CN85102699A - Directly produce p-Xylol by toluene - Google Patents
Directly produce p-Xylol by toluene Download PDFInfo
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- CN85102699A CN85102699A CN 85102699 CN85102699A CN85102699A CN 85102699 A CN85102699 A CN 85102699A CN 85102699 CN85102699 CN 85102699 CN 85102699 A CN85102699 A CN 85102699A CN 85102699 A CN85102699 A CN 85102699A
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- phosphorus
- toluene
- xylol
- magnesium
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- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 title claims abstract description 113
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical compound CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 239000003054 catalyst Substances 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 14
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 13
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 claims abstract description 10
- 230000004048 modification Effects 0.000 claims abstract description 10
- 238000012986 modification Methods 0.000 claims abstract description 10
- GZHCNRONBGZNAH-UHFFFAOYSA-N phosphanylidynelanthanum Chemical compound [La]#P GZHCNRONBGZNAH-UHFFFAOYSA-N 0.000 claims abstract description 8
- LWNCNSOPVUCKJL-UHFFFAOYSA-N [Mg].[P] Chemical compound [Mg].[P] LWNCNSOPVUCKJL-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000006243 chemical reaction Methods 0.000 claims description 19
- 229910052739 hydrogen Inorganic materials 0.000 claims description 14
- 239000001257 hydrogen Substances 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 11
- 229910021536 Zeolite Inorganic materials 0.000 claims description 11
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 11
- 238000007323 disproportionation reaction Methods 0.000 claims description 11
- 239000010457 zeolite Substances 0.000 claims description 11
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 10
- 230000008569 process Effects 0.000 claims description 9
- 238000002360 preparation method Methods 0.000 claims description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 6
- 238000005516 engineering process Methods 0.000 claims description 4
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 claims description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
- 150000002500 ions Chemical class 0.000 claims description 3
- UEGPKNKPLBYCNK-UHFFFAOYSA-L magnesium acetate Chemical compound [Mg+2].CC([O-])=O.CC([O-])=O UEGPKNKPLBYCNK-UHFFFAOYSA-L 0.000 claims description 3
- 235000011285 magnesium acetate Nutrition 0.000 claims description 3
- 238000000465 moulding Methods 0.000 claims description 3
- 229910052698 phosphorus Inorganic materials 0.000 claims description 3
- 239000011574 phosphorus Substances 0.000 claims description 3
- 229910052747 lanthanoid Inorganic materials 0.000 claims description 2
- 150000002602 lanthanoids Chemical class 0.000 claims description 2
- 229940069446 magnesium acetate Drugs 0.000 claims description 2
- 239000011654 magnesium acetate Substances 0.000 claims description 2
- 150000002681 magnesium compounds Chemical class 0.000 claims description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 2
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical group OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 claims 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims 1
- HKMHSMCTSWRGAV-UHFFFAOYSA-N toluene;1,4-xylene Chemical compound CC1=CC=CC=C1.CC1=CC=C(C)C=C1 HKMHSMCTSWRGAV-UHFFFAOYSA-N 0.000 claims 1
- OSBSFAARYOCBHB-UHFFFAOYSA-N tetrapropylammonium Chemical group CCC[N+](CCC)(CCC)CCC OSBSFAARYOCBHB-UHFFFAOYSA-N 0.000 abstract description 7
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 17
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 12
- 238000001035 drying Methods 0.000 description 8
- XPNGNIFUDRPBFJ-UHFFFAOYSA-N (2-methylphenyl)methanol Chemical compound CC1=CC=CC=C1CO XPNGNIFUDRPBFJ-UHFFFAOYSA-N 0.000 description 7
- 238000005804 alkylation reaction Methods 0.000 description 7
- 206010013786 Dry skin Diseases 0.000 description 6
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 4
- 230000029936 alkylation Effects 0.000 description 4
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical group [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 4
- 239000011777 magnesium Substances 0.000 description 4
- 229910052749 magnesium Inorganic materials 0.000 description 4
- 239000003643 water by type Substances 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 238000007598 dipping method Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000012452 mother liquor Substances 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 229910052746 lanthanum Inorganic materials 0.000 description 2
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- 241000370738 Chlorion Species 0.000 description 1
- 241001269238 Data Species 0.000 description 1
- 102000004160 Phosphoric Monoester Hydrolases Human genes 0.000 description 1
- 108090000608 Phosphoric Monoester Hydrolases Proteins 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 230000001404 mediated effect Effects 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000002352 surface water Substances 0.000 description 1
Landscapes
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention belongs to the method for producing p-Xylol.Directly produce p-Xylol from industrialized angle by toluene.This method catalyst system therefor is to replace the tetrapropyl ammonium salt with cheap ammoniacal liquor or more cheap n-Butyl Amine 99, and by phosphorus-magnesium, phosphorus-lanthanum or phosphorus-mishmetal modification and getting is for the industrialization of directly being produced p-Xylol by toluene provides operational condition.
Description
The invention belongs to the method for producing p-Xylol.
P-Xylol is a main raw material of producing polyester, and existing production technique is that processes such as separation make the adjacent meta-isomer of dimethylbenzene be converted into p-Xylol with the isomerization of blended dimethylbenzene process.Directly producing p-Xylol by toluene is a kind of novel process of developing, and it can select disproportionation or toluene-methanol alkylation to realize by toluene.This research is at first begun by U.S. Mobil company, and it is at U.S.4, and at first having reported in 011,276 patent with phosphorus-magnesium-ZSM-5 is that toluene disproportionation catalyst can obtain p-Xylol concentration and reaches 98.2%, and toluene conversion is 24% little experiment.After this many countries have all delivered relevant achievement in research, from prior art, can obtain p-Xylol though make the catalyzer toluene disproportionation with phosphorus-magnesium-ZSM-5, owing to used the tetrapropyl ammonium salt during synthetic ZSM-5, make it cost an arm and a leg.Existing in addition directly to produce the work experimental size of p-Xylol by toluene very little, and data do not repeat, and the consequence deviation that obtains under the identical or close condition is very big, does not have the analytical data of overall product again.Therefore, be difficult to provide reliable experimental for industrialization.
The objective of the invention is to invent and carry out the technology that toluene is directly produced p-Xylol from industrialized angle.This technology catalyst system therefor does not contain expensive tetrapropyl ammonium salt, but replaces the tetrapropyl ammonium salt with cheap ammoniacal liquor or more cheap n-Butyl Amine 99.By phosphorus-magnesium, phosphorus-lanthanum or phosphorus-mishmetal modification and getting.
The present invention is made up of Preparation of Catalyst and toluene disproportionation or toluene-methanol alkylation reaction process two portions.
One, Preparation of catalysts
Preparation of catalysts comprises the synthetic of zeolite, hydrogen type catalyst preparation and with different ions modification three parts.
1, zeolite is synthetic
Synthetic ZSM-5 type zeolite is to use water glass, and acidifying Tai-Ace S 150, ammoniacal liquor and water are that raw material is made A by a certain percentage, two kinds of solution of B, and add an amount of crystal seed, in the crystallization narrow-necked earthen jar, become glue, and in chosen temperature 170 ℃ ± 3, under reactant self pressure through 48～60 hours crystallization processs.Reaction product cooling back branch removes mother liquor, washs to PH=9 with deionized water, filters, and is drying to obtain the NaZSM-5 zeolite powder.
2, the preparation of hydrogen type catalyst
With NaZSM-5 zeolite powder and α-Al
2O
3-H
2O by weight (65～80: 35～20), add an amount of rare nitric acid and mediate, through extruded moulding (φ 1.5～2mm column) in 120 ℃ dry 3 hours down, 540 ℃ of roastings 3 hours and obtain Na type ZSM-5 catalyzer.This kind catalyzer 0.4N NH
4NO
3(2.4ml/ restrains catalyzer) uses the 0.6MHCl(38ml/g catalyzer again in normal temperature exchange secondary) soaked 24 hours, remove mother liquor, wash to there not being chlorion (adding Silver Nitrate detects) with deionized water.Drying (120 ℃) and roasting (540 ℃, 3 hours) can make Hydrogen ZSM-5 catalyzer.
3, the preparation of different ions modified catalyst
Carry phosphorus respectively on Hydrogen ZSM-5 zeolite, magnesium and lanthanum and mishmetal can be made into the catalyzer of different performance.Used phosphide mainly is a phosphoric acid, the amount of being written into is 1%～2%(weight of catalyzer), magnesium compound is mainly magnesium acetate, the amount of being written into is 1%～20%(weight), lanthanide is mainly lanthanum nitrate, the amount of being written into is 1%～20%(weight), mishmetal is a muriate, the amount of being written into is 1%～20%(weight).These compounds can be stated from separately on the Hydrogen ZSM-5, also can carry wherein any after carrying phosphorus again, through the modification rear catalyst 520～550 ℃ of following roastings 3～6 hours.Can make P-Mg-ZSM-5(phosphorus-magnesium-ZSM-5) so respectively, the modified catalyst of P-La-ZSM-5(phosphorus-lanthanum-ZSM-5) and P-Re-ZSM-5(phosphorus-mishmetal-ZSM-5).
Two, the technology of toluene disproportionation or toluene-methanol alkylation reaction
Hydrogen ZSM-5 catalyzer or the various modified catalyst made with aforesaid method can carry out toluene disproportionation and toluene-methanol alkylation reaction respectively in atmospheric fixed bed reactor of flow type and the pressurization static bed reactor of flow type.Toluene disproportionation process is 490 ℃～540 ℃ in temperature, and pressure is 0.4～0.9MPa(absolute pressure), weight space velocity is 3～7 o'clock
-1, carry out under the condition of hydrocarbon/toluene (molecular ratio)=3～7.It is 350 °～400 ℃ that toluene-methanol alkylation is reflected at temperature, and pressure is 0.3～2MPa(absolute pressure), air speed is 2～6 o'clock
-1, toluene and methanol (mol ratio) is to carry out under 2～6 the condition.
The atmospheric fixed bed reactor of flow type is generally adorned catalyzer one gram, but reaction parameters such as system thinking temperature of reaction, hydrogen-hydrocarbon ratio, air speed also can be investigated activity stability by continuous operation.Pressurization static bed reactor dress catalyzer 20～50 grams except that can investigating above-mentioned reaction parameter, also can be considered the influence of pressure change and obtain reliable material balance data.
Effect of the present invention:
1, owing to replaces expensive tetrapropyl ammonium salt with cheap ammoniacal liquor or more cheap n-Butyl Amine 99, phosphorus-magnesium in addition again, phosphorus-lanthanum, phosphorus-mishmetal are produced P-Mg-ZSM-5 and P-La-ZSM-5 and P-Re-ZSM-5 modified catalyst, make the price of such catalyzer greatly reduce.Ammoniacal liquor, n-Butyl Amine 99, the price of tetrapropyl ammonium salt sees the following form.
| The name of an article | Price unit/liter |
| Ammoniacal liquor | 2.84 |
| N-Butyl Amine 99 | 71.8 |
| The tetrapropyl ammonium salt | 177.0 |
2, use P-Mg-ZSM-5, P-La-ZSM-5, the P-Re-ZSM-5 modified catalyst makes toluene select disproportionation or toluene-methanol alkylation to produce p-Xylol.Under selected condition, through running experiment for a long time, obtained the multiple material balance, product distributes, experimental datas such as catalyst carbon deposition and operational condition.Thereby the industrialization process of selecting disproportionation or toluene-methanol alkylation to produce p-Xylol by toluene for exploitation provides experimental basis.
Inventive embodiments:
1, water intaking glass 1883.88 gram (modulus 3.32) adds crystal seed 20 grams and 83.58 gram water are made into B solution, and other gets 44.4 and restrains Tai-Ace S 150 (Al
2(SO
4)
318H
2O) the 83.8 gram vitriol oils and 2054 gram water are made into A solution.A solution is once added in the B solution, add concentration simultaneously and be 747 milliliters of 25% ammoniacal liquor, heat-flash stirs after 50 minutes and be heated to 170 ℃ ± 2 under airtight and quiescent conditions, made the reactant crystallization 48 hours, to be cooledly open crystallizing kettle to normal temperature and tell mother liquor, solid product is washed till PH ≈ 9 with deionized water, and 120 ℃ of dryings 3 hours, the gained white solid was NaZSM-5 through X-ray analysis.
The reaction mixture that obtains by above-mentioned batching is SiO
2: Al
2O
3: Na
2O: NH
3: H
2O=80: 1: 8.5: 150: 3500 if replace ammoniacal liquor to contain organic amine ionic NaZSM-5 zeolite with making with quadrat method with n-Butyl Amine 99, and used n-Butyl Amine 99 amount is 1.22mol.NaZSM-5 zeolite 80 grams that the method for taking makes add α-Al
2O
3.H
2The O20 gram is mediated with a small amount of 10% rare nitric acid, and (φ 1.5～2.0m/m, long 5～10m/m) in 540 ℃ of roastings 3 hours, uses 0.4NNH more then in 120 ℃ of dryings with the banded extruder extrusion molding
4NO
3Exchange twice by (2.4 milliliters/gram catalyzer), with the rare HCl(38 milliliter of 0.6N/gram catalyzer) soaked overnight, be washed to no Cl
-, in 120 ℃ of dryings, 540 ℃ of roastings promptly made HZSM-5 in 3 hours.If when synthetic NaZSM-5 zeolite, used n-Butyl Amine 99, at first at N
2Remove organic amine in 6 hours in 540 ℃ of roastings under the air-flow, add α-Al again
2O
3-H
2O(α-one water aluminum oxide) behind kneading, the extruded moulding, carries out NH again
4NO
3, operation such as rare HCl exchange.
Got HZSM-5 catalyzer 65 gram adding 85% phosphatase 11,4.49 grams and 91 gram water loggings bubbles 24 hours, dry down in 120 ℃ 540 ℃ of following roastings 3 hours, get 7.2 gram magnesium acetates again and add 41 gram water, with above-mentioned phosphorus-carried catalyzer dipping after 24 hours in 120 ℃ of dryings, promptly got in 3 hours 540 ℃ of roastings and to carry the P-MgZSM-5 catalyzer.
2, get HZSM-5 2 grams except that behind the surface water (200 ℃ following 2 hours), add 0.4ml85%H
3PO
4With 3.74ml water retting 20 hours, in 120 ℃ of dryings, 540 ℃ of following roastings 3 hours phosphorus-carried catalyzer.Get 2 gram phosphorus-carried catalyzers, add 0.247 gram, 98% lanthanum nitrate (La(NO
3)
34H
2O) and 8.0 ml waters, dipping under 90 ℃ of waters bath with thermostatic control after 6 hours in 120 ℃ of dryings, 540 ℃ of roastings obtained carrying a P-La-ZSM-5 catalyzer in 6 hours.
3, get n-Butyl Amine 99 synthetic ZSM-5 and α-Al
2O
3-H
2The HZSM-510 gram that O makes adds 85% phosphoric acid, 8 grams and 20 ml waters soaked 12 hours, dry down in 120 ℃, 540 ℃ of following roastings 3 hours, getting 1.33 gram lanthanum nitrates again, to add 10 ml waters dry down in 120 ℃ after 6 hours with above-mentioned phosphorus-carried catalyzer dipping, 540 ℃ of roastings 3 hours, must carry phosphorus-lanthanum catalyst (P-La-ZSM-5).
4, get 30 phosphorus-magnesium-modified ammoniacal liquor synthetic ZSM-5 catalyzer of making as stated above of gram, it is phosphorous 4.86%, contains magnesium 1.22%, this catalyzer code name be P-MgDGA in 525 ℃ of temperature of reaction, pressure 0.5MPa(absolute pressure), during weight space velocity 7
-1, hydrogen/toluene (molecular ratio) is continuous operation 33 hours under 6 the condition.Toluene conversion is 18.7%, and the concentration of p-Xylol in xylol is 96.04%.
5, get phosphorus-magnesium-modified that 30 grams make as stated above with ammoniacal liquor synthetic ZSM-5 catalyzer, it is phosphorous 4.86%, contains magnesium 1.22%, this catalyzer code name is P-Mg-DGA-01.In 535 ℃ of temperature of reaction, pressure 0.5MPa(absolute pressure), during weight space velocity 5.8
-1, hydrogen/toluene (molecular ratio) is continuous operation 145 hours under 6 the condition, and toluene conversion is 14～16%, and dimethylbenzene/benzene is 0.64～0.70, and the concentration of p-Xylol in xylol is 92～94%.The catalyzer carbon content is 1.69%.Liquid yield 96.5%.
6, get phosphorus-magnesium-modified that 30 grams make as stated above with ammoniacal liquor synthetic ZSM-5 catalyzer, it is phosphorous 1.8%, contains magnesium 3.4%, this catalyzer code name is P-MgDGA-02.In 530～540 ℃ of temperature of reaction, pressure 0.5MPa(absolute pressure), weight space velocity 4.5～5 o'clock
-1Hydrogen/toluene (molecular ratio) is under 6 the condition, continuous operation 200 hours, and toluene conversion is 14～17%, and dimethylbenzene/benzene is 0.75～0.82, and the concentration of p-Xylol in xylol is 92-94%, and the catalyzer carbon content is 2.2%, liquid yield 96%.
7, get 1 phosphorus-lanthanum modification of making as stated above of gram it is phosphorous 2.98% with ammoniacal liquor synthetic ZSM-5 catalyzer, contain lanthanum 3.53%.This catalyzer code name is P-LaDGA.In 530 ℃ of temperature of reaction, pressure 0.2MPa(absolute pressure) during weight space velocity 4
-1Hydrogen/toluene (molecular ratio) is to carry out toluene disproportionation process under 4 the condition, toluene conversion 14%, dimethylbenzene/benzene is 0.92, the concentration of p-Xylol in xylol is 94%.
8, getting the 30 P-La-ZSM-5 catalyzer code names made by example 3 of gram is P-LaIDG-03, in 512 ℃ of temperature of reaction, and pressure 0.51MPa(absolute pressure), during weight space velocity 4.6
-1And under the condition of hydrogen/toluene (molecular ratio) 6.3, turned round 100 hours, the concentration 93～95% of average 15～17% p-Xylol of toluene conversion in xylol, the diformazan benzene/methylbenzene is 0.83～0.93.Liquid yield 98%.
9, getting 1 gram code name is that the catalyzer of P-MgDGA-02 faces 400 ℃ of H-H reaction temperature in normal pressure, during weight space velocity 6
-1, toluene and methanol (molecular ratio) is 3 its toluene conversion 24.5%, the concentration of p-Xylol in xylol is 95.8%.
10, getting 1 gram code name is that the catalyzer of P-LaDGA-02 is operated under the condition identical with example 9, obtains toluene conversion 25.3%, and the concentration of p-Xylol in xylol is 92.4%.
Claims (2)
1, a kind of Hydrogen ZSM-5 zeolite catalyst that is used for directly being produced by toluene p-Xylol is a synthetic ZSM-5 zeolite in the presence of ammoniacal liquor or n-Butyl Amine 99, through adding α--water aluminum oxide (α-Al
2OH
2O) extruded moulding, with the ammonium nitrate exchange, dilute hydrochloric acid is handled, it is characterized in that passing through again phosphorus-magnesium, phosphorus-lanthanum, phosphorus-mishmetal two-pack modification, used phosphide is a phosphoric acid, and the amount of being written into is 1%～20% (weight), and magnesium compound is a magnesium acetate, the amount of being written into is 1%～20% (weight), and lanthanide is a lanthanum nitrate, and the amount of being written into is that 1%～20% (weight) mishmetal is a muriate, the amount of being written into is 1%～20%, the preparation modified catalyst is at first used the phosphorus modification, and then other ion of load; Through the modification rear catalyst 520～550 ℃ of following roastings 3～6 hours.
2, a kind ofly directly produce the technology of p-Xylol, it is characterized in that by toluene:
(1) through phosphorus-magnesium, phosphorus-lanthanum, the catalyzer of phosphorus-mishmetal modification, 490 ℃～540 ℃ of temperature of reaction, pressure is 3～8 kilograms/cm
2Weight space velocity is 3～7 o'clock
-1, carry out toluene disproportionation process under the operational condition of hydrogen/toluene (molecular ratio)=3～7.
(2) through phosphorus-magnesium, phosphorus-lanthanum, the catalyzer of phosphorus-mishmetal modification is 350 ℃～4000 ℃ in temperature, pressure is 0.2～2MPa(absolute pressure), air speed is 2～6 o'clock
-1, toluene and methanol (mol ratio) is under 2～6 the condition, carries out toluene-methyl alcohol and select alkylated reaction in fixed-bed reactor.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 85102699 CN85102699A (en) | 1985-04-01 | 1985-04-01 | Directly produce p-Xylol by toluene |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 85102699 CN85102699A (en) | 1985-04-01 | 1985-04-01 | Directly produce p-Xylol by toluene |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN85102699A true CN85102699A (en) | 1986-09-17 |
Family
ID=4792692
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 85102699 Pending CN85102699A (en) | 1985-04-01 | 1985-04-01 | Directly produce p-Xylol by toluene |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN85102699A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104117384A (en) * | 2013-04-28 | 2014-10-29 | 中国石油化工股份有限公司 | Toluene methylation catalyst and method for producing p-xylene in presence of same |
| CN105018128A (en) * | 2014-04-24 | 2015-11-04 | 中国石油化工股份有限公司 | Method and catalyst for preparing high-octane rating gasoline component |
-
1985
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104117384A (en) * | 2013-04-28 | 2014-10-29 | 中国石油化工股份有限公司 | Toluene methylation catalyst and method for producing p-xylene in presence of same |
| CN105018128A (en) * | 2014-04-24 | 2015-11-04 | 中国石油化工股份有限公司 | Method and catalyst for preparing high-octane rating gasoline component |
| CN105018128B (en) * | 2014-04-24 | 2017-03-22 | 中国石油化工股份有限公司 | Method and catalyst for preparing high-octane rating gasoline component |
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