CN1110628A - Preparation of silicon/magnesium-mixed rear-earth modified catalyzer and its appliance - Google Patents
Preparation of silicon/magnesium-mixed rear-earth modified catalyzer and its appliance Download PDFInfo
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- CN1110628A CN1110628A CN 94110202 CN94110202A CN1110628A CN 1110628 A CN1110628 A CN 1110628A CN 94110202 CN94110202 CN 94110202 CN 94110202 A CN94110202 A CN 94110202A CN 1110628 A CN1110628 A CN 1110628A
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Abstract
The Si(or Mg)-mixed rare-earth modified (ZSM-5) zeolite molecular sieve catalyst is used to one-step synthesis of high-concentration (95-98%) p-dialkyl benzene in preparing p-methyl isopropylbenzene by alkylation of toluene and propene, p-ethyl toluene by ethylation of toluene and alcohol, p-xylene by alkylation of toluene and methanol, p-diethyl benzene by ethylation of ethylbenzene and ethylene, or p-diethylbenzene by alkylation of ethylbenzene and alcohol. The said catalyst is prepared by using ammonia water or orgamie amine as templet agent through exchange of ammonium nitrate, modifying with La-rich mixed rare-earth, baking and calcining. Its advantages include high shape selectivity, good activity and stability and long service life (1-1.5 years).
Description
The invention belongs to silicon (or magnesium)-mishmetal modified ZSM-5 zeolite molecular sieve catalyst preparation and the toluene propylated, ethylize, methylate and the ethylbenzene ethylation reaction in the application of synthetic multiple p dialkyl benzene.
Be raw material with toluene or ethylbenzene both at home and abroad, in the presence of catalyzer, carry out alkylated reaction, can obtain simultaneously the neighbour,, to the mixture of three kinds of dialkyl benzene isomer equilibrium composition.If seek out have industrial Practical significance, when mainly being the dialkyl benzene of contraposition, to need just to have to also the mixture fractionation by adsorption is carried out isomerization again, make neighbour, meta-isomer be transformed into cyclic monomer base benzene.So, the industrial complicacy that just increases production technique increases facility investment, and energy consumption also increases, and has strengthened process cost.Therefore, the development of shape-selective catalyst with use the important topic just become people's development researches.
Chinese patent CN85102764A has reported us and has utilized phosphorus-rare earth modified ZSM-5 zeolite molecular sieve, be applied to the synthetic of toluene disproportionation and toluene, ethylene alkylation, make the concentration of p-Xylol reach 90～95%, concentration to methyl-ethyl benzene reaches 95～97%, but this patent activity of such catalysts stability is not carried out long running, and only successive reaction is 100 hours; Afterwards, U.S. Pat P4,950,835 adopt silicon-Hydrogen modified ZSM-5 catalyst, be applied in toluene and ethylbenzene alkylation and the disproportionation reaction, increased p-Diethylbenzene, p-Xylol or, but do not see data and the condition that specifically provides catalyzer long running stability the yield of ethyltoluene; Nineteen ninety Chinese patent application publication number CN 1045930A has introduced with magnesium, aluminium modified ZSM-5 zeolite molecular sieve catalyst, ethylbenzene, ethanol are carried out alkylated reaction one-step synthesis p-diethylbenzene, make the transformation efficiency of ethylbenzene reach 5～10%, the selectivity of p-Diethylbenzene reaches 95～98%, application surface only limits to the preparation of p-Diethylbenzene, does not see the concrete data and the condition of 1200 hours catalyzer one way life-spans long running.
The objective of the invention is to make full use of that china natural resources is abundant, low-cost mishmetal comes the modulation zeolite molecular sieve, prepare have high shape selectivity, the catalyzer of excellent activity stability, extensively, directly synthesize the multiple p dialkyl benzene of high density, and on full scale plant, use the effect that obtains long running.
If only carry out toluene, propylene alkylated reaction system cymene with the H-ZSM-5 zeolite [molecular sieve, obtained adjacent,, the mixture of para-isomeride, it consists of: ortho position 1～5%, a position 65～69%, contraposition about 30%.Clearly, the content of p-Methylisopropylbenzene is very low.If this catalyzer is handled with mishmetal exchange or dipping modification, the result has just differed widely.
The present invention adopts ammoniacal liquor or organic amine to make Na type ZSM-5 zeolite molecular sieve as template, then with the aluminum oxide extruded moulding, exchange with ammonium nitrate again, after obtaining H type ZSM-5, handle with the mishmetal modification that contains rich lanthanum, carry out finishing with estersil at last, liquid deposition, the silicon of gained (or magnesium)-mishmetal modified ZSM-5 zeolite molecular sieve catalyst is used for toluene, propylene alkylation to prepare p-Methylisopropylbenzene; Toluene, ethanol ethylize system to ethyltoluene; Toluene, methanol alkylation system p-Xylol; Ethylbenzene, ethylene ethyl system p-Diethylbenzene; In the reaction such as ethylbenzene, ethanol alkylation system p-Diethylbenzene, all obtained the p dialkyl benzene of high density, shown that this catalyzer has very high shape selectivity, good activity stability, on the industrialness device of preparation p-Diethylbenzene, realized the satisfactory result of long running.
Of the present inventionly specifically be constructed as follows:
Five processing steps have been passed through in the preparation of one eka-silicon (or magnesium)-mishmetal modified ZSM-5 zeolite molecular sieve catalyst:
1. zeolite molecular sieve is synthetic
Adopt the solution of water glass, Tai-Ace S 150, sulfuric acid, ammoniacal liquor to be added in the autoclave, at 150～200 ℃, crystal seed exists down, crystallization 30～100 hours, resultant after filtration, washing, 120 ℃ of dryings make the former powder of ZSM-5 zeolite molecular sieve.
2. the ratio of components with zeolite molecular sieve and aluminum oxide is 50～85: 50～15, with 10% rare nitric acid is tackiness agent, be squeezed into φ 0.8～1.5 the garden cylindricality or with the mishmetal compression molding, after 80～120 ℃ of dryings, make Na type ZSM-5 zeolite molecular sieve 400～600 ℃ of roastings.
With Na type ZSM-5 with 0.3～1.0N NH
4NO
3Exchange, 20～80 ℃ of temperature exchange 2～4 times, and each 1 hour, washing, dry, roasting made H type ZSM-5 catalyzer.
4. H type ZSM-5 catalyzer is exchanged modification with mishmetal.Mishmetal is the carbonated rare earth with technical grade, and as in oxide compound, content is 72.62%, and impurity is 27.38%, contains abundant lanthanum (La) in the mishmetal, and lanthanum-oxides/rare earth oxide 〉=40%, modification processing method have five kinds:
A. H-ZSM-5 is exchanged 20～90 ℃ of temperature, 1 hour with mishmetal;
B. H-ZSM-5 is flooded 0～30 ℃ of temperature, 2～40 hours with mishmetal;
C. H-ZSM-5 is used water vapor earlier,, flood with mishmetal again 400～700 ℃ of processing;
D. H-ZSM-5 is first with 150～200 ℃ of high temperature poach, flood with mishmetal again;
E. with Na-ZSM-5 and mishmetal double elements by 60～90% and 40～10% weight ratio compression moldings, 540 ℃ of roastings 3 hours, make behind the H-ZSM-5 again the oxide compound dipping with magnesium, 0～30 ℃ of temperature, 5～30 hours;
5. with the catalyzer after the above-mentioned the whole bag of tricks processing modification, carry out finishing, liquid deposition with methyl silicate or ethyl ester more at last.Promptly with toluene, dimethylbenzene, normal hexane, hexanaphthene equal solvent dilution estersil, dipping steams and removes thinner.
Catalyzer after modification is handled can change the surface acid property of zeolite [molecular sieve on the one hand, and the also size of may command zeolite cavity is improved its shape selectivity energy on the other hand.
Silicon-mishmetal modified ZSM-5 zeolite molecular sieve catalyst with aforesaid method makes is used for toluene, propylene alkylated reaction system p-Methylisopropylbenzene, and the mol ratio of toluene and propylene is 10, and under the normal pressure, 240～260 ℃ of temperature of reaction, toluene by weight air speed are 3.4h
-1, continuous operation 328 hours, the transformation efficiency of toluene are 6.65%, the selectivity of p-Methylisopropylbenzene is 95.53%, and ortho position content 0.18%, right /=8.23, catalyzer follow procedure intensification air burns method regeneration four times, obtains excellent activity stability and regeneration repeatability.
Other application example can see the embodiment of back of the present invention for details.Advantage of the present invention: carry out alkylated reaction with silicon (or magnesium)-mishmetal modified ZSM-5 zeolite molecular sieve catalyst, the p dialkyl benzene that can synthesize multiple high density, the catalyzer that utilizes aboundresources, low-cost mishmetal to make, the life-span is long, anti-carbon deposit performance is good, and reproducibility is good; Catalyzer is by modifying and decorating, and active reduction is very little, increases substantially selectivity, strengthens the intensity of anti-hydro-thermal performance and catalyzer; Use the industrial raw material synthesis of molecular sieve, cost is low, pollutes little; Good stability is arranged, regeneration repeatability, catalyst activity and para-selectivity on full scale plant.
Embodiment 1
With silicon-mishmetal modified ZSM-5 zeolite molecular sieve catalyst, producing ethylbenzene, ethanol alkylation per year on 600 tons of p-Diethylbenzene devices test situation.
In the Preparation of Catalyst, ZSM-5 zeolite and Al
2O
3The carrier ratio is 80: 20, and it is 4.3% that hydrogen type catalyst carries the mishmetal amount, and the siliceous deposits amount is 3.1%, and the reactivity worth of this catalyzer is as follows:
Reaction conditions: 340 ℃ of temperature, feed weight air speed 6h
-1, ethylbenzene/ethanol mol ratio=9.5/1.0 the results are shown in following table:
The transformation efficiency of ethylbenzene is 8.5%, and the selectivity of p-Diethylbenzene is 96.25%, continuous operation 300 hours.
Embodiment 2
With silicon-mishmetal modified ZSM-5 zeolite molecular sieve catalyst, with ethylbenzene, ethylene alkylation system p-Diethylbenzene.
With ammoniacal liquor template synthetic zeolite and Al
2O
3The carrier ratio is 80: 20, be exchanged into hydrogen type catalyst by foregoing method, this catalyzer carries mishmetal amount 2.0%, regenerates 550 ℃ down with steam-treated modification in 3 hours, the depositing silicon amount is 3.0% more at last, with this catalyzer carry out ethylbenzene, vinyl alkyl is combined to p-Diethylbenzene.
Reaction conditions: 360 ℃ of temperature, ethylbenzene weight space velocity 5h
-1, ethylbenzene/ethylene molar ratio=3/1, N
2/ ethylene molar ratio 5/1, successive reaction 400 hours, conversion of ethylbenzene is 19.20%, para-selectivity is 95.08%.
Embodiment 3
With silicon-mishmetal modified ZSM-5 zeolite molecular sieve catalyst, carry out toluene, ethylene alkylation system p-methyl-ethylbenzene.
Make template synthetic zeolite and Al with ammoniacal liquor
2O
3The carrier ratio is 70: 30, be exchanged into hydrogen type catalyst by foregoing method, use steam-treated 5 hours down at 550 ℃, carrying the mishmetal amount then is 1.0%, the depositing silicon amount is 3.0%, carries out toluene, the synthetic p-methyl-ethylbenzene of ethylene alkylation with this catalyzer:
Reaction conditions: toluene/ethylene molar ratio=3.45/1,390 ℃ of temperature of reaction, toluene by weight air speed 6h
-1, N
2/ ethylene molar ratio is 5/1, and toluene conversion is 12.87%, and the selectivity of p-methyl-ethylbenzene is 95.98%.
Embodiment 4
With silicon-mishmetal modified ZSM-5 zeolite molecular sieve catalyst, carry out toluene, propylene alkylation to prepare p-Methylisopropylbenzene.
With n-Butyl Amine 99 template synthetic zeolite and Al
2O
3The carrier ratio is 80: 20,10% aqueous nitric acid is a tackiness agent, moulding, drying, roasting, get hydrogen type catalyst with conventional ion exchange system again, under 500 ℃,, carry mishmetal amount 0.5% through steam-treated 2 hours, the depositing silicon amount is 1%, carries out toluene, propylene alkylated reaction with this catalyzer.
Reaction conditions: toluene/propylene mol ratio is 10/1, normal pressure, and 240～260 ℃ of temperature of reaction, toluene by weight air speed are 3.4h
-1, continuous operation 310 hours, toluene conversion 6.65%, the selectivity of p-Methylisopropylbenzene are 96.07%, ortho position content 0.74%.
Embodiment 5
With magnesium-mishmetal modified ZSM-5 zeolite molecular sieve catalyst, carry out toluene, methanol alkylation system p-Xylol.
Make template synthetic zeolite and mishmetal with ammoniacal liquor, part by weight by 60～90% and 40～10% mixes, compression molding, 540 ℃ of roastings 3 hours, after the exchange of 0.4N ammonium nitrate solution room temperature, oven dry, roasting, use the rare nitric acid exchange of 0.6N, washing, oven dry, roasting again, obtain the double elements hydrogen type catalyst, carry out magnesium-modifiedly again, MgO dipping carrying capacity is by 1.7～4.0 oven dry, roasting.Carry out toluene, methanol alkylation system p-Xylol with this catalyzer:
Reaction conditions: toluene and methanol mol ratio=2/1,465 ℃ of temperature of reaction, toluene by weight air speed are 2h
-1, toluene conversion and p-Xylol selectivity are as follows: table 2
Table 2
| Catalyzer MgO content (%) | Toluene conversion (%) | P-Xylol selectivity (%) |
| 1.7 | 17.9 | 91.6 |
| 2.2 | 17.0 | 92.2 |
| 3.1 | 16.0 | 94.2 |
| 4.0 | 17.1 | 95.6 |
Embodiment 6
Make template synthetic zeolite and mishmetal with quadrol,, be exchanged into Hydrogen double elements catalyzer, carry MgO again, be written into by 3% and make modified catalyst according to embodiment 5 methods by 80% and 20% mixed.Carry out toluene, methanol alkylation system p-Xylol with this catalyzer:
Reaction conditions: toluene and methanol mol ratio=2/1,460 ℃ of temperature of reaction, toluene by weight air speed 2h
-1, continuous operation 300 hours, toluene conversion 26～29%, p-Xylol selectivity 97～98%, catalyzer has good stability and regenerability.
Embodiment 7
Make the mishmetal mixed pressuring plate of template synthetic zeolite powder and 20% with quadrol, be exchanged into hydrogen type catalyst and magnesium-modified, carry magnesium amount 3% by embodiment 5 methods.With carrying out toluene, the synthetic p-Xylol of methanol alkylation in this catalyzer, normal pressure, the fixed bed:
Reaction conditions: toluene and methanol mol ratio=2/1,435～480 ℃ of temperature of reaction, toluene by weight air speed are 2h
-1, toluene conversion and p-Xylol selectivity are as follows:
Embodiment 8
Press the hydrogen type catalyst of embodiment 7 methods preparation, carry magnesium amount 4%, on evaluating apparatus, investigate the influence of weight space velocity toluene, methanol alkylation reaction with this catalyzer:
Reaction conditions: toluene and methanol mol ratio 2=/1,455 ℃ of temperature of reaction, N
2/ material=10, the result is as follows:
Embodiment 9
In evaluating apparatus, carry out toluene, methanol alkylation reaction with 1 gram of the modified catalyst among the embodiment 8, estimate of the influence of toluene and methanol mol ratio reactivity worth:
Reaction conditions: 460 ℃ of temperature of reaction, toluene by weight air speed 2h
-1, N
2/ material=10.
Table 5
| The toluene and methanol mol ratio | Reactivity worth | |
| Toluene conversion (%) | P-Xylol selectivity (%) | |
| 1:1 | 33.81 | 97.52 |
| 2:1 | 28.42 | 97.88 |
| 3:1 | 20.41 | 98.24 |
| 4:1 | 18.34 | 98.64 |
Claims (10)
1, a class is used for silicon (or magnesium) the mishmetal modified ZSM-5 zeolite molecular sieve catalyst that alkylated reaction prepares the high density p dialkyl benzene, it is characterized in that this catalyzer is synthesizing through zeolite molecular sieve, with aluminum oxide extrusion molding (or elder generation and mishmetal compression molding), then Na-ZSM-5 and the ammonium nitrate that obtains is exchanged into the H-ZSM-5 catalyzer, carry out modification with mishmetal exchange or dipping or with steam-treated or with the high temperature poach again, carry out five step of finishing process with the estersil liquid deposition at last and make.
2, according to the described catalyzer of claim 1, it is characterized in that said mishmetal is the carbonated rare earth that adopts technical grade, its component is as in oxide compound, the content of rare earth is 72.62%, all the other are impurity, contain abundant lanthanum (La) in the mishmetal, lanthanum-oxides/rare earth oxide 〉=40%.
3, according to claim 1,2 described Preparation of catalysts methods, it is characterized in that the synthetic of zeolite molecular sieve, be to adopt ammoniacal liquor to make template, raw material is water glass, Tai-Ace S 150, sulfuric acid, ammoniacal liquor and water, raw material is counted by oxide compound:
Scope
OH
-/SiO
20.001～0.75
NH
+ 4/NH
+ 4＋Na
+0.65～0.94
H
2O/OH
-150～400
SiO
2/Al
2O
330～400
Synthesis condition: in autoclave, 150～200 ℃ of crystallization temperatures, crystallization 30～100 hours; As making template with organic amine (quadrol, n-Butyl Amine 99), raw material is water glass, Tai-Ace S 150, sulfuric acid, quadrol and water, and raw material is counted by oxide compound
Scope
OH
-/SiO
20.001～1.00
RN
+/RN
+Na
+0.30～1.00
H
2O/OH
-60～245
SiO
2/Al
2O
320～1000
Synthesis condition: with ammoniacal liquor is template.
4, according to claim 1,2 described Preparation of catalysts methods, when it is characterized in that H-ZSM-5 and mishmetal carry out modification, can adopt 20～90 ℃ of exchanges 1 hour, also can adopt at 0～30 ℃ and flood 2～40 hours, also can adopt earlier with water vapor after 400～700 ℃ of processing, flood with mishmetal again, or earlier with 150～200 ℃ high temperature poach, flood with mishmetal again, after above-mentioned the whole bag of tricks is handled modification, drying, roasting are carried out finishing with methyl silicate or ethyl ester liquid deposition at last.
5, according to claim 1,2 described Preparation of catalysts methods, it is characterized in that earlier Na-ZSM-5 and mishmetal double elements by 60～90% and 40～10% weight ratio compression moldings, 540 ℃ of roastings 3 hours, use magnesium oxide (MgO) dipping, oven dry, roasting again after making H-ZSM-5, make magnesium-mishmetal modified ZSM-5 catalyst.
6, can be used for the directly full scale plant of synthetic p-Diethylbenzene of ethylbenzene, ethanol alkylation according to claim 1,2,4 described catalyzer, it is characterized in that it is 4.3% that this catalyzer carries the mishmetal amount, the siliceous deposits amount is 3.1%, temperature of reaction when synthetic is 340 ℃, ethylbenzene and alcoholic acid mol ratio are 9.5, and the ethylbenzene weight space velocity is 6 hours
-1, conversion of ethylbenzene is 8.5%, the p-Diethylbenzene selectivity is 96.25%, continuous operation 300 hours.
7, can be used for the directly synthetic p-Diethylbenzene of ethylbenzene, ethanol alkylation according to claim 1,2,4 described catalyzer, it is characterized in that it is 2.0% that this catalyzer carries the mishmetal amount, at 550 ℃ with steam-treated 3 hours, the siliceous deposits amount is 3.0%, temperature of reaction when synthetic is 360 ℃, the mol ratio of ethylbenzene and ethene is 2, and the ethylbenzene weight space velocity is 5 hours
-1, conversion of ethylbenzene is 19.20%, the p-Diethylbenzene selectivity is 95.08%.
8, can be used for toluene, propylene alkylation to prepare to the toluene isopropyl benzene according to claim 1,2,4 described catalyzer, when it is characterized in that synthesizing, temperature of reaction is 240～260 ℃, and the mol ratio of toluene and propylene is 10, and the toluene by weight air speed is 3.4 hours
-1, toluene conversion is 6.65%, the p-Methylisopropylbenzene selectivity is 96.07%, continuous operation 310 hours.
9, can be used for toluene, methanol alkylation system p-Xylol according to claim 1,2,5 described catalyzer, it is characterized in that this catalyzer makes template with ammoniacal liquor, carrying the magnesium oxide amount is 4.0%, temperature of reaction when synthetic is 465 ℃, the mol ratio of toluene and methyl alcohol is 2, and the toluene by weight air speed is 2 hours
-1, toluene conversion is 17.1%, and the p-Xylol selectivity is 95.6%, and if catalyzer is made template with quadrol, carrying the magnesium oxide amount is 3%, and the temperature of reaction when synthetic is 460 ℃, and the mol ratio of toluene and methyl alcohol is 2, and the toluene by weight air speed is 2 hours
-1, toluene conversion is 26～29%, the p-Xylol selectivity is 97～98%, continuous operation 300 hours.
10, can be used for toluene, ethylene alkylation system p-methyl-ethylbenzene according to claim 1,2,4 described catalyzer, it is characterized in that this catalyzer makes template with ammoniacal liquor, at 550 ℃ with steam-treated 5 hours, carrying the mishmetal amount is 1.0%, the siliceous deposits amount is 3.0%, temperature of reaction when synthetic is 390 ℃, and the mol ratio of toluene and ethene is 3.45, and the toluene by weight air speed is 6 hours
-1, toluene conversion is 12.87%, the p-methyl-ethylbenzene selectivity is 95.98%.
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|---|---|---|---|
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|---|---|---|---|
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| CN1079285C (en) * | 1997-06-06 | 2002-02-20 | 中国石油化工总公司 | Catalyst for alkylation of benzene and ethylbenzene manufactured from ethylene |
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| CN85102764B (en) * | 1985-04-01 | 1988-02-24 | 大连工学院 | Preparation and application of zeolite catalyst modified by rare earth |
| US4950835A (en) * | 1989-10-24 | 1990-08-21 | Taiwan Styrene Monomer Corporation | Novel silicon-modified catalyst Si/HZSM-5, it's preparation, and a process for synthesizing high purity p-dialkyl benzene from monoalkyl benzene by using said catalyst |
| CN1045930A (en) * | 1990-03-15 | 1990-10-10 | 南开大学 | The catalyzer that is used for the synthetic p-diethylbenzene of ethylbenzene-ethanol alkylation |
| 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 |
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| CN102343275A (en) * | 2011-07-28 | 2012-02-08 | 北京服装学院 | HZSM-5 molecular sieve catalyst used in synthesis of p-diethylbenzene and preparation method thereof |
| CN102895989A (en) * | 2012-05-25 | 2013-01-30 | 南京大学 | Method for eliminating acidity of external surface of ZSM-5 molecular sieve catalyst |
| 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 |
| CN107913727A (en) * | 2017-10-31 | 2018-04-17 | 中海油天津化工研究设计院有限公司 | A kind of ethylbenzene is efficiently alkylated the preparation method of p-Diethylbenzene catalyst processed |
| CN107913727B (en) * | 2017-10-31 | 2020-05-29 | 中海油天津化工研究设计院有限公司 | Preparation method of catalyst for preparing p-diethylbenzene by efficiently alkylating ethylbenzene |
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