CN102372545A - Method for preparing olefin by alcohol dehydration - Google Patents
Method for preparing olefin by alcohol dehydration Download PDFInfo
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- CN102372545A CN102372545A CN2010102607754A CN201010260775A CN102372545A CN 102372545 A CN102372545 A CN 102372545A CN 2010102607754 A CN2010102607754 A CN 2010102607754A CN 201010260775 A CN201010260775 A CN 201010260775A CN 102372545 A CN102372545 A CN 102372545A
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Abstract
The invention relates to a method for preparing olefin by alcohol dehydration, and mainly aims to solve the problems of low selectivity of existing aluminum catalysts, strong acidity of existing molecular sieve catalysts, easy occurrence of side reaction, coking and deactivation. The method of the invention brings an alcohol raw material into contact with a catalyst. And the catalyst comprises the following components by weight: a) 30-90 parts of a porous material, which consists of Al2O3 and nSiO2 in a mole ratio, wherein, n=10-80, the XRD (x-ray diffraction) spectrum has a d-spacing maximum in the range of 9.5-9.9 angstroms, 6.7-7.1 angstroms, 4.4-4.8 angstroms, 3.8-4.0 angstroms, 3.6-3.8 angstroms and 3.1-3.7 angstroms; b) 10-70 parts of alumina. The technical method of the invention well solves the above problems, and can be used in the industrial production of olefin through alcohol dehydration.
Description
Technical field
The present invention relates to a kind of method of producing olefin hydrocarbon with alcohols dehydration
Background technology
The producing olefin hydrocarbon with alcohols dehydration catalyst for reaction tends to use aluminium oxide catalyst traditionally.But aluminum oxide is during as the alcohols dehydration catalyzer, and the dehydration reaction temperature is high, and general temperature of reaction is greater than 350 ℃, and energy consumption is big, poor selectivity.In addition, aluminium oxide catalyst can produce some unwanted side reactions in the catalyzing alcohols dehydration, like saturated hydrocarbons, unsaturated polymer, carbon monoxide, and some other unwanted side reaction, like aldehydes, acid etc.
In early days, people such as Miller (US2378236) are natural clay, after carrying out modification and handle like wilkinite, polynite etc. and 25% hot sulfuric acid, as the catalyzer of ethanol dehydration alkene.It has higher selectivity, but catalyst preparation process is seriously polluted, and its temperature of reaction is greater than 275 ℃, the not high easy inactivation of stability.
The eighties, the gama-alumina that people such as Wu (US4234752) disclose a kind of alkali modification is used for C
2～C
20The catalyzer of dehydration of alcohols system alkene, but its temperature of reaction is higher, and do not have stability data.
After the eighties, molecular sieve begins to be used for ethanol dehydration alkene, like ZSM-5, has obtained certain progress.But its acidity is stronger, is easy to produce side reaction, coking and deactivation.Especially ZSM-5 zeolite catalyst initial activity is high especially, and operation factors is changed sensitivity, the particularly fluctuation of temperature of reaction and air speed; Must strictly control, otherwise " temperature runaway " phenomenon might occur, cause olefinic polymerization; Produce " green oil ", finally cause catalyzer coking inactivation.
The SAPO-34 aluminophosphate molecular sieve also is used to the producing olefin hydrocarbon with alcohols dehydration catalyst for reaction, but its 8 Yuans annular apertures are less, C
4Or C
4Above alkene is difficult to diffuse out.
Summary of the invention
Technical problem to be solved by this invention is that existing aluminium oxide catalyst selectivity is lower, and existing sieve catalyst acidity is stronger, is prone to produce side reaction, and the problem of coking and deactivation provides a kind of new method that is used for producing olefin hydrocarbon with alcohols dehydration.This method has advantages of high catalytic activity and selectivity, and the advantage of stronger anti-coking performance is arranged.
For solving the problems of the technologies described above, the technical scheme that the present invention adopts is following: a kind of method of producing olefin hydrocarbon with alcohols dehydration, comprise alcohols feedstock is contacted with catalyzer that react generation alkene, wherein catalyst system therefor is in parts by weight under condition for validity,
Comprise following component:
A) 30～90 parts porous material; Wherein said porous material comprises the composition of following molar relationship: Al
2O
3: nSiO
2, n=10 in the formula～80, the XRD diffracting spectrum of said porous material is 9.7 ± 0.2, and there is d-spacing peak at 6.9 ± 0.2,4.6 ± 0.2,3.9 ± 01,3.7 ± 0.1 and 3.4 ± 0.3 dust places;
B) 10～70 parts aluminum oxide.
In the technique scheme, the condition for validity preferable range that alcohols feedstock contacts with catalyzer is: range of reaction temperature is 200～300 ℃, and preferable range is 220～290 ℃; The reaction pressure scope is 0.02～1MPa, and preferable range is 0.05～1MPa; Liquid phase air speed scope is 0.2～3 hour
-1, preferable range is 0.5～2 hour
-1Said alcohols preferred version is selected from C
2～C
14Alcohol.Said porous material comprises the composition of following molar relationship: Al
2O
3: nSiO
2, the preferable range of n is 13～70 in the formula, more preferably scope is 15～60.In parts by weight, the consumption of porous material is 35～85 parts.Said aluminum oxide preferred version is for being selected from γ-Al
2O
3
The preparation method of porous material is following among the present invention: silicon source, aluminium source, template R, alkali and water are mixed, and mixture is with molar ratio computing SiO
2/ Al
2O
3=13～70, H
2O/SiO
2=10～70, R/SiO
2=0.01～0.5, OH
-/ SiO
2=0.2～0.6, be under 140～170 ℃ of conditions with said mixture in temperature, crystallization was taken out after 18～120 hours, made said porous material through washing, drying.Wherein said template R is selected from least a of (ETMAOH) in tetraethyl ammonium hydroxide (TEAOH), hexahydropyridine, pyridine, dimethyl-diethylammonium volatile caustic (DMDEAOH) or the ethyl-trimethyl volatile caustic.Said silicon source is selected from least a in soft silica, silicon sol, silica gel, zeyssatite or the water glass; Said aluminium source is selected from least a in white lake, aluminum isopropylate, ASBD, sodium aluminate, Tai-Ace S 150, aluminum nitrate, aluminum chloride or the aluminum oxide, and said alkali is selected from least a in Lithium Hydroxide MonoHydrate, sodium hydroxide, Pottasium Hydroxide, rubidium hydroxide or the cesium hydroxide; Mixture is following with the molar ratio computing preferable range: SiO
2/ Al
2O
3=15～60, H
2O/SiO
2=15～60, R/SiO
2=0.04～0.3, OH
-/ SiO
2=0.3～0.5.
The Preparation of catalysts method is following among the present invention: earlier synthetic porous material and activated alumina are mixed; Add sticker mix pinch, moulding, drying, roasting; Process catalyst precursor; With ammonium salt solution wherein sodium ion is exchanged again, again through super-dry, calcination activation, promptly get the catalyzer finished product at last.
Porous material crystal habit among the present invention is the thin layer sheet structure, or the sheet aggregate, and its acid hydroxy group mainly is distributed in the interior and outside surface of cage of porous material, and bigger reactant molecule is easy to pass in and out the duct of this porous material.Porous material acidity than ZSM-5 a little less than, and its huge surfactivity center has overcome space steric effect and the side reaction of molecular sieve pore passage to the bigger alcohols of molecular weight.Because porous material is the thin layer sheet structure, there is 1/3rd acidic site to be distributed in its surface, quite a few carries out the alcohols dehydration reaction in the outside surface active site of porous material.Because surface reaction outside, concentration of reactants are difficult for rich long-pending, and help the bigger alkanol molecule reaction of volume.Therefore, the porous material catalyzer helps unit molecule and the bigger alkanol molecule reaction of volume, promptly helps dehydration generation alkene in the alkanol molecule; In addition, carry out, lack effective concentration and carry out dimolecular reaction owing to be reflected at main outside surface at porous material---dehydration generates ether between alkanol molecule, and alkene has comparative advantage in the reaction product.On the other hand, porous material is the thin layer sheet structure, makes its duct short, is easy to diffusion, thereby has improved its anti-coking performance greatly.Therefore the porous material catalyzer is difficult for coking in reaction process, and side reaction is few, and dehydration reaction efficient is high, and olefine selective is high, can reach more than 98%, has obtained better technical effect.
Description of drawings
Fig. 1 is the X-ray diffraction spectrum of poromerics.
Through embodiment the present invention is done further elaboration below.
Embodiment
[embodiment 1]
With sodium hydroxide 2.2 gram, silicon sol (40 weight %) 16 grams, ASBD 1.4 grams, dimethyl-diethylammonium volatile caustic (20 weight %) 6.4 grams, zero(ppm) water 26 grams, to mix and stir, the mol ratio of each component is SiO
2/ Al
2O
3=36, H
2O/SiO
2=20, OH
-/ SiO
2=0.43, R/SiO
2=0.1.Said mixture, elevated temperature to 160 ℃ crystallization rotating the baking oven dynamic crystallization after 48 hours, with the crystallizing kettle cool to room temperature, through centrifugal, washing, filtration, was put into 100 ℃ of dryings of baking oven 8 hours with product again.X-ray powder diffraction data are seen table 1.
Table 1
Synthetic porous material 40 gram and 40 is restrained aluminum oxide mix, mixed powder and rare nitric acid (0.6 weight %) mix by 80: 20 weight ratio and pinch, moulding, drying.550 ℃ of roastings promptly got catalyzer of the present invention after 6 hours in air.
The catalyzer of processing is carried out the exchange of 3 secondary ions with 0.4 volumetric molar concentration ammonium chloride solution,, last 3 hours, handle the back sodium content less than 50ppm at every turn at 75 ℃.With the catalyzer after the exchange of above-mentioned ammonium at room temperature filter, drying, activation 4 hours under 500 ℃ of temperature in air, cool to room temperature is subsequent use.This catalyzer is used for ethanol dehydration reaction, is 250 ℃ in temperature of reaction, and reaction pressure is a normal pressure, and the liquid air speed is 0.8 hour
-1Check and rate under the condition, the result sees table 6.
[embodiment 2]
With sodium hydroxide 2.1 gram, silicon sol (40 weight %) 16 grams, ASBD 0.8 gram, dimethyl-diethylammonium volatile caustic (20 weight %) 9 grams, zero(ppm) water 26 grams, to mix and stir, the mol ratio of each component is SiO
2/ Al
2O
3=65, H
2O/SiO
2=17, OH
-/ SiO
2=0.49, R/SiO
2=0.14.Said mixture, elevated temperature to 160 ℃ crystallization rotating the baking oven dynamic crystallization after 48 hours, with the crystallizing kettle cool to room temperature, through centrifugal, washing, filtration, was put into 100 ℃ of dryings of baking oven 8 hours with product again.X-ray powder diffraction data are seen table 2.
Table 2
Synthetic porous material 40 gram and 70 is restrained aluminum oxide mix, mixed powder and rare nitric acid (0.6 weight %) mix by 80: 20 weight ratio and pinch, moulding, drying.550 ℃ of roastings promptly got catalyzer of the present invention after 6 hours in air.
The catalyzer of processing is carried out the exchange of 3 secondary ions with 0.4 volumetric molar concentration ammonium chloride solution,, last 3 hours, handle the back sodium content less than 50ppm at every turn at 75 ℃.With the catalyzer after the exchange of above-mentioned ammonium at room temperature filter, drying, activation 4 hours under 500 ℃ of temperature in air, cool to room temperature is subsequent use.This catalyzer is used for ethanol dehydration reaction, is 220 ℃ in temperature of reaction, and reaction pressure is 1.0MPa, and the liquid air speed is 1.3 hours
-1Check and rate under the condition, the result sees table 6.
[embodiment 3]
With sodium hydroxide 1.7 gram, silicon sol (40 weight %) 16 grams, ASBD 3.5 grams, dimethyl-diethylammonium volatile caustic (20 weight %) 25 grams, zero(ppm) water 95 grams, to mix and stir, the mol ratio of each component is SiO
2/ Al
2O
3=15, H
2O/SiO
2=60, OH
-/ SiO
2=0.40, R/SiO
2=0.40.Said mixture, elevated temperature to 150 ℃ crystallization rotating the baking oven dynamic crystallization after 48 hours, with the crystallizing kettle cool to room temperature, through centrifugal, washing, filtration, was put into 100 ℃ of dryings of baking oven 8 hours with product again.X-ray powder diffraction data are seen table 3.
Table 3
Synthetic porous material 40 gram and 5 is restrained aluminum oxide mix, mixed powder and rare nitric acid (0.6 weight %) mix by 80: 20 weight ratio and pinch, moulding, drying.550 ℃ of roastings promptly got catalyzer of the present invention after 6 hours in air.
The catalyzer of processing is carried out the exchange of 3 secondary ions with 0.4 volumetric molar concentration ammonium chloride solution,, last 3 hours, handle the back sodium content less than 50ppm at every turn at 75 ℃.With the catalyzer after the exchange of above-mentioned ammonium at room temperature filter, drying, activation 4 hours under 500 ℃ of temperature in air, cool to room temperature is subsequent use.This catalyzer is used for ethanol dehydration reaction, is 290 ℃ in temperature of reaction, and reaction pressure is 0.05MPa, and the liquid air speed is 0.5 hour
-1Check and rate under the condition, the result sees table 6.
[embodiment 4]
With sodium hydroxide 1.8 gram, tetraethoxy 20 grams, aluminum isopropylate 1 gram, ethyl-trimethyl volatile caustic (20 weight %) 12 grams, zero(ppm) water 50 grams, to mix and stir, the mol ratio of each component is SiO
2/ Al
2O
3=39, H
2O/SiO
2=31, OH
-/ SiO
2=0.33, R/SiO
2=0.24.Said mixture, elevated temperature to 160 ℃ crystallization rotating the baking oven dynamic crystallization after 56 hours, with the crystallizing kettle cool to room temperature, through centrifugal, washing, filtration, was put into 100 ℃ of dryings of baking oven 8 hours with product again.X-ray powder diffraction data are seen table 4.
Table 4
Synthetic porous material 40 gram and 25 is restrained aluminum oxide mix, mixed powder and rare nitric acid (0.6 weight %) mix by 80: 20 weight ratio and pinch, moulding, drying.550 ℃ of roastings promptly got catalyzer of the present invention after 6 hours in air.
The catalyzer of processing is carried out the exchange of 3 secondary ions with 0.4 volumetric molar concentration ammonium chloride solution,, last 3 hours, handle the back sodium content less than 50ppm at every turn at 75 ℃.With the catalyzer after the exchange of above-mentioned ammonium at room temperature filter, drying, activation 4 hours under 500 ℃ of temperature in air, cool to room temperature is subsequent use.This catalyzer is used for ethanol dehydration reaction, is 250 ℃ in temperature of reaction, and reaction pressure is a normal pressure, and the liquid air speed is 2.0 hours
-1Check and rate under the condition, the result sees table 6.
[embodiment 5]
With sodium hydroxide 1.1 gram, silicon sol 16 grams, ASBD 1.4 grams, hexahydropyridine 0.4 gram, zero(ppm) water 36 grams, to mix and stir, the mol ratio of each component is SiO
2/ Al
2O
3=37, H
2O/SiO
2=19, OH
-/ SiO
2=0.25, R/SiO
2=0.04.Said mixture, elevated temperature to 150 ℃ crystallization rotating the baking oven dynamic crystallization after 18 hours, with the crystallizing kettle cool to room temperature, through centrifugal, washing, filtration, was put into 100 ℃ of dryings of baking oven 8 hours with product again.X-ray powder diffraction data are seen table 5.
Table 5
Synthetic porous material 40 gram and 40 is restrained aluminum oxide mix, mixed powder and rare nitric acid (0.6 weight %) mix by 80: 20 weight ratio and pinch, moulding, drying.550 ℃ of roastings promptly got catalyzer of the present invention after 6 hours in air.
The catalyzer of processing is carried out the exchange of 3 secondary ions with 0.4 volumetric molar concentration ammonium chloride solution,, last 3 hours, handle the back sodium content less than 50ppm at every turn at 75 ℃.With the catalyzer after the exchange of above-mentioned ammonium at room temperature filter, drying, activation 4 hours under 500 ℃ of temperature in air, cool to room temperature is subsequent use.This catalyzer is used for ethanol dehydration reaction, is 280 ℃ in temperature of reaction, and reaction pressure is 0.7MPa, and the liquid air speed is 1.0 hours
-1Check and rate under the condition, the result sees table 6.
Table 6
[embodiment 6]
The catalyzer that [embodiment 1～5] makes is used for 3-methyl isophthalic acid-butanols dehydration reaction, is 275 ℃ in temperature of reaction, and reaction pressure is a normal pressure, and the liquid air speed is 0.6 hour
-1Check and rate under the condition, the result sees table 7.
Table 7
[embodiment 7]
The catalyzer that [embodiment 1～5] makes is used for 2, and 11-dimethyl--2-lauryl alcohol dehydration reaction is 280 ℃ in temperature of reaction, and reaction pressure is a normal pressure, and the liquid air speed is 0.3 hour
-1Check and rate under the condition, the result sees table 8.
Table 8
Claims (8)
1. the method for a producing olefin hydrocarbon with alcohols dehydration comprises alcohols feedstock is contacted with catalyzer under condition for validity, and reaction generates alkene, and wherein catalyst system therefor comprises following component in parts by weight:
A) 30～90 parts porous material; Wherein said porous material comprises the composition of following molar relationship: Al
2O
3: nSiO
2, n=10 in the formula～80, the XRD diffracting spectrum of said porous material is 9.7 ± 0.2, and there is d-spacing peak at 6.9 ± 0.2,4.6 ± 0.2,3.9 ± 0.1,3.7 ± 0.1 and 3.4 ± 0.3 dust places;
B) 10～70 parts aluminum oxide.
2. according to the method for the said producing olefin hydrocarbon with alcohols dehydration of claim 1, it is characterized in that the condition for validity that alcohols feedstock contacts with catalyzer is: 200～300 ℃ of temperature of reaction, reaction pressure 0.02～1MPa, liquid phase air speed 0.2～3 hour
-1
3. according to the method for the said producing olefin hydrocarbon with alcohols dehydration of claim 2, it is characterized in that temperature of reaction is 220～290 ℃, reaction pressure is 0.05～1MPa, and the liquid phase air speed is 0.5～2 hour
-1
4. according to the method for the said producing olefin hydrocarbon with alcohols dehydration of claim 1, it is characterized in that said alcohols is C
2～C
14Alcohol.
5. according to the method for the said producing olefin hydrocarbon with alcohols dehydration of claim 1, it is characterized in that said porous material comprises the composition of following molar relationship: Al
2O
3: nSiO
2, n=13 in the formula～70.
6. according to the method for the said producing olefin hydrocarbon with alcohols dehydration of claim 5, it is characterized in that said porous material comprises the composition of following molar relationship: Al
2O
3: nSiO
2, n=15 in the formula～60.
7. according to the method for the said producing olefin hydrocarbon with alcohols dehydration of claim 1, it is characterized in that the consumption of porous material is 35～85 parts in parts by weight.
8. according to the method for the said producing olefin hydrocarbon with alcohols dehydration of claim 1, it is characterized in that said aluminum oxide is γ-Al
2O
3
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103664452A (en) * | 2012-09-05 | 2014-03-26 | 中国石油化工股份有限公司 | Method for producing ethylene by dehydration of alcohol |
| CN111718237A (en) * | 2020-07-07 | 2020-09-29 | 万华化学集团股份有限公司 | Preparation method of bio-based isomeric tridecanol |
| WO2024080319A1 (en) * | 2022-10-13 | 2024-04-18 | 株式会社クラレ | 3-methyl-1-butene, and production method of 3-methyl-1-butene polymer |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1124973A (en) * | 1993-04-26 | 1996-06-19 | 美孚石油公司 | Synthetic layered material, MCM-56, its synthesis and use |
| CN101239728A (en) * | 2007-02-07 | 2008-08-13 | 中国石油化工股份有限公司 | Micro-pore zeolite, preparation method and application thereof |
| CN101492333A (en) * | 2008-01-23 | 2009-07-29 | 中国石油化工股份有限公司 | Method for producing olefin hydrocarbon with alcohols dehydration |
-
2010
- 2010-08-23 CN CN2010102607754A patent/CN102372545B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1124973A (en) * | 1993-04-26 | 1996-06-19 | 美孚石油公司 | Synthetic layered material, MCM-56, its synthesis and use |
| CN101239728A (en) * | 2007-02-07 | 2008-08-13 | 中国石油化工股份有限公司 | Micro-pore zeolite, preparation method and application thereof |
| CN101492333A (en) * | 2008-01-23 | 2009-07-29 | 中国石油化工股份有限公司 | Method for producing olefin hydrocarbon with alcohols dehydration |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103664452A (en) * | 2012-09-05 | 2014-03-26 | 中国石油化工股份有限公司 | Method for producing ethylene by dehydration of alcohol |
| CN103664452B (en) * | 2012-09-05 | 2015-07-08 | 中国石油化工股份有限公司 | Method for producing ethylene by dehydration of alcohol |
| CN111718237A (en) * | 2020-07-07 | 2020-09-29 | 万华化学集团股份有限公司 | Preparation method of bio-based isomeric tridecanol |
| WO2024080319A1 (en) * | 2022-10-13 | 2024-04-18 | 株式会社クラレ | 3-methyl-1-butene, and production method of 3-methyl-1-butene polymer |
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