CN1066071C - Preparation of modified macro-porous zeolite catalyst and synthetic isopropyl aromatic hydrocarbon - Google Patents
Preparation of modified macro-porous zeolite catalyst and synthetic isopropyl aromatic hydrocarbon Download PDFInfo
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- CN1066071C CN1066071C CN94112680A CN94112680A CN1066071C CN 1066071 C CN1066071 C CN 1066071C CN 94112680 A CN94112680 A CN 94112680A CN 94112680 A CN94112680 A CN 94112680A CN 1066071 C CN1066071 C CN 1066071C
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- 239000003054 catalyst Substances 0.000 title claims abstract description 101
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 title claims abstract description 11
- 229910021536 Zeolite Inorganic materials 0.000 title claims abstract description 10
- 239000010457 zeolite Substances 0.000 title claims abstract description 10
- 238000002360 preparation method Methods 0.000 title claims description 14
- -1 isopropyl aromatic hydrocarbon Chemical class 0.000 title description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims abstract description 81
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims abstract description 63
- 238000006243 chemical reaction Methods 0.000 claims abstract description 45
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 claims abstract description 30
- QQONPFPTGQHPMA-UHFFFAOYSA-N Propene Chemical compound CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims abstract description 27
- 238000000034 method Methods 0.000 claims abstract description 22
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000002808 molecular sieve Substances 0.000 claims abstract description 19
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 25
- 239000007864 aqueous solution Substances 0.000 claims description 16
- HFPZCAJZSCWRBC-UHFFFAOYSA-N p-cymene Chemical compound CC(C)C1=CC=C(C)C=C1 HFPZCAJZSCWRBC-UHFFFAOYSA-N 0.000 claims description 12
- ZCZDJNBPZPSQPZ-UHFFFAOYSA-N benzene;prop-1-ene Chemical group CC=C.C1=CC=CC=C1 ZCZDJNBPZPSQPZ-UHFFFAOYSA-N 0.000 claims description 8
- 150000002500 ions Chemical class 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- 229910017604 nitric acid Inorganic materials 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 6
- 238000012545 processing Methods 0.000 claims description 5
- 206010013786 Dry skin Diseases 0.000 claims description 4
- 238000009992 mercerising Methods 0.000 claims description 4
- 230000004048 modification Effects 0.000 claims description 4
- 238000012986 modification Methods 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 239000000843 powder Substances 0.000 claims description 4
- 239000000243 solution Substances 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 3
- 238000005342 ion exchange Methods 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- 229910052684 Cerium Inorganic materials 0.000 claims description 2
- 239000012159 carrier gas Substances 0.000 claims description 2
- 239000003153 chemical reaction reagent Substances 0.000 claims description 2
- 229910021641 deionized water Inorganic materials 0.000 claims description 2
- 238000001125 extrusion Methods 0.000 claims description 2
- 238000000227 grinding Methods 0.000 claims description 2
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 2
- 229910052746 lanthanum Inorganic materials 0.000 claims description 2
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 2
- 150000002910 rare earth metals Chemical class 0.000 claims description 2
- 238000007598 dipping method Methods 0.000 claims 2
- 229910001420 alkaline earth metal ion Inorganic materials 0.000 claims 1
- 230000002152 alkylating effect Effects 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 14
- 230000008929 regeneration Effects 0.000 abstract description 6
- 238000011069 regeneration method Methods 0.000 abstract description 6
- 230000008901 benefit Effects 0.000 abstract description 2
- 238000005260 corrosion Methods 0.000 abstract description 2
- 230000007797 corrosion Effects 0.000 abstract description 2
- OGMSGZZPTQNTIK-UHFFFAOYSA-N 1-methyl-2-prop-1-en-2-ylbenzene Chemical compound CC(=C)C1=CC=CC=C1C OGMSGZZPTQNTIK-UHFFFAOYSA-N 0.000 abstract 1
- 125000000217 alkyl group Chemical group 0.000 abstract 1
- 238000009792 diffusion process Methods 0.000 abstract 1
- 230000002779 inactivation Effects 0.000 abstract 1
- 238000004519 manufacturing process Methods 0.000 abstract 1
- 230000007704 transition Effects 0.000 abstract 1
- OKIRBHVFJGXOIS-UHFFFAOYSA-N 1,2-di(propan-2-yl)benzene Chemical compound CC(C)C1=CC=CC=C1C(C)C OKIRBHVFJGXOIS-UHFFFAOYSA-N 0.000 description 15
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 12
- 230000029936 alkylation Effects 0.000 description 7
- 238000005804 alkylation reaction Methods 0.000 description 7
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 6
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 6
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 238000010555 transalkylation reaction Methods 0.000 description 6
- 230000009849 deactivation Effects 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 230000008859 change Effects 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000011835 investigation Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- UNEATYXSUBPPKP-UHFFFAOYSA-N 1,3-Diisopropylbenzene Chemical compound CC(C)C1=CC=CC(C(C)C)=C1 UNEATYXSUBPPKP-UHFFFAOYSA-N 0.000 description 2
- SPPWGCYEYAMHDT-UHFFFAOYSA-N 1,4-di(propan-2-yl)benzene Chemical compound CC(C)C1=CC=C(C(C)C)C=C1 SPPWGCYEYAMHDT-UHFFFAOYSA-N 0.000 description 2
- WWRCMNKATXZARA-UHFFFAOYSA-N 1-Isopropyl-2-methylbenzene Chemical compound CC(C)C1=CC=CC=C1C WWRCMNKATXZARA-UHFFFAOYSA-N 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000003442 catalytic alkylation reaction Methods 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- MTJGVAJYTOXFJH-UHFFFAOYSA-N 3-aminonaphthalene-1,5-disulfonic acid Chemical compound C1=CC=C(S(O)(=O)=O)C2=CC(N)=CC(S(O)(=O)=O)=C21 MTJGVAJYTOXFJH-UHFFFAOYSA-N 0.000 description 1
- 241001120493 Arene Species 0.000 description 1
- 238000007171 acid catalysis Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- FBXXLIYVIJIGRE-UHFFFAOYSA-N cumene 1,2-di(propan-2-yl)benzene Chemical compound CC(C)C1=CC=CC=C1.CC(C)C1=CC=CC=C1C(C)C FBXXLIYVIJIGRE-UHFFFAOYSA-N 0.000 description 1
- 229930007927 cymene Natural products 0.000 description 1
- 238000007336 electrophilic substitution reaction Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000012263 liquid product Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229910052680 mordenite Inorganic materials 0.000 description 1
- SYSQUGFVNFXIIT-UHFFFAOYSA-N n-[4-(1,3-benzoxazol-2-yl)phenyl]-4-nitrobenzenesulfonamide Chemical class C1=CC([N+](=O)[O-])=CC=C1S(=O)(=O)NC1=CC=C(C=2OC3=CC=CC=C3N=2)C=C1 SYSQUGFVNFXIIT-UHFFFAOYSA-N 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 238000009832 plasma treatment Methods 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 238000009418 renovation Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The present invention relates to a method for preparing modified macroporous zeolite molecular sieve catalysts, which synthesizes Y type, beta type, mercerizing type, ZSM-5 type, ZSM-12 type, etc. 10 catalysts with different properties. The catalysts can respectively used for the isopropylation reaction of benzene or toluene with propene to prepare cumene and isopropenyl toluene. Additionally, the inactivation, regeneration, long operation and alkyl transition properties of the catalyst are researched. The catalyst not only has the advantage of production efficiency improvement, but also has the characteristics of no corrosion, no pollution, high low-temperature reaction activity, small internal diffusion resistance, high selectivity, good activity stability, multiple regeneration, good repetitiveness, etc.
Description
The present invention relates to the preparation of modified zeolite catalyst, and carry out arenes catalytic isopropylation system cumene and derivative thereof with it.
The technology of existing industrial production cumene and isopropyl toluene, what mainly contain American UOP company and be representative makes the synthetic method of catalyst and the alchlor complexometry that companies such as SUMITOMO CHEMICAL, Mitsui and U.S. Monsanto/Lummus Crast adopt with solid phosphoric acid.These methods are that employing benzene or toluene are raw material, carry out electrophilic substitution reaction with the isopropylating agent propylene.The reaction condition of solid phosphoric acid method is 190～250 ℃ of reaction temperatures, pressure 3.0MPa, and the mol ratio of aromatic hydrocarbons/propylene is 6～10; And the reaction temperature of alchlor complexometry is 100～120 ℃, pressure 0.1～0.3MPa, and the mol ratio of aromatic hydrocarbons/propylene is 3～5.In recent years, U.S. G.R.Meima report adopts modified mordenite to make catalyst, at 175 ℃, and synthesizing iso-propylbenzene under the normal pressure, the mol ratio of its benzene/propylene is 7.7, weight space velocity is 1.0hr
-1, the selectivity of isopropylbenzene is 94.7% (mole), turns round continuously 900 hours, and is activity stabilized.Robort A.Innes then adopts and carries out benzene, propylene alkylation synthesizing iso-propylbenzene and the accessory substance diisopropylbenzene (DIPB) is carried out transalkylation on the H beta-zeolite catalyst, 160 ℃ of reaction temperatures, pressure 600Psig, the mol ratio of benzene/propylene is 7.43, weight space velocity is 4.6hr
-1, the running continuously through 500 hours, propylene conversion 100%, the selectivity of isopropylbenzene is 93.1%, the product purity height, (weight) % that product distributes is: isopropylbenzene 93.1, p-Diisopropylbenzene 2.7, m-Diisopropylbenzene 4.1, other is 0.1 years old.This catalyst also has very strong transalkylation ability.U.S. Mobil, Oil.Co. have reported employing HZSM-12 catalyst and have been used for toluene, propylene alkylation to prepare isopropyl toluene, 260 ℃ of reaction temperatures, and pressure 500Psig, toluene/propylene mol ratio is 6.25, the weight space velocity of toluene is 5.7hr
-1, the propylene weight air speed is 0.4hr
-1Condition under, in the isopropyl toluene that obtains, the neighbour:: right=5.3: 63.7: 31.0, because its reaction temperature height, neighbour in the isopropyl toluene of generation-isopropyl toluene content is higher.Because neighbour-isopropyl toluene not only itself is difficult to oxidation, but also to, the oxidation of cymene plays resistance inhibitor action, therefore, reduce the content that reaction temperature helps reducing o-isopropyl methylbenzene, thereby improve the reaction speed of isopropyl toluene in oxidizing process.From following table as can be seen, reduce reaction temperature and just can reach the content that reduces neighbour-isopropyl toluene, but that reaction temperature is spent is low when being unfavorable for that product reaches thermodynamical equilibrium, then must improve activity of such catalysts.
Isopropyl toluene equilibrium composition table one under the different temperatures
| Reaction temperature (℃) | P-Cymene (%) | Between-isopropyl toluene (%) | Neighbour-isopropyl toluene (%) |
| 100 190 210 250 310 | 30.08 30.45 30.54 30.43 30.29 | 68.59 66.99 66.58 66.03 65.05 | 1.30 2.56 2.89 3.55 4.66 |
Adopt solid phosphoric acid catalyst or aluminium trichloride complex catalyst to be used for the aromatic hydrocarbons isopropylation, exist equipment corrosion serious, technological process is long, problems such as reaction mass post processing trouble and environmental pollution.Especially solid phosphoric acid catalysis is active low, in toluene, propylene hydrocarbonylation synthetic isopropyl toluene process, o-isopropyl methylbenzene content is up to 40%, when entering oxidation, must further make it isomerization with aluminium trichloride complex catalyst, neighbour-isopropyl toluene content is reduced to about 3%, just can enters next step reaction.
The objective of the invention is above-mentioned shortcoming at solid phosphoric acid method and the existence of alchlor complexometry, by adopting the large aperture molecular sieve catalyst to carry out the isopropylation system isopropyl aromatic hydrocarbon of aromatic hydrocarbons, thus overcome in the past the molecular sieve catalyst reaction temperature higher, cause problems such as selectivity is low, energy consumption is big.
The modified technique of large aperture zeolite molecular sieve catalyst mainly adopts following process to prepare to have the low-temperature reactivity height, inside diffusional resistance is little, selectivity is high, activity stability is good, and through characteristics such as good regeneration repeatability repeatedly.
(1) preparation of molecular sieve catalyst:
The molecular sieve that obtains through hydrothermal synthesis method (comprising Y type, β type, mercerising, ZSM-12) former powder and α-Al
2O
3H
2O or Al (OH)
3Dried glue mixed grinding is even, and its ratio is molecular sieve: Al
2O
3=90～50: 10～50 (being as the criterion with butt) promptly add Al
2O
3Content be 10～50% (weight), suitable scope is 15～35%.With 3～10% aqueous solution of nitric acid blendings, mix pinch, extruded moulding (can be garden column type or trifolium-shaped), specification is Φ 1～4mm, length 2～10mm, the catalyst of extruded moulding be through 120 ℃ of dryings 2～4 hours, and stand-by after 6 hours in 540 ℃ of roastings.
(2) exchange is handled with modification:
Reagent treatment is NH
3-HNO
3-H
2The O mixed system, early stage is with Na in the exchange molecular sieve
+Ion is main, uses to contain NH
4 +Ion concentration is the aqueous solution of 0.4～0.6N.Molecular sieve is placed in the water solution system of ammoniacal liquor that temperature is room temperature～100 ℃ and nitric acid and carried out ion-exchange 1～4 hour, exchange finishes, and outwells exchange liquid, spends deionised water, in 120 ℃ of dryings, again in 540 ℃ of roastings, as than repeating twice.In the processing procedure of later stage, use to have H based on reaming
+-NH
4 +-H
2The aqueous solution of O ion is handled, and temperature is room temperature～200 ℃.Made modified molecular sieve catalyst,, enlarged the inner duct of catalyst, improved the catalyst inside diffusional resistance because modification is handled with high catalytic activity and high selectivity.
(3) ion processing of modified molecular screen:
For further improving the heat endurance of catalyst, help regeneration and repeat, use mishmetal (to contain La
3+, Ce
3+Ion is main aqueous solution of nitric acid) and alkaline-earth metal (Mg, Ca) plasma treatment.
The temperature of handling is room temperature～170 ℃, adopts 110～140 ℃ of evaporates to dryness, in 500～600 ℃ of roastings, handles rear catalyst 0.05～1.5% (weight) that increases weight through the method.
The Modified Zeolite Y that makes in order to the top method, be used for toluene-propylene alkylation catalytic reaction, temperature is 140 ℃, pressure 0.5MPa (gauge pressure), the toluene by weight air speed is 1.06, and the mol ratio of toluene/propylene is 8.9, and then the ratio of three of isopropyl toluene kinds of isomers is right in the product:: adjacent=30.2: 66.4: 3.4, the alkylation selectivity is 99.5%, and activity stability does not have significant change in 390 hours turn round continuously.
Catalyst to above-mentioned preparation carries out rapid deactivation, regeneration test 11 times, and catalyst activity, selectivity and activity stability do not have significant change.The condition of rapid deactivation is that big weight space velocity is 10～20hr
-1, it is low that toluene/the propylene mol ratio is 3～5,250～290 ℃ of high temperature after turning round continuously in 6～10 hours, take out catalyst, through N from reactor
2Air-blowing is swept, and places Muffle furnace temperature-programmed calcination under oxygenous situation, and initial temperature is 250 ℃, and final temperature is 500～560 ℃, and oxygen concentration is 0.3～21%.
With the beta molecular sieve catalyst of above-mentioned (1) (2) (3) method processing, in 140 ℃, pressure 3.5MPa (gauge pressure), weight space velocity 1.23hr
-1, benzene/propylene mol ratio is 6.27, during loaded catalyst 20 grams, and the running continuously through 1008 hours, catalyst activity is stable, and propylene conversion is not less than 99%, isopropylation selectivity 100%, this is the most outstanding achievement that the present invention obtains.
The beta molecular sieve catalyst of handling with above-mentioned (1) (2) (3) method is used for diisopropylbenzene (DIPB) and benzene carries out transalkylation reaction, 200～220 ℃ of reaction temperatures, mix diisopropylbenzene (DIPB): under the condition of benzene=1: 5～10 (mol ratio), operating pressure 3.0MPa, the weight of material air speed is 1.06, the running continuously through 1000 hours, diisopropylbenzene (DIPB) transalkylation rate 〉=85%, selectivity is 〉=97%.
Through big air speed WHSV 5～10hr
-1, it is low that benzene/the propylene mol ratio is 2～3, and rapid deactivation and catalyst shift out reactor, and temperature programming in Muffle furnace in the presence of oxygen (0.3～21%), is regenerated 20 times, and catalyst activity does not have significant change, and activity stability is good.
By above Preparation of catalysts and be applied to benzene or toluene carries out the isopropylation result and shows, modified macroporous footpath zeolite molecular sieve catalyst not only can be enhanced productivity, and catalyst has, and no burn into is pollution-free, low-temperature reactivity is high, inside diffusional resistance is little, selectivity is high, activity stability is good, repeatedly advantage such as good regeneration repeatability is a kind of comparatively ideal novel alkylation catalyst.
Embodiment 1
Take by weighing 8g molecular screen primary powder (dehydration back weight), get SB powder (commercially available Al
2O
3) 2.63g (dehydration back dry basis 2.0g), mix, grind, with 10% aqueous solution of nitric acid, 6～10ml blending, mix and pinch into bulk again, extrusion, catalyst bar diameter is Φ 1mm, dry 120 ℃, 2～4 hours, adopt Muffle furnace in 540 ℃ of roastings 6 hours again, use 0.6N NH
4 +NO
3 -Aqueous solution ion-exchange, 4 milliliters/gram catalyst, exchange is 2 hours in 80 ℃ of aqueous solution, outwells exchange liquid, uses with volume NH again
4NO
3Aqueous solution exchange is once outwelled exchange liquid, uses with the washing of volume deionized water once, places 120 ℃ of baking ovens dry (no time limit is as the criterion to parch) to use Muffle furnace in 540 ℃ of roastings 6 hours again.Tool prepares 1
#, 2
#, 3
#, 4
#, 5
#Molecular sieve catalyst, that is:
1
#-ZSM-5 type catalyst, 2
#-mercerising type catalyst,
3
#-ZSM-12 type catalyst, 4
#-Y type catalyst, 5
#-β type catalyst.
Embodiment 2
To prepare in the example 11
#, 2
#, 3
#, 4
#, 5
#Molecular sieve catalyst and industrial solid phosphoric acid catalyst carry out toluene one propylene alkylated reaction, and evaluating apparatus adopts the small stationary bed bioreactor, reactor inside diameter Φ 8mm, and loaded catalyst 1.0g, reaction condition and reaction result such as table two:
Different catalysts catalysis toluene-propylene alkylation
*Table two
*Reaction pressure is normal pressure, with N
2Be carrier gas, various material proportions all are the basis of calculation with the mole
Embodiment 3
To 4 of preparation in the example 1
#Catalyst is handled, and uses 0.6N NH again
4NO
3The aqueous solution 80 ℃ of exchanges twice, is outwelled raffinate, washing, drying, roasting (being same as example 1 processing method), obtains 6
#Catalyst.With 6
#Catalyst is contained in the reactor, at NH
3: HNO
3=2: 1, (NH
3+ HNO
3) concentration is 8% (in the aqueous solution), 5ml/ gram catalyst was handled 24 hours in 170 ℃, taking-up, washing, drying, and 540 ℃ of roastings 6 hours obtain 7
#Catalyst.
Embodiment 4
Through example 1 handled 5
#Catalyst in room temperature, is used 0.4N HNO
3The aqueous solution is handled 2 hours (5ml/ restrains catalyst), and washing, drying in 540 ℃ of roastings 6 hours, obtain 8
#Catalyst.
Embodiment 5
With 6
#, 7
#Catalyst carries out toluene-propylene alkylated reaction, and answering pressure is 5kg/cm
2(gauge pressure), toluene by weight air speed 1.08hr
-1
The 4.0g catalyst of in Φ 10mm reactor, packing into, N
2: C
3 -=2.9: 1 (mol ratio), reaction result such as table three are investigated in running continuously:
Toluene-propylene alkylated reaction table three is investigated in running continuously
Embodiment 6
With 7
#, 8
#Catalyst carries out benzene-propylene catalytic alkylation reaction, and its reaction condition is 70 ℃, benzene weight space velocity 5.28hr
-1, benzene/propylene=5.6 (mol ratio), normal pressure, at Φ 8mm catalyst in reactor charge weight 1.0 grams, reaction result such as table four:
Benzene-propylene catalytic alkylation reaction table four
| Catalyst | Benzene conversion ratio % | Isopropylbenzene selectivity % | Product is formed % (mole) | ||||
| Non-aromatic | Benzene | C 7～8 | Isopropylbenzene | Diisopropylbenzene (DIPB) | |||
| 7 = 8 = | 10.44 17.41 | 88.84 92.57 | 0.34 0.45 | 89.19 82.31 | 0.06 0.03 | 9.25 16.00 | 1.16 1.32 |
Embodiment 7
Adopt commercially available mishmetal (containing La, Ce etc.) 1.0g, use 0.4N HNO
3The 10ml dissolving is filtered, and is standby.Take by weighing 7
#, 8
#Each 1.0g of catalyst is immersed in and contains in the certain amount of mixed rare earth salpeter solution, at 120 ℃ of evaporates to dryness, and roasting 6 hours (540 ℃), this moment, the catalyst weightening finish 0.3%, obtained 10
#Catalyst.
Embodiment 8
With 10
#Catalyst carries out benzene-propylene rapid deactivation experiment, 140 ℃ of rapid deactivation conditions, benzene/propylene=2, weight space velocity 10hr
-1, pressure 5kg/cm
2, reduce to 50% of initial activity through 8～10 hours benzene conversion ratios, stop reaction and from reactor, pour out catalyst, in Muffle furnace, regenerate, renovation process adopts temperature programming, is warmed up to 540 ℃, is incubated 6 hours, process above-mentioned steps 4 times, this catalyst is carried out benzene-propylene alkylated reaction, and its reaction result and fresh catalyst coincide, catalyst activity, the selectivity no change is through running investigation activity stability is stable continuously.
Embodiment 9
Adopt 10
#Catalyst is at 140 ℃, pressure 3.5MPa, and benzene/propylene=6.3, the weight of material air speed is 1.13hr
-1, loaded catalyst 20 grams, tube inner diameter Φ 14mm, logistics is charging from bottom to top, and it the results are shown in Table five:
Benzene-propylene alkylation investigation table five that turns round continuously
| Accumulated time (hour) | Liquid product is formed % (mole) | Catalytic performance | ||||||||
| Non-aromatic | Benzene | C 7～8 | Isopropylbenzene | M-Diisopropylbenzene | P-Diisopropylbenzene | Adjacent diisopropylbenzene (DIPB) | ＞C 1: aromatic hydrocarbons | C B％ | S C％ | |
| 48 264 408 792 1008 | / | 85.83 85.46 85.04 85.61 86.35 | / | 13.30 13.50 13.89 13.40 13.47 | 0.55 0.57 0.57 0.48 0.56 | 0.32 0.47 0.50 0.51 0.61 | / / | / / | 14.20 14.54 14.96 14.39 14.65 | 93.86 92.78 92.85 93.12 92.87 |
Embodiment 1O
To 10
#Catalyst carries out the transalkylation of diisopropylbenzene (DIPB) and benzene under 200 ℃ of conditions investigates, as table six:
Diisopropylbenzene (DIPB) and benzene liquid phase transalkylation investigation table six
| Accumulated time (hour) | Material is formed % (mole) | Isopropylbenzene/∑ two is different | ||||||||
| Non-aromatic | Benzene | C 7～8 | Isopropylbenzene | N-proplbenzene | Between-two different | Right-two is different | Adjacent-two is different | ＞C 1： | ||
| (reaction mass) 20 30 60 | 0.17 0.71 0.41 0.47 | 92.58 87.01 87.70 87.75 | / 0.14 0.10 0.09 | 1.47 11.38 11.02 10.93 | / 0.06 0.04 0.04 | 3.26 0.26 0.25 0.30 | 2.15 0.44 0.47 0.42 | / | / | 0.25 16.26 15.10 15.17 |
Claims (11)
1. a class is used for the preparation method of alkylating zeolite molecular sieve catalyst, it is characterized in that this catalyst is the preparation through zeolite molecular sieve, exchange then and modification, make ion processing or rare earth dipping at last, make modified macroporous footpath zeolite molecular sieve catalyst; The preparation of zeolite molecular sieve be Y type that hydrothermal synthesis method is obtained, β type, mercerising, ZSM-5, ZSM-12 molecular screen primary powder respectively with α-Al
2O
3H
2O or Al (OH)
3, press molecular sieve: Al
2O
3=90～50: 10～50 percentage by weight mixed grindings are even, again with 3～10% aqueous solution of nitric acid blendings, mix pinch, extrusion becomes Φ 1～4mm, long 2～10mm column type or trifolium-shaped catalyst, in 120 ℃ of dryings 2～4 hours, 540 ℃ of roastings formed in 6 hours; Exchange is 0.4～0.6N NH with the reagent that modification is handled
4 +NO
3 -The aqueous solution ℃ carried out ion-exchange 1～4 hour in room temperature～100, exchange twice, and washing, 120 ℃ of dryings, H is used in 540 ℃ of roastings again
+-NH
4 +-H
2The O deionized water solution, ℃ reaming is handled in room temperature～200; Ion processing is with containing La
3+, Ce
3+Ion be main mishmetal aqueous solution of nitric acid and contain Mg, the Ca alkaline-earth metal ions is handled, dipping temperature is room temperature～170 ℃, behind 110～140 ℃ of evaporates to dryness, in 500～600 ℃ of roastings, make make 1
#-ZSM-5 type, 2
#-mercerising type, 3
#-ZSM-12 type, 4
#-Y type and 5
#-β-type catalyst all can increase weight 0.05～1.50%.
2. according to claim 1 described 1
#The purposes of-ZSM-5 type catalyst is characterized in that this catalyst is used for the alkylated reaction of toluene-propylene, under normal pressure, with N
2Be carrier gas, 250 ℃ of reaction temperatures, the mol ratio of toluene/propylene are 8, and the toluene by weight air speed is 4.1hr
-1, can make isopropyl toluene.
3. according to the described Preparation of catalysts method of claim 1, it is characterized in that with make 4
#-Y type catalyst is used 0.6N NH again
4NO
3The aqueous solution, at 80 ℃ of exchange secondaries, washing, dry, roasting can make 6
#Catalyst.
4. according to described in the claim 36
#The purposes of catalyst is characterized in that carrying out toluene-propylene alkylated reaction with it, and gauge pressure is 5kg/cm
2, the toluene by weight air speed is 1.08h
-1, reaction temperature is 250 ℃, can make isopropyl toluene.
5. according to the method for Preparation of catalysts described in the claim 3, it is characterized in that with make 6
#Catalyst is at NH
3: HNO
3=2: 1, NH
3+ HNO
3Concentration be 8%, handled 24 hours at 170 ℃, washing, dry, 540 ℃ of roastings 6 hours make 7
#Catalyst.
6. according to described in the claim 57
#The purposes of catalyst is characterized in that carrying out toluene-propylene alkylated reaction with it, and the mol ratio of toluene/propylene is 8.9, and gauge pressure is 0.5MPa, and the weight space velocity of toluene is 1.06hr
-1, reaction temperature is 140 ℃, can make isopropyl toluene.
7. according to described in the claim 57
#The purposes of catalyst is characterized in that this catalyst is carried out the alkylated reaction of benzene-propylene, and the mol ratio of benzene/propylene is 5.6, and under the normal pressure, reaction temperature is 70 ℃, and the benzene weight space velocity is 5.28hr
-1, can make isopropylbenzene.
8. according to the described Preparation of catalysts method of claim 1, it is characterized in that with make 5
#-β type catalyst was at room temperature handled 2 hours with the 0.4N aqueous solution of nitric acid, washing, dry, 540 ℃ of roastings 6 hours, make 8
#Catalyst.
9. according to described in the claim 88
#The purposes of catalyst is characterized in that carrying out with it the alkylated reaction of benzene-propylene, and the mol ratio of benzene/propylene is 5.6, and under the normal pressure, reaction temperature is 70 ℃, and the benzene weight space velocity is 5.28hr
-1, can make isopropylbenzene.
10. according to the method for Preparation of catalysts described in the claim 8, it is characterized in that with make 8
#Catalyst and the mishmetal that contains La, Ce flood in the 0.4N salpeter solution, and at 120 ℃ of evaporates to dryness, then 540 ℃ of roastings 6 hours, make 10 of weightening finish 0.3%
#Catalyst.
11. according to described in the claim 10 10
#The purposes of catalyst is characterized in that carrying out with it the alkylated reaction of benzene-propylene, and the mol ratio of benzene/propylene is 6.3, and pressure is 3.5MPa, 140 ℃ of reaction temperatures, and the benzene weight space velocity is 1.13hr
-1, can make isopropylbenzene.
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| CN94112680A CN1066071C (en) | 1994-12-13 | 1994-12-13 | Preparation of modified macro-porous zeolite catalyst and synthetic isopropyl aromatic hydrocarbon |
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|---|---|---|---|
| CN94112680A CN1066071C (en) | 1994-12-13 | 1994-12-13 | Preparation of modified macro-porous zeolite catalyst and synthetic isopropyl aromatic hydrocarbon |
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| CN1066071C true CN1066071C (en) | 2001-05-23 |
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Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1133499C (en) * | 1997-10-22 | 2004-01-07 | 中国科学院大连化学物理研究所 | Catalyst for preparing toluene by cracking isopropyl methybenzene and preparation thereof |
| CN1100615C (en) * | 1998-12-28 | 2003-02-05 | 北京燕山石油化工公司研究院 | Modified zeolite catalyst and its application in preparing 2-tert-butyl-4-methyl phenol |
| CN101157444B (en) * | 2002-10-18 | 2012-09-05 | 孟山都技术公司 | Use of metal supported copper catalysts for reforming alcohols |
| CN101575218B (en) * | 2009-06-02 | 2011-09-28 | 北京师范大学 | Novel foam zeolite block and preparation method thereof |
| CN103030518B (en) * | 2011-09-29 | 2015-02-11 | 中国石油化工股份有限公司 | Method for preparing isopropylbenzene through diisopropylbenzene transalkylation |
| CN103372459B (en) * | 2012-04-12 | 2015-04-15 | 中国石油化工股份有限公司 | Cyclane hydro-conversion catalyst, preparation method and applications |
| CN109665541B (en) * | 2017-10-17 | 2022-04-01 | 中国石油化工股份有限公司 | Synthesis method of ZSM-12 type zeolite molecular sieve with low silica-alumina ratio |
| CN112142549B (en) * | 2019-06-26 | 2023-08-29 | 中国石油化工股份有限公司 | Synthesis method of methyl isopropyl benzene |
| CN114762832B (en) * | 2021-01-12 | 2023-12-08 | 洛阳市科创石化科技开发有限公司 | Preparation method and application of catalyst for producing mixed propylbenzene by alkylation of benzene and carbon tetraolefin |
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| EP0432814A1 (en) * | 1989-11-16 | 1991-06-19 | ENIRICERCHE S.p.A. | Process for alkylating benzene |
| US5081323A (en) * | 1987-12-17 | 1992-01-14 | Chevron Research And Technology Company | Liquid phase alkylation or transalkylation process using zeolite beta |
| CN1068977A (en) * | 1991-07-12 | 1993-02-17 | 加利福尼亚友联石油公司 | The alkylation catalyst of hydration and using method thereof |
| CN1074392A (en) * | 1992-01-13 | 1993-07-21 | 中国科学院大连化学物理研究所 | The zeolite catalyst of preparing ethyl benzene from alkylated styrene |
| CN1172353A (en) * | 1996-07-10 | 1998-02-04 | 本田技研工业株式会社 | Cell charge-discharge structure for electric auxiliary bicycle |
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|---|---|---|---|---|
| US5081323A (en) * | 1987-12-17 | 1992-01-14 | Chevron Research And Technology Company | Liquid phase alkylation or transalkylation process using zeolite beta |
| EP0432814A1 (en) * | 1989-11-16 | 1991-06-19 | ENIRICERCHE S.p.A. | Process for alkylating benzene |
| CN1068977A (en) * | 1991-07-12 | 1993-02-17 | 加利福尼亚友联石油公司 | The alkylation catalyst of hydration and using method thereof |
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