gained after the dissolving evenly, at room temperature stirred 20 minutes, heating evaporation falls acetone, 120 ℃ of dryings 3 hours, obtaining the boric acid charge capacity is the B/Al-HMCM-41 composite solid acid catalyst of 50wt%, is designated as CAT-23 catalyzer (embodiment 23).
(3) be that the hydrofluoric acid aqueous solution of 0.167mol/L carried out the room temperature dip treating 24 hours to the Al-HMCM-41 mesopore molecular sieves of 10 gram embodiment 1 gained with 100 ml concns, then carried out 110 ℃ of dryings 5 hours and 200 ℃ of roastings processing in 3 hours, obtaining the F charge capacity is the F/Al-HMCM-41 composite solid acid catalyst of 3.0Wt%, is designated as CAT-24 catalyzer (embodiment 24).
(4) according to the method for embodiment 24, preparation Neutral ammonium fluoride charge capacity is the loaded modified NH of 3.0wt%
4F/Al-HMCM-41 composite solid acid catalyst is designated as CAT-25(embodiment 25).
(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-HMCM-41 composite solid acid catalyst.The phosphorus heteropoly tungstic acid aqueous solution that with 100 ml concns is 0.008mol/L carried out the room temperature dip treating 24 hours to the Al-HMCM-41 mesopore molecular sieves of 10 gram embodiment, 1 gained, then carried out 110 ℃ of dryings 3 hours and 300 ℃ of calcination process 3 hours, obtained PW
12Charge capacity is the PW of 20wt%
12/ Al-HMCM-41 composite solid acid catalyst is designated as CAT-26(embodiment 26).
(6) with the loaded modified SiW of silicotungstic heteropolyacid (Shenyang becomes bright chemical reagent work) preparation silicotungstic heteropolyacid
12/ Al-HMCM-41 composite solid acid catalyst.The silicotungstic heteropolyacid aqueous solution that with 100 ml concns is 0.013mol/L carried out the room temperature dip treating 24 hours to the Al-HMCM-41 mesopore molecular sieves of 10 gram embodiment, 1 gained, then carried out 110 ℃ of dryings 3 hours and 300 ℃ of calcination process 3 hours, obtained SiW
12Charge capacity is the SiW of 30wt%
12/ Al-HMCM-41 composite solid acid catalyst is designated as CAT-27(embodiment 27).
(7) with the loaded modified PMo of phosphato-molybdic heteropolyacid (the emerging chemical reagent work in Shenyang) preparation phosphato-molybdic heteropolyacid
12/ Al-HMCM-41 composite solid acid catalyst.The phosphato-molybdic heteropolyacid aqueous solution that with 100 ml concns is 0.025mol/L carried out the room temperature dip treating 24 hours to the Al-HMCM-41 mesopore molecular sieves of 10 gram embodiment, 1 gained, then carried out 110 ℃ of dryings 3 hours and 300 ℃ of calcination process 3 hours, obtained PMo
12Charge capacity is the PMo of 30wt%
12/ Al-HMCM-41 composite solid acid catalyst is designated as CAT-28(embodiment 28).
(8) the loaded modified Cs of preparation phosphorus heteropoly tungstic acid cesium salt
2.5H
0.5PW
12/ Al-HMCM-41 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 the Al-HMCM-41 molecular sieve of 10 gram embodiment, 1 gained 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-HMCM-41 composite solid acid catalyst is designated as CAT-29(embodiment 29).
(9) the loaded modified Cs of preparation silicotungstic heteropolyacid cesium salt
2.5H
0.5SiW
12/ Al-HMCM-41 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 the Al-HMCM-41 molecular sieve of 10 gram embodiment, 1 gained 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-HMCM-41 composite solid acid catalyst is designated as CAT-30(embodiment 30).
(10) the loaded modified Cs of preparation phosphato-molybdic heteropolyacid cesium salt
2.5H
0.5PMo
12/ Al-HMCM-41 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 the Al-HMCM-41 molecular sieve of 10 gram embodiment, 1 gained 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-HMCM-41 composite solid acid catalyst is designated as CAT-31(embodiment 31).
(11) the loaded modified AlCl of preparation aluminum chloride
3/ Al-HMCM-41 composite solid acid catalyst.
With the Al-HMCM-41 molecular sieve 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-HMCM-41 composite solid acid catalyst is designated as CAT-32(embodiment 32).
(12) according to the method for embodiment 32, preparation zinc chloride charge capacity is the loaded modified ZnCl of 20wt%
2/ Al-HMCM-41 composite solid acid catalyst is designated as CAT-33(embodiment 33).
(13) according to the method for embodiment 32, preparation iron(ic) chloride charge capacity is the loaded modified FeCl of 20wt%
3/ Al-HMCM-41 composite solid acid catalyst is designated as CAT-34(embodiment 34).
(14) according to the method for embodiment 32, preparation cupric chloride charge capacity is the loaded modified CuCl of 20wt%
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 5.0 gram catalyzer (seeing Table 2) are seated in the reactor middle part, and quartz sand is filled up at the reactor two ends.At pressure 1.0MPa, 220 ℃ of temperature, mass space velocity 1.0h
-1Under the condition, catalytic reforming generation oil to certain petrochemical enterprise naphtha fraction 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 raw material bromine index is 835.6mgBr/100g, and the experimental result of refined products bromine index is listed in table 2.
Can be found out by table 2 data, the refined products bromine index of prepared catalyst under reaction conditions takes off the alkene rate greater than 92% less than 65 mgBr/100g, and the sustained reaction operating time was longer than 90 days, illustrate that prepared catalyst has higher deolefination catalytic activity, has good activity stability.
Table 2
Embodiment 71:
Investigate temperature of reaction catalytic reforming is generated the impact that oil removes 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 2.0MPa, mass space velocity 1.0h
-1Under the condition, catalytic reforming generation oil 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 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 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 deolefination.
Table 3
Embodiment 72:
Investigate mass space velocity catalytic reforming is generated the impact that oil removes 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 220 ℃ of pressure 1.5MPa, temperature, catalytic reforming is generated oil remove 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 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, take off the alkene rate and reduce and increase along with mass space velocity, this explanation suitably reduces mass space velocity and is conducive to improve the alkene rate of taking off.
Table 4
Embodiment 73:
Catalytic reforming generates oil 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.Generate the reaction experiment that continues to remove alkene under the condition of oily inlet amount 5.0g/h in pressure 1.0MPa, 220 ℃ of 50 ℃, second temperature of reactor of first temperature of reactor, 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 as can be known, through 100 days lasting catalytic reformate deolefination reaction, the refined products bromine index took off the alkene rate all the time more than 95% less than 42 mgBr/100g, shows that catalyzer has good activity stability under this operational condition.
Embodiment 74:
BTX aromatics 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 4.0MPa, 10～200 ℃ of first temperature of reactor and mass space velocity 0.2～15 hour
-1, second 220 ℃ of temperature of reactor and mass space velocity 1.0 hours
-1Condition under the BTX aromatics of reforming remove the reaction experiment of alkene, bromine index with 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, and the refined products bromine index measurement result of different condition being adsorbed pre-treatment and the reaction of definite condition catalysis deolefination is listed in table 6.
Table 6
As can be seen from Table 6, BTX aromatics is through the absorption pre-treatment of different condition and the catalysis deolefination reaction 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 75:
Adopt the BTX aromatics of two reactors in series reaction units 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.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 the reformation BTX aromatics inlet amount 5.0g/h of pressure 1.5MPa, 220 ℃ of 100 ℃, second temperature of reactor of first temperature of reactor, catalytic reforming/aromatic extraction unit production, continue the reaction experiment of arene engaging scraping alkene, 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.The 1790 type gas chromatographs with long 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 BTX aromatics raw material and refined products, the results are shown in Table 8.
Table 7
From table 7 data as can be known, through 100 days lasting aromatic hydrocarbons deolefination reaction, take off the alkene rate all the time more than 94%, show that catalyzer has good activity stability under this operational condition, the device stable operation time is long.
Table 8
As can be seen from Table 8, the BTX aromatics purified product of process catalyst treatment keeps identical substantially with raw material on forming, and BTX aromatics does not change on forming substantially, illustrates that this catalyzer can satisfy industrial production to the requirement of quality product.
Embodiment 76:
Carry out benzene and remove the reaction experiment of 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, 250 ℃ of temperature, mass space velocity 3.0h
-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 38.8mgBr/100g.
Embodiment 77:
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 4.0MPa, 260 ℃ 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 80.0mgBr/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. method of utilizing alkene in the HMCM-41 type mesopore molecular sieve Arene removal is characterized in that described method is: 30～350 ℃ 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 removing the aromatic hydrocarbons of alkene; Described aromatic hydrocarbons is the aromatic hydrocarbons that reformed oil, reformed arene or steam cracking device generate;
Described solid acid catalyst is to contain the HMCM-41 type mesoporous molecular sieve catalyst of substituted element M or contain the composite solid acid catalyst that the loaded modified compound of HMCM-41 mesoporous molecular sieve catalyst of substituted element M obtains; The Si atomic ratio is 0.01～1:1 in described M and the molecular sieve;
Described substituted element M is following one or more mixture: (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 following one or more mixture: 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 as claimed in claim 1 the method for alkene in the HMCM-41 type mesopore molecular sieve Arene removal, it is characterized in that the described HMCM-41 mesoporous molecular sieve catalyst preparation method who contains substituted element M is: according to MO
N/2: SiO
2: CTMAB:NaOH:ETHA: H
2The amount proportioning 1:1～100:0.5 of the raw material of O～3:0.5～5:0～30:50～300 is with precursor, silicon source, cetyl trimethylammonium bromide template, sodium hydroxide, dehydrated alcohol and the H of the substituted element M of respective amount
2O mixes, and mixes 1～10 hour under 50～100 ℃ of temperature condition, and crystallization is 2 hours～5 days under 100～200 ℃ of conditions, after filtration, the washing, obtain crystallization product; Then, crystallization product is at 2～10 hours removed template methods of 1～8 hour, 300～600 ℃ roastings of 50～150 ℃ of dryings; Be that the aqueous ammonium nitrate solution of 0.5～1.5mol/L stirs under 60～100 ℃ of temperature and carried out ion-exchange in 1～10 hour with concentration again, again through 50～150 ℃ of dryings 1～8 hour, 300～600 ℃ of roastings 2～10 hours obtain containing Jie's HMCM-41 scintilla sieve catalyst of substituted element M, MO
N/2Middle M is the substituted metal element, and n is the valence electron number of substituted element M.
3. utilize as claimed in claim 1 the method for alkene in the HMCM-41 type mesopore molecular sieve Arene removal, the precursor that it is characterized in that described substituted element M is the oxide compound of M, the acid of M, the oxyhydroxide of M or the salt of M.
4. utilize as claimed in claim 1 or 2 the method for alkene in the HMCM-41 type mesopore molecular sieve Arene removal, 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, aluminium colloidal sol, alumina gel or Tai-Ace S 150.
5. utilize as claimed in claim 2 the method for alkene in the HMCM-41 type mesopore molecular sieve Arene removal, it is characterized in that described silicon source is silicon sol, tetraethoxy or methyl silicate.
6. utilize as claimed in claim 1 the method for alkene in the HMCM-41 type mesopore molecular sieve Arene removal, it is characterized in that described composite solid acid catalyst makes as follows: require to calculate the modified compound consumption according to the modified compound charge capacity with respect to carrier, be dissolved in the solution that obtains in the solvent with modified compound the HMCM-41 mesopore molecular sieve that contains substituted element M is carried out dip treating, then through super-dry or/and roasting, 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 ethanol.
7. utilize as claimed in claim 1 the method for alkene in the HMCM-41 type mesopore molecular sieve Arene removal, it is characterized in that 100～300 ℃ of described temperature of reaction, pressure 0.2～4.0MPa, mass space velocity 0.5～10.0 hour
-1
8. utilize as claimed in claim 1 the method for alkene in the HMCM-41 type mesopore molecular sieve Arene removal, it is characterized in that described aromatic hydrocarbons is benzene, toluene or the dimethylbenzene after reformed arene or steam cracking aromatic hydrocarbons separate.
9. utilize as claimed in claim 1 the method for alkene in the HMCM-41 type mesopore molecular sieve Arene removal, also pass through adsorbent bed absorption pre-treatment before it is characterized in that described aromatic hydrocarbons and solid acid catalyst contacting, 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 mixture: 13X molecular sieve, HY molecular sieve, atlapulgite, gac, HUSY molecular sieve or acidic ion exchange resin.
10. utilize as claimed in claim 1 the method for alkene in the HMCM-41 type mesopore molecular sieve Arene removal, it is characterized in that described reaction is to carry out in the reactor of two or more serial or parallel connections.
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