CN1169889A - Catalyst of alkyl benzene with straight chain made by alkylation from benzene and straight chain olefin and its application - Google Patents
Catalyst of alkyl benzene with straight chain made by alkylation from benzene and straight chain olefin and its application Download PDFInfo
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- CN1169889A CN1169889A CN96115437A CN96115437A CN1169889A CN 1169889 A CN1169889 A CN 1169889A CN 96115437 A CN96115437 A CN 96115437A CN 96115437 A CN96115437 A CN 96115437A CN 1169889 A CN1169889 A CN 1169889A
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Abstract
An HY-type molecular sieve catalyst which has go through metallic ion exchange and acid treatment can be used to prepare linea alkylbenzene (LAB) by the alkanisation reaction of C10 -C14 straight chain olefin on benzene at 120 -300 deg. C, 1.0 -5.0 MPa, 1 -20/h of weight space speed, 0.5/1 -25/1 (benzene/olefin) of mole ratio, and high transform rate. Its advantages are simple preparing process, good gravity nature, and simple regengration process.
Description
The present invention relates to a kind of by C
10～C
14Normal olefine and benzene alkylation producing linear alkylbenzene (LAB) through ion-exchange and acid-treated y-type zeolite molecular sieve catalyst.On this catalyzer, C
10～C
14But normal olefine high conversion ground and benzene alkylation reaction highly selective are converted into LINEAR ALKYL BENZENE (LAB), and this method for preparing catalyst is simple, and good reproducibility, catalyzer have higher activity and selectivity and catalyzed reaction stability and regenerability.
The reaction of traditional F riedel-Crafts type as aromatic hydrocarbon and normal olefine alkylated reaction, is mainly used A1Cl
3, BF
3, H
2SO
4, H
3PO
4, Lewis acid such as HF are as catalyzer, for C
10～C
14Normal olefine and benzene alkylation producing linear alkylbenzene utilize above-mentioned traditional catalyzer will generate 2-, 3-, 4-, the isomer of every alkylbenzene such as 5-.With AlCl
3Catalyzer is an example, its C
12Contain multiple isomer in the reaction product of normal olefine and benzene alkylation system alkylbenzene, wherein the selectivity of 2-alkylbenzene is 30%, because 2-alkylbenzene biological degradability is best, it is the industrial product that needs most, thereby the catalyzer that requires to be developed has the selectivity of higher 2-alkylbenzene isomer.Present industrial the most frequently used HF catalyzer, its C
12The selectivity of 2-alkylbenzene has only about 20% in the reaction product of normal olefine and benzene alkylation system alkylbenzene, H
2SO
4The C of catalyzer
12Normal olefine and benzene alkylation can reach 41% 2-alkylbenzene selectivity.But, above-mentioned HF, H
2SO
4Big especially to the corrodibility of equipment Deng homogeneous phase acid type catalyzer, catalyzer be difficult for to reclaim or regeneration, for this reason, impel chemists constantly research with exploitation to the conversion unit non-corrosiveness, and easily regeneration or the solid acid catalyst that reclaims.
From the beginning of the eighties, chemists begin one's study by the heterogeneous catalyst of Friedel-Crafts reaction production of linear alkylbenzene, and have obtained very big progress.As U.S.Pat4477585,4547605,4301317 grades adopt ZSM series molecular sieve as catalyzer, and to reach olefin conversion be 94%, and the LAB selectivity is 73% result; U.S.Pat5003121 and U.S.Pat5034565 reach olefin conversion 〉=98%, the good result of LAB selectivity 85% with the clay of pillared clays or rare earth ion dipping; CN1072353 adopts the Y zeolite of ion-exchange as catalyzer, can reach the good result of olefin conversion＞99%LAB selectivity 99%, but its catalyst life is very short, and its catalyst regeneration is frequent; The U.S.Pat5157158 sial, perhaps magnesosilicate is modified through polyvalent metal ion, or uses H
2SO
4, acid-treated catalyzer such as HF, olefin conversion＞95%, the LAB selectivity is greater than 85%, and the one way life-span of catalyzer reached more than 300 hours.
The purpose of this invention is to provide a kind of with benzene and C
10～C
14Normal olefine alkylation to prepare linear alkylbenzene catalyzer, this Preparation of catalysts method and utilize this catalyzer to carry out C
10～C
14Normal olefine and benzene alkylation reaction.
Catalyzer of the present invention adopts through the HY of metal ion-modified processing type molecular sieve catalyst, i.e. MHY molecular sieve catalyst, and metal ion is Fe
3+, Zr
4+, Ti
4+, one or more ions in alkaline-earth metal ions or the rare earth ion, the weight content of metal ion are 0.01～2.5%.In addition, for a change catalyzer is to the catalytic performance of reaction, and in the work-ing life of particularly improving catalyzer, through the distribution of acid treatment with adjusting catalyst acid center, used acid is H to catalyzer MHY molecular sieve of the present invention again
2SO
4, NH
4HSO
4, H
3PO
4, (NH
4)
2HPO
4, NH
4H
2PO
4, HNO
3, HCl, H
3BO
3, HF, NH
4F, or HF+NH4F make the MHY type molecular sieve catalyst of modification.Preparation of catalysts process of the present invention is undertaken by following step.
1. with Na-Y molecular sieve compression molding or the moulding of interpolation binding agent.When adding the binding agent moulding, can add Al in 1/10～1/2 ratio (weight ratio) in the catalyzer
2O
3, SiO
2, ZrO
2, TiO
4, MgO, CaO, kaolin, polynite, one or more in the binding agents such as bentonite are with the HNO of 0.5～6.0M
3Mechanically mixing is even, makes shaping of catalyst, and moulding process can carry out according to a conventional method.
2. in the ratio of 2～30ml/g, with the NH of 0.2～2.0M
4NO
3Solution mixes with molecular sieve, carry out ion-exchange 1～4 time at 50～100 ℃ with the Na-Y molecular sieve, after distilled water (2～20ml/g molecular sieve) washing 1～4 time, through 120 ℃ of oven dry 1～3h, 400～700 ℃ of roasting 1～6h, promptly get the HY molecular sieve, Na ion residues amount should be less than 10% in the HY molecular sieve.Above-mentioned HY molecular sieve is the ion exchange method of molecular sieve routinely also, carries out ion-exchange with diluted acid and NaY molecular sieve and prepares the HY molecular sieve.
3. in the ratio of 2～30ml/g, with above-mentioned HY molecular sieve and 0.5～2.0M alkaline-earth metal ions, rare earth ion, and Fe
3+, Zr
4+, Ti
4+In one or more ionic nitrate solutions mix, under 50～100 ℃ of stirrings, carry out ion-exchange 1～4 time, and with behind the distilled water wash 1～4 time, through 60～120 ℃ of oven dry 1～10 hour, 400～700 ℃ of roastings 1～10 hour promptly get metal ion molecular sieve MHY.
4. in the ratio of 2～30ml/g, with the H of above-mentioned MHY molecular sieve and 0.1～6M
2SO
4, NH
4HSO
4, H
3PO
4, (NH
4)
2HPO
4, HNO
3, HCl, H
3BO
3, HF, NH
4F, or NH
4One or more solution among the F mix, and at 20 ℃～100 ℃, react 0.3～20 hour, the excessive solution of inclining then, 60～120 ℃ of oven dry 1～10 hour, 400 ℃～700 ℃ roastings 1～10 hour, repeat 2～4 times, promptly get acid-treated MHY molecular sieve catalyst.Zhi Bei catalyzer has the olefin conversion of very high normal olefine and benzene alkylation reaction producing linear alkylbenzene and very high LAB selectivity like this, and catalyzer has catalytic stability preferably; The alkene per pass conversion reaches 97～99%, and the LAB selectivity reaches 90～99%, and wherein the selectivity of 2-alkylbenzene isomer can reach about 30%, and the catalyzer one way life-span reaches 150～300 hours.
When adopting fixed-bed reactor to carry out above-mentioned reaction, its reaction conditions is: benzene and C
10～C
14The olefin charging, the benzene olefin hydrocarbon molecules is than=0.5/1～25/1, and the charging air speed is 1～20h
-1, 120～300 ℃ of temperature of reaction, reaction pressure 0.5～5MPa.
In addition, following method is adopted in the regeneration of decaying catalyst of the present invention:
With benzene and C
10～C
13Normal paraffin (by 1: 1～1 0: 1 mol ratio) mixing solutions wash remove carbon deposit make catalyst activity obtain regeneration, regeneration condition is: temperature is 100～300 ℃, the best is 120 ℃～250 ℃, pressure is 0.5～5.0MPa, the best is 1.0～3.5MPa, and the parallel feeding air speed is 1.0～20.0h
-1, regeneration 1～20h.
Give detailed explanation below by example to content of the present invention:
The preparation of embodiment 1 ion-exchange type HY molecular sieve
With Na-Y molecular sieve 100g compression molding, add the NH of 1000mk 1.0M
4NO
3In the solution (80～90 ℃ water-baths), carry out ion-exchange 3 times, and under identical temperature, wash 3 times with 1000ml distilled water, then, baking 2h under 120 ℃, 550 ℃ of roasting 4h promptly get Hydrogen HY molecular sieve-4 A
1In the 100gNa-Y molecular sieve, add 20g kaolin mixing moulding, carry out the HY molecular sieve-4 A that ion-exchange obtains containing binding agent by above-mentioned identical method again
2
Embodiment 2 metal ion exchanged type catalyst B, C, D, the preparation of E and F
Get molecular sieve-4 A
1Sr (the NO of 20g and 2000ml0.5M
3)
2Solution mixes, and carries out ion-exchange 2 times at 80～90 ℃, and washs for 4 times with the distillation moisture of 800ml, and through 120 ℃ of baking 2h, 550 ℃ of roasting 4h 4 times so repeatedly, get catalyst B
1Get molecular sieve-4 A
220g repeats aforesaid method and makes catalyst B
2Get molecular sieve-4 A respectively with identical method
1And A
2, the La (NO of employing 0.25M
3)
3Solution exchanges, and obtains catalyzer C
1And C
2Get molecular sieve-4 A
120g, the Sr (NO of employing 0.5M
3)
2La (the NO of solution 100ml+0.25M
3)
3Solution 100ml exchanges jointly, obtains catalyzer D.Get molecular sieve-4 A
1, the Fe (NO of employing 0.25M
3)
3Solution exchanges as stated above, obtains catalyzer E.Get molecular sieve-4 A
2, the Zr (NO of employing 0.5M
3)
4Solution exchanges as stated above, obtains catalyzer F.
Embodiment 3 (NH
4)
2HPO
4The Preparation of catalysts of modifying
(NH with 100ml0.1M
4)
2HPO
4Solution is handled 2h at 80 ℃ to 10g catalyzer D, the surplus solution that inclines, and through 120 ℃ of baking 2h, 550 ℃ of roasting 3h, and repeat 1 time, promptly get catalyzer DI.
Embodiment 4 H
3PO
4The Preparation of catalysts of modifying
H with 100ml0.1M
3PO
4Solution at 80 ℃ to 10g catalyzer C
1Handle 2h, the surplus solution that inclines, through 120 ℃ of baking 2h, 550 ℃ of roasting 3h, and repeat 1 time, promptly get catalyzer CI.Handle catalyzer F with above-mentioned same procedure and obtain catalyzer FI.
Embodiment 5 benzene and 1-laurylene reaction system dodecylbenzene experiment 1
Molecular sieve-4 A 2g is packed in the reaction tubes of reactor inside diameter 9mm, at the N of 200ml/min
2Behind 350 ℃ of activation 1h, be 20h under purging with the air speed
-1Speed pump into 20ml in advance with the benzene of 4A molecular sieve and silica gel dehydration to be full of the entire reaction system, make reactor be warming up to 100 ℃ then, and with 20h
-1Air speed pump in advance benzene alkene mixing raw material 20ml with 4A molecular sieve and silica gel dehydration, the benzene with in the abundant substitution reaction system is warming up to 170 ℃ at last, in benzene/1-laurylene molecular ratio=15/1, air speed is 4h
-1, reaction pressure is under the reaction conditions of 2.8MPa, carries out benzene and olefin alkylation reaction, its reaction result sees Table 1.Utilize catalyst B respectively
1And B
2Repeat above-mentioned experiment, its reaction result sees Table 1.
Embodiment 6 benzene and 1-laurylene reaction system dodecylbenzene experiment 2
With catalyzer C
12g packs in the reaction tubes of reactor inside diameter 9mm, under the pretreatment conditions such as catalyst activation identical with embodiment 5 to catalyzer C
1After handling, adopt and embodiment 5 identical operations programs and following condition, promptly at 180 ℃, mixing raw material (benzene/1-laurylene=18/1), air speed is 6h
-1, reaction pressure is under the condition of 3.4MPa, to catalyzer C
1Carry out benzene and C
12The evaluation of olefine reaction performance, its reaction result sees Table 1.Use catalyzer C
2Replaced C
1Repeat above-mentioned experiment, its reaction result sees Table 1.
Embodiment 7 benzene and 1-laurylene reaction system dodecylbenzene experiment 3
Catalyzer D2g is packed in the reaction tubes of reactor inside diameter 9mm, after under the pretreatment conditions such as catalyst activation identical catalyzer D being handled with embodiment 5, adopt and embodiment 5 identical operations programs and following condition, promptly at 190 ℃, (benzene/1-laurylene=12/1, air speed are 2h to mixing raw material
-1, reaction pressure is under the condition of 2.2MPa, and catalyzer D is carried out benzene and C
12The evaluation of olefine reaction performance, its reaction result sees Table 1.Replace D to repeat above-mentioned experiment with catalyzer DI, its reaction result sees Table 1.
Embodiment 8 benzene and 1-laurylene reaction system dodecylbenzene experiment 4
Catalyzer E2g is packed in the reaction tubes of reactor inside diameter 9mm, after under the pretreatment conditions such as catalyst activation identical catalyzer E being handled with embodiment 5, adopt and embodiment 5 identical operations programs and following condition, promptly at 170 ℃, (benzene/1-laurylene=12/1, air speed are 4h to mixing raw material
-1, reaction pressure is under the condition of 3.2MPa, and catalyzer E is carried out benzene and C
12The evaluation of olefine reaction performance, its reaction result sees Table 1.Replace E to repeat above-mentioned experiment with catalyzer EI, its reaction result sees Table 1.
Embodiment 9 benzene and 1-laurylene reaction system dodecylbenzene experiment 5
Catalyzer F2g is packed in the reaction tubes of reactor inside diameter 9mm, after under the sharp activation grade of the catalysis identical pretreatment condition catalyzer F being handled with embodiment 5, adopt and embodiment 5 identical operations programs and following condition, promptly at 180 ℃, (benzene/1-laurylene=16/1, air speed are 6h to mixing raw material
-1, reaction pressure is under the condition of 3.0MPa, and catalyzer F is carried out benzene and C
12The evaluation of olefine reaction performance, its reaction result sees Table 1.Replace F to repeat province with catalyzer FI and state experiment, its reaction result sees Table 1.
The regeneration tests of embodiment 10 catalyzer
With the catalyzer FI of embodiment 9 through benzene and 1-laurylene alkylated reaction inactivation, be that 3/1 benzene and octane mixing solutions wash catalyzer is regenerated with mol ratio, its regeneration condition is: 150 ℃ of temperature, pressure 2.8MPa, the parallel feeding air speed is 4.0h
-1, the recovery time is 8h.
Embodiment 11 regeneration rear catalyst benzene and 1-laurylene reaction system dodecylbenzene experiment 6
Catalyzer EI2g after the regeneration is packed in the reaction tubes of reactor inside diameter 9mm, after under the pretreatment conditions such as catalyst activation identical catalyzer EI being handled with embodiment 5, adopt and embodiment 8 identical operations program and reaction conditionss, promptly at 170 ℃, mixing raw material (benzene/1-laurylene=12/1), air speed is 4h
-1, reaction pressure is under the condition of 3.2MPa, to carrying out benzene and C through regenerated catalyzer EI
12The evaluation of olefine reaction performance, its reaction result sees Table 1.
The reaction result embodiment catalyzer 1-laurylene of table 1 embodiment catalyzer benzene/1-laurylene reaction system dodecylbenzene changes straight chain dodecyl dodecylbenzene 2-dodecylbenzene catalyzer
Change rate (%) benzene selective (%) linear lag (%) selectivity (%) stability (h) 5 A 97.73 94.42 97.79 26.43 60 5 B
197.06 94.95 97.69 27.14 100 5 B
296.49 93.99 98.00 27.09 110 6 C
199.52 91.68 97.34 25.93 100 6 C
298.98 92.41 98.02 26.41 120 7 D, 99.73 92.37 98.46 29.59 100 7 DI, 98.04 96.98 98.45 29.41＞200 8 E, 97.36 96.59 98.21 29.59 100 8 EI, 96.27 95.44 97.96 28.93＞210 9 F, 97.84 93.45 98.12 26.65 100 9 FI, 96.10 94.24 97.91 27.01＞210 11 regeneration EI 97.50 96.12 98.19 29.41＞200
By above-mentioned example, method for preparing catalyst of the present invention is simple, good reproducibility, catalyzer has higher activity and selectivity and catalyzed reaction stability, and easily regenerates and reclaim, and the reclaiming process of catalyzer is simple, can be reflected on the same device, with be reflected at identical condition under carry out, saved time and energy, utilize the benzene and the C of this catalyzer
10～C
14The olefin alkylation reaction product can be used for producing biological degradability and the reasonable washing composition of emulsifying property, thereby can improve the quality of products, and reduces environmental pollution, has very big economic benefit and social benefit.
Claims (7)
1. one kind is used for benzene and C
10～C
14The Y molecular sieve catalyzer of normal olefine alkylated reaction system linear alkylbenzene is characterized in that being MHY, and M is a metal cations Fe
3+, Zr
4+, Ti
4+, one or more ions of alkaline-earth metal ions or rare earth ion, the weight content of metal ion are 0.01～2.5%.
2. according to the described catalyzer of claim 1, it is characterized in that the MHY molecular sieve is the MHY catalyzer after acid treatment.
3. according to the described catalyzer of claim 1, it is characterized in that to add Al by 1/10～1/2 weight ratio in the catalyzer
2O
3, SiO
2, ZrO
2, TiO
4, MgO, CaO, kaolin, polynite, one or more in the binding agents such as bentonite.
4. one kind according to the described Preparation of catalysts method of claim 1, it is characterized in that with 0.1～3.0MNH
4 +After salts solution carries out ion-exchange and makes the HY molecular sieve, again with the alkaline-earth metal ions that contains one or more 0.1～6.0M, rare earth ion, Fe
3+, Zr
4+Or Ti
4+The ionic aqueous solution carries out ion-exchange, and drying and roasting obtain catalyzer; Roasting was carried out under 400～700 ℃ 1～10 hour.
5. according to the described Preparation of catalysts method of claim 4, it is characterized in that catalyzer handles with acid again, used acid is H
2SO
4, NH
4HSO
4, H
3PO
4, (NH
4)
2HPO
4, NH
4H
2PO
4, HNO
3, HCl, H
3BO
3, HF, NH
4F, or HF+NH
4F handles, and gets catalyzer after drying and the roasting.
6. a utilization is carried out benzene and C according to the described catalyzer of claim 1
10～C
14Normal olefine alkylated reaction system linear alkylbenzene reaction process, it is characterized in that reaction conditions is: reaction temperature is 120～300 ℃, and reaction pressure is 0.5～5.0Mpa, and the reaction weight space velocity is 1～20h
-1, benzene/alkene (mol ratio) is 0.5/1-25/1.
7. according to the described reaction process of claim 6, it is characterized in that catalyst regeneration process is with benzene and C
10～C
13Normal paraffin (by 1: 1～10: 1 mol ratio) mixing solutions wash remove carbon deposit make catalyst activity obtain regeneration; Regeneration condition is: temperature is 100～300 ℃, and pressure is 0.5～5.0MPa, and the parallel feeding air speed is 1.0～20.0h
-1, regeneration 1～20h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN96115437A CN1077808C (en) | 1996-07-05 | 1996-07-05 | Catalyst of alkyl benzene with straight chain made by alkylation from benzene and straight chain olefin and its application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN96115437A CN1077808C (en) | 1996-07-05 | 1996-07-05 | Catalyst of alkyl benzene with straight chain made by alkylation from benzene and straight chain olefin and its application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1169889A true CN1169889A (en) | 1998-01-14 |
| CN1077808C CN1077808C (en) | 2002-01-16 |
Family
ID=5122690
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN96115437A Expired - Fee Related CN1077808C (en) | 1996-07-05 | 1996-07-05 | Catalyst of alkyl benzene with straight chain made by alkylation from benzene and straight chain olefin and its application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1077808C (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101844086B (en) * | 2009-03-25 | 2012-07-18 | 中国科学院大连化学物理研究所 | Method for preparing molybdenum based-catalyst for disproportionation of 1-butylene for preparing propylene |
| CN102874838A (en) * | 2012-08-05 | 2013-01-16 | 青岛惠城石化科技有限公司 | Method for regulating composition of Y-type molecular sieve |
| CN109985611A (en) * | 2019-04-28 | 2019-07-09 | 中国科学院兰州化学物理研究所 | A kind of catalyst and preparation method thereof, a kind of preparation method of N- alkyl imidazole compound |
| CN112642476A (en) * | 2019-10-09 | 2021-04-13 | 中国石油化工股份有限公司 | Activity control method for in-situ coke removal of aromatic hydrocarbon olefin removal catalyst and application thereof |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5157158A (en) * | 1988-08-03 | 1992-10-20 | Petroquimica Espanola, S.A. Petresa | Alkylation of aromatic hydrocarbons |
| US5003121A (en) * | 1989-08-28 | 1991-03-26 | Uop | Production of alkyl aromatic compounds |
| CN1034276C (en) * | 1991-11-20 | 1997-03-19 | 中国石化金陵石化公司烷基苯厂 | Solid acid catalyst for olefine hydrocarbons and phenyl alkylate |
| 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 |
-
1996
- 1996-07-05 CN CN96115437A patent/CN1077808C/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101844086B (en) * | 2009-03-25 | 2012-07-18 | 中国科学院大连化学物理研究所 | Method for preparing molybdenum based-catalyst for disproportionation of 1-butylene for preparing propylene |
| CN102874838A (en) * | 2012-08-05 | 2013-01-16 | 青岛惠城石化科技有限公司 | Method for regulating composition of Y-type molecular sieve |
| CN109985611A (en) * | 2019-04-28 | 2019-07-09 | 中国科学院兰州化学物理研究所 | A kind of catalyst and preparation method thereof, a kind of preparation method of N- alkyl imidazole compound |
| CN112642476A (en) * | 2019-10-09 | 2021-04-13 | 中国石油化工股份有限公司 | Activity control method for in-situ coke removal of aromatic hydrocarbon olefin removal catalyst and application thereof |
| CN112642476B (en) * | 2019-10-09 | 2023-04-07 | 中国石油化工股份有限公司 | Activity control method for in-situ coke removal of aromatic hydrocarbon olefin removal catalyst and application thereof |
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|---|---|
| CN1077808C (en) | 2002-01-16 |
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