CN1236850C - Modified Beta molecular sieve catalyst process for alkylation of isoalkane and isoalkene - Google Patents
Modified Beta molecular sieve catalyst process for alkylation of isoalkane and isoalkene Download PDFInfo
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- CN1236850C CN1236850C CNB021555982A CN02155598A CN1236850C CN 1236850 C CN1236850 C CN 1236850C CN B021555982 A CNB021555982 A CN B021555982A CN 02155598 A CN02155598 A CN 02155598A CN 1236850 C CN1236850 C CN 1236850C
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- molecular sieve
- beta molecular
- catalyst
- isoparaffin
- sample
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- 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
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Abstract
The present invention relates to a method for a modified beta molecular sieve catalyst for alkylation of isoalkane and isoalkene, which comprises the following steps: firstly, a beta molecular sieve or a beta molecular sieve and a mixture shaped by an adhesive are prepared into a sample of which the diameter is from 0.5mm to 1cm, the thickness is from 0.1mm to 1cm particle size; secondly, the beta molecular sieve or the beta molecular sieve and the mixture shaped by an adhesive are made into a hydrogen type sample; thirdly, according to the proportion by weight of 3 to 25 of the solution to solid, a citric acid solution of which the concentration is from 0.05 to 3.50 mol/l is added, the hydrogen type sample and the citric acid solution are treated for 0.5 to 12 hours under the condition of water bath heating at the temperature of 50 to 90DEG C, the liquid is spilled out, and the solid sample is dried at a low temperature and calcined at the temperature of 350 to 650 DEG C to obtain the modified beta molecular sieve catalyst. The catalyst obtained by the method has high reaction activity, and the activity stability is effectively lengthened.
Description
Technical field
The present invention relates to a kind of method of modifying that is used for the Beta molecular sieve catalyst of isoparaffin and olefin alkylation, specifically, is a kind of method of the modification Beta molecular sieve catalyst of handling through citric acid (beta-hydroxy tricarballylic acid), and this catalyst is used for C
4～C
6Isoparaffin and C
3～C
5The alkylation of monoolefine has very high activity and stable preferably.
Background technology
The alkylated reaction of isoparaffin and alkene is meant that the alkane and the olefine reaction that have alkyl group generate the branched more process of high molecular weight material that has, and are often referred to C
4-C
6Isoparaffin and C
3-C
5The course of reaction of monoolefine, the product of this alkylated reaction, the gasoline alkylate that generates as iso-butane and butene reaction has high octane number and low Reid vapour pressure, is a kind of gasoline ready-mixed oil of combustion cleaning, is the best blend component of gasoline.Present industrial production alkylate oil process still adopts traditional alkylation process before 50 years, be concentrated sulfuric acid method and hydrofluoric acid method, to produce a large amount of spent acid in the sulfuric acid process alkylation process, hydrofluoric acid is highly volatile then, there is the problem of serious environment pollutions such as spent acid recovery and equipment corrosion in these two kinds of methods, therefore develop free of contamination solid acid catalyst, to replace H
2SO
4With the HF liquid acid catalyst, become the important subject of petrochemical field, reported many solid acid catalysts that are used for the abovementioned alkyl process in recent years, molecular sieve catalyst is an important class wherein.
USP 4,300, and 015 has reported a kind of catalyst that is used for alkylation process, makes catalyst with the large pore molecular sieve after the polyvalent metal ion modification, improves reactivity and selectivity; USP 5,012, and 033 has reported the catalyst and the technology of a kind of isoparaffin and olefin alkylation, adopt with the acid-treated molecular sieve catalyst of Louis (Lewis), make under the condition that is reflected at higher space velocity and low alkane/alkene ratio to carry out.
Application number is that 97122136.7 Chinese patent has been reported a kind of isoparaffin and olefin alkylation process, use be Y zeolite, ZSM-20, MCM-36 and beta-zeolite catalyst with the trivalent metal ion modification.
Application number is that 00117060.0 Chinese patent has been reported a kind of preparation method who is used for iso-butane and butene alkylated modified beta molecular sieve, promote with ammonium sulfate again after promptly the beta-molecular sieve behind the dealuminzation being flooded with slaine, perhaps to the beta-molecular sieve TiCl behind the dealuminzation
4Modification is perhaps carried out calorize to the beta-molecular sieve behind the dealuminzation with aluminium salt.
Summary of the invention
The objective of the invention is to develop one one kinds of method of modifying that are used for the Beta molecular sieve catalyst of isoparaffin and olefin alkylation, with compare before the modification, not only reactivity is higher to use the catalyst that this method obtains, and active stability is effectively prolonged.
Catalyst provided by the present invention, its preparation method is: at first with the mixture after Beta molecular sieve or Beta molecular sieve and the binding agent moulding, be prepared into that to have diameter be 0.5mm～1cm, thickness is the sample of 0.1mm～1cm granularity, then be made into the Hydrogen sample with conventional method, be 3～25 ratio then according to the weight ratio of solution/solid, adding concentration is the citric acid solution of 0.05～3.50mol/l, under 50～90 ℃ condition of water bath heating, handled 0.5～12 hour, liquid is poured out, solid sample is through low temperature drying, 350～650 ℃ of roastings promptly obtain required modification Beta molecular sieve catalyst.
Be at least a in aluminium oxide, silica or the clay wherein with the molecular sieve molded binding agent of Beta.
Sample before the citric acid treatment can be pure Beta molecular sieve, also can be the mixture of Beta molecular sieve and binding agent moulding, and binding agent is aluminium oxide, silica, clay or their mixture.Sample is columned or ball shape.
Said sample can be columned, spherical, can also be any irregularly shaped.
Sample before the citric acid treatment is the Hydrogen sample that adopts conventional method to make.
The concentration of preferable citric acid solution is 0.15～2.0mol/l.
The preferable citric acid solution and the weight ratio of processed solid sample are 5～25, and the preferable time of handling with citric acid solution is 1～10 hour.
The catalyst that is used for isoparaffin and olefin alkylation provided by the invention, said C
4～C
6The preferred iso-butane of isoparaffin, C
3～C
5The preferred 1-butylene of monoolefine or 2-butylene or the mixture of the two.
The purposes of catalyst in isoparaffin and olefin alkylation reaction, said isoparaffin is C
4～C
6Isoparaffin, preferred iso-butane, alkene is C
3～C
5Monoolefine, preferred 1-butylene or 2-butylene or the mixture of the two.
The applied alkylation process of catalyst provided by the invention can carry out in various reactors, for example fixed bed reactors, batch reactor, moving-burden bed reactor, fluidized-bed reactor and paste state bed reactor, selected reaction condition has no particular limits.
The invention provides a kind of method that is used for the molecular sieve catalyst of isoparaffin and olefin alkylation, handle with the mixture of citric acid solution after to Beta molecular sieve or Beta molecular sieve and binding agent moulding.Citric acid (beta-hydroxy tricarballylic acid) is a kind of nontoxic organic matter, be widely used as the acid and the medicated premix of food, beverage, therefore adopt citric acid that the Beta molecular sieve is carried out modification, can not cause any murder by poisoning, this catalyst has eco-friendly characteristics.
Description of drawings
Fig. 1 is catalyst A and H-70Beta-30Al
2O
3The alkylation properties comparison diagram.
The specific embodiment
Below by example the present invention is further elaborated, but the present invention is not produced any restriction.
Example 1
With the conventional method prepared sizes is 20～40 purpose Beta molecular sieve (SiO
2/ Al
2O
3=30, as follows) with the mixture of aluminium oxide moulding, and be exchanged into Hydrogen, note is made H-70Beta-30Al
2O
3, wherein the weight content of Beta molecular sieve and aluminium oxide is respectively 70% and 30%.Get 15g H-70Beta-30Al
2O
3, adding 105g concentration is the citric acid solution of 0.6mol/L, under 75 ℃ of water-bath heating, handles 6h, liquid is separated with solid, and solid sample spends deionised water for several times, is 6 ~ 7 until the pH value of cleaning fluid, with the solid sample oven dry, through 540 ℃ of roasting 5h, obtain required catalyst A then.
Example 2
Preparing granular size with conventional method is the Beta molecular sieve of Φ 1.2 * (2～4) and the mixture of Ludox moulding, and is exchanged into Hydrogen, and note is made H-75Beta-25SiO
2, wherein the weight content of Beta molecular sieve and silica is respectively 75% and 25%.Get 15g H-70Beta-25SiO
2, adding 150g concentration is the citric acid solution of 0.4mol/L, under 80 ℃ of water-bath heating, handles 8h, liquid is separated with solid, and solid sample spends deionised water for several times, is 6 ~ 7 until the pH value of cleaning fluid, with the solid sample oven dry, through 600 ℃ of roasting 5h, obtain required catalyst B then.
Example 3
With the pure Beta molecular sieve of conventional method preparation 16～32 purposes, and be exchanged into Hydrogen, note is made H-Beta.Get 15g H-Beta, adding 225g concentration is the citric acid solution of 1.0mol/L, under 85 ℃ of water-bath heating, handle 4h, liquid is separated with solid, solid sample spends deionised water for several times, pH value until cleaning fluid is 6 ~ 7, with the solid sample oven dry,, obtain required catalyst C then through 520 ℃ of roasting 5h.
Example 4
With the mixture of conventional method preparation 50～70 purpose Beta molecular sieves and the moulding of aluminium colloidal sol, and be exchanged into Hydrogen, note is made H-80Beta-20Al
2O
3, wherein the weight content of Beta molecular sieve and aluminium oxide is respectively 80% and 20%.Get 15g H-80Beta-20Al
2O
3, adding 90g concentration is the citric acid solution of 1.3mol/L, under 85 ℃ of water-bath heating, handles 3h, liquid is separated with solid, and solid sample spends deionised water for several times, is 6 ~ 7 until the pH value of cleaning fluid, with the solid sample oven dry,, obtain required catalyst D then through 540 ℃ of roasting 6h.
Example 5
Respectively with the catalyst A and the contrast sample H-70Beta-30Al thereof of example 1 preparation
2O
3, be used for the alkylated reaction of iso-butane and 1-butylene, adopt continuous fixed-bed reactor, the catalyst loading amount is 10g.Catalyst is at N
2Preliminary treatment is 2 hours in the atmosphere, under 500 ℃ of conditions, then at 80 ℃, 3.0MPa, iso-butane/1-butylene mol ratio 20 and 1-butylene mass space velocity 0.2h
-1Reaction condition under, carry out alkylated reaction, from the reaction result of listing in Fig. 1 as can be seen, same H-70Beta-30Al
2O
3Compare, catalyst A not only has high reaction activity, and the selectivity of its activity and purpose product TMP prolongs in time and the speed that reduces obviously reduces.
Example 6
The mixture that is made into iso-butane and industrial hybrid C 4 is that (percentage composition of each component is reaction raw materials in the industrial hybrid C 4: propylene 0.19, propane 1.23, iso-butane 39.88,1-butylene 17.85,1,3-butadiene 0.21, normal butane 10.85, trans 2-butylene 17.98, cis 2-butylene 12.02), investigate the catalyst B of example 2 preparations and contrast sample H-75Beta-25SiO
2Alkylation properties, iso-butane/butylene mol ratio is 18.9, the butylene mass space velocity is 0.2h
-1, the remaining reaction process conditions are identical with example 5, and reaction result is listed in table 1.
Table 1, catalyst B and H-75Beta-25SiO
2Alkylation properties relatively
| TOS(min) | B | H-75Beta-25SiO 2 | ||
| Butene conversion (%) | TMP/C 5+ | Butene conversion (%) | TMP/C 5+ | |
| 40 | 96.0 | 21.78 | 98.0 | 21.66 |
| 60 | 99.0 | 21.07 | 99.2 | 18.50 |
| 80 | 99.6 | 19.80 | 98.2 | 17.61 |
| 100 | 99.8 | 18.63 | 98.0 | 15.87 |
| 120 | 99.9 | 17.25 | 74.0 | 8.92 |
| 140 | 99.7 | 15.93 | 53.1 | 4.68 |
| 160 | 87.2 | 12.65 | - | - |
| 180 | 62.8 | 7.78 | - | - |
Example 7
With the catalyst C and the contrast sample H-Beta thereof of example 3 preparations, be used for the alkylated reaction of iso-butane and 1-butylene respectively, 1-butylene mass space velocity is 0.3h
-1, the remaining reaction process conditions are identical with example 5, and reaction result is listed in table 2.
Table 2, the alkylation properties of catalyst C and H-Beta are relatively
| TOS(min) | C | H-Beta | ||
| Butene conversion (%) | TMP/C 5+ | Butene conversion (%) | TMP/C 5+ | |
| 40 | 97.2 | 23.19 | 98.9 | 22.36 |
| 60 | 99.2 | 22.24 | 99.5 | 20.17 |
| 80 | 99.6 | 20.62 | 99.7 | 17.82 |
| 100 | 99.7 | 19.73 | 99.5 | 14.91 |
| 120 | 99.5 | 18.61 | 67.4 | 7.64 |
| 140 | 99.4 | 16.49 | 45.6 | 5.13 |
| 160 | 81.6 | 13.18 | - | - |
| 180 | 59.4 | 8.29 | - | - |
Example 8
Respectively with the catalyst D and the contrast sample H-80Beta-20Al thereof of example 4 preparation
2O
3, being used for the alkylated reaction of iso-butane and 2-butylene, the mol ratio of iso-butane/2-butylene is 38.5,2-butylene mass space velocity is 0.12h
-1, the remaining reaction process conditions are identical with example 5, and reaction result is listed in table 3.
Table 3, the alkylation properties of catalyst C and H-Beta are relatively
| TOS(min) | D | H-80Beta-20Al 2O 3 | ||
| 2-butene conversion (%) | TMP/C 5+ | 2-T alkene conversion ratio (%) | TMP/C 5+ | |
| 30 | 99.6 | 29.01 | 99.0 | 26.56 |
| 60 | 100 | 27.34 | 99.6 | 27.32 |
| 90 | 100 | 26.43 | 100 | 26.70 |
| 120 | 100 | 24.92 | 100 | 26.07 |
| 150 | 100 | 25.12 | 100 | 23.97 |
| 180 | 100 | 20.02 | 99.4 | 12.56 |
| 210 | 99.6 | 16.09 | 88.2 | 8.86 |
| 240 | 99.5 | 11.35 | - | - |
| 270 | 89.9 | 8.85 | - | - |
Claims (5)
1. method of modifying that is used for the Beta molecular sieve catalyst of isoparaffin and olefin alkylation, it is characterized in that: at first with the mixture after Beta molecular sieve or Beta molecular sieve and the binding agent moulding, be prepared into that to have diameter be 0.5mm～1cm, thickness is the sample of 0.1mm～1cm granularity, then be made into the Hydrogen sample with conventional method, be 3～25 ratio then according to the weight ratio of solution/solid, adding concentration is the citric acid solution of 0.05～3.50mol/l, under 50～90 ℃ condition of water bath heating, handled 0.5～12 hour, liquid is poured out, solid sample is through low temperature drying, 350～650 ℃ of roastings promptly obtain required modification Beta molecular sieve catalyst.
2. a kind of method of modifying that is used for the Beta molecular sieve catalyst of isoparaffin and olefin alkylation according to claim 1, it is characterized in that: the sample before the citric acid treatment is pure Beta molecular sieve, or the mixture of Beta molecular sieve and binding agent moulding, with the molecular sieve molded binding agent of Beta be at least a in aluminium oxide, silica or the clay.
3. a kind of method of modifying that is used for the Beta molecular sieve catalyst of isoparaffin and olefin alkylation according to claim 1 is characterized in that: the sample before the citric acid treatment is columned or ball shape.
4. the purposes of catalyst in isoparaffin and olefin alkylation reaction that make of the method for claim 1 is characterized in that said isoparaffin is C
4~ C
6Isoparaffin, alkene are C
3~ C
5Monoolefine.
5. the purposes of catalyst in isoparaffin and olefin alkylation reaction that make of the method for claim 1, it is characterized in that said alkylated reaction carries out in fixed bed reactors, batch reactor, fluidized-bed reactor or paste state bed reactor.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021555982A CN1236850C (en) | 2002-12-13 | 2002-12-13 | Modified Beta molecular sieve catalyst process for alkylation of isoalkane and isoalkene |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021555982A CN1236850C (en) | 2002-12-13 | 2002-12-13 | Modified Beta molecular sieve catalyst process for alkylation of isoalkane and isoalkene |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1506160A CN1506160A (en) | 2004-06-23 |
| CN1236850C true CN1236850C (en) | 2006-01-18 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB021555982A Expired - Fee Related CN1236850C (en) | 2002-12-13 | 2002-12-13 | Modified Beta molecular sieve catalyst process for alkylation of isoalkane and isoalkene |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102441415B (en) * | 2010-10-13 | 2013-08-28 | 中国石油化工股份有限公司 | Alkane hydroisomerization catalyst and preparation method and application thereof |
| CN114247469A (en) * | 2020-09-24 | 2022-03-29 | 中国科学院大连化学物理研究所 | Preparation method of olefin |
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| CN1506160A (en) | 2004-06-23 |
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Granted publication date: 20060118 Termination date: 20201213 |