CN102806101A - Catalyst for preparing ethylene by conversion of ethanol and preparation method of catalyst - Google Patents
Catalyst for preparing ethylene by conversion of ethanol and preparation method of catalyst Download PDFInfo
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- CN102806101A CN102806101A CN2012102859932A CN201210285993A CN102806101A CN 102806101 A CN102806101 A CN 102806101A CN 2012102859932 A CN2012102859932 A CN 2012102859932A CN 201210285993 A CN201210285993 A CN 201210285993A CN 102806101 A CN102806101 A CN 102806101A
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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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- 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
- Y02P20/584—Recycling of catalysts
Abstract
The invention discloses a catalyst for preparing ethylene by conversion of ethanol and a preparation method of the catalyst. The catalyst comprises, by weight, 70-100 parts of HZSM-5 molecular sieves, 1-30 parts of binders, 1-15 parts of extrusion assistants and 0.01-10 parts of impurity element modifiers, wherein the binders can be one or multiple of sesban powder, Xuyong porcelain clay, pseudo-boehmite powder, kaolin and clay; the binders can be one or multiple of oxalic acid, citric acid, plyvinyl alcohol, starch and methylcellulose; and the impurity element modifiers can be mixture of three of or more than three of soluble compounds containing elements of P, Fe, Zn, K, Ce, La, Sr, Ba, Ca, Mg, Mo or Mn. The catalyst has high strength and hydrothermal stability, can be used for reaction for preparing the ethylene by dehydration of ethanol solution with wide concentration range (20%-100%), and has the advantages of low reaction temperature (220 DEG C-300 DEG C), high activity and ethylene selectivity, long regeneration period and the like.
Description
Technical field
The present invention relates to a kind of Catalysts and its preparation method by ethanol conversion system ethene.
Background technology
Ethene is important petrochemical industry basic material, can be in order to produce multiple important Organic Chemicals.Yet because oil supply is in short supply, the rise of crude oil price and traditional petroleum path are produced the environmental problem that ethene brings, and non-traditional petroleum path is produced ethene will have very big market prospects.The bio-ethanol industry obtains flourish these needs that catered to just at present, and along with the maturation of bio-ethanol technology, the continuous reduction of bio-ethanol cost makes the alcohol production ethylene process have more economic advantages simultaneously.
Catalyst is the research emphasis of ethylene prepared by catalytic dehydration of ethylene.At present, the ethanol dehydration catalyst is mainly modified alumina catalyst in the industry.It is to use high concentration ethanol (more than 95%) that there is subject matter in this type catalyst, and operating temperature is higher than 350 ℃, the lower (0.3h of air speed
-1～0.6h
-1), yield of ethene low (70～90%), energy consumption is big.And zeolite has than highly acid and duct and selects the shape effect, is a kind of novel ethanol dehydration catalyst.Wherein, The HZSM-5 molecular sieve because have that hydrothermally stable is good, the catalytic reaction temperature is low, active high, air speed is high and to advantages such as the material concentration requirement are low; Becoming the catalyst of studying at most in the producing ethylene from dehydration of ethanol reaction, also is the molecular sieve catalysts that is hopeful in the biological ethane industry, to obtain industrial applications most.Like U.S. Pat 4670620 reports, be catalyst with Ca, Fe or La modification Pentasil type zeolite molecular sieve, at 250～370 ℃, 0.1～2h
-1Under the air speed condition, ethanol conversion and yield of ethene yield of ethene>99%, but it still adopts a large amount of helium as carrier gas, and reaction temperature is still higher; Chinese patent CN86101615 report adopts aluminium oxide and silica-rich zeolite molecular sieve prepared by co-precipitation catalyst, and it is ethylene reaction produced to carry out the straight alcohol dehydration, at 250～390 ℃, 1～3h
-1Under the air speed condition, ethanol conversion 96%, ethylene selectivity 98%, but its still to adopt high concentration ethanol be reaction raw materials.Chinese patent CN 101274286 reports, its air speed is at 0.1～10h
-1Under the condition, its conversion ratio and selectivity are near 100%.Describe from its patent, though do not use inert gas dilution, the operating condition of long-life (1000 h) still with high concentration ethanol as charging.From above-mentioned three patents; Though adopt molecular sieve to be superior to aluminium oxide catalyst as catalyst; But still exist the concentration of alcohol height maybe need adopt Macrodilution gas; Reaction temperature is still higher, and the present invention adopts assorted elements compounding modified HZSM-5 molecular sieve as catalyst, has higher intensity and hydrothermal stability; It is ethylene reaction produced to can be used for the dehydration of low operating temperature (220 ℃～300 ℃), broad concentration range (20%～100%) ethanolic solution, and have that reaction temperature is low, catalyst activity and selectivity advantages of higher.
Summary of the invention
The preparation method who the purpose of this invention is to provide a kind of catalyst for ethanol delydration to ethylene.The catalyst that this method is produced has higher-strength and hydrothermal stability, and it is ethylene reaction produced to can be used for broad concentration range ethanolic solution dehydration, and have that reaction temperature is low, catalyst activity and selectivity advantages of higher.
For realizing above-mentioned purpose, the present invention adopts following technical scheme:
A kind of catalyst by ethanol conversion system ethene is characterized in that comprising following component: the HZSM-5 molecular sieve of 70～100 weight portions, 1-30 parts by weight of adhesive, the extrusion aid of 1-15 weight portion, the assorted element modifier of 0.01-10 weight portion.
In above-mentioned arbitrary technical scheme, preferred silica alumina ratio is the HZSM-5 molecular sieve of 25-200; More preferably the silica alumina ratio below the crystal grain 5 μ m is the HZSM-5 molecular sieve of 25-100.
In above-mentioned arbitrary technical scheme, preferred 1-20 parts by weight of adhesive; Binding agent can be selected from one or more in sesbania powder, Xuyong china clay, aluminium hydroxide, boehmite, kaolin or the clay; In preferred sesbania powder, Xuyong china clay or the clay one or more.
In above-mentioned arbitrary technical scheme, the extrusion aid of preferred 1-10 weight portion; Extrusion aid can be selected from one or more in oxalic acid, citric acid, polyvinyl alcohol, starch or the methylcellulose; In optimization citric acid, polyvinyl alcohol or the methylcellulose one or more.
In above-mentioned arbitrary technical scheme, the assorted element modifier of preferred 0.05-10 weight portion; The more preferably assorted element modifier of 0.05-8 weight portion; Assorted element modifier is the mixture that contains the soluble compound of P, Fe, Zn, K, Ce, La, Sr, Ba, Ca, Mg, Mo or Mn element more than three kinds or three kinds; The preferred mixture that contains the soluble compound of P, Fe, Ce, K, Sr, Mg or Zn element more than three kinds or three kinds; Preferred soluble compound includes but not limited to phosphoric acid, lanthanum nitrate, strontium nitrate, ferric nitrate, magnesium nitrate, manganese nitrate, cerous nitrate, potassium nitrate, nitric acid molybdenum, zinc nitrate; Promptly preferred assorted element modifier is selected from the mixture more than three kinds or three kinds in phosphoric acid, lanthanum nitrate, strontium nitrate, ferric nitrate, magnesium nitrate, manganese nitrate, cerous nitrate, potassium nitrate, nitric acid molybdenum, the zinc nitrate.
The described Preparation of catalysts method by ethanol conversion system ethene of as above arbitrary technical scheme is characterized in that comprising the steps:
A, the HZMS-5 molecular sieve powder is added in the entry, obtain homogeneous slurry;
B, in the slurries that steps A obtains, under agitation slowly add assorted element modifier, obtain homogeneous slurry;
C, in the slurries that step B obtains, add binding agent and extrusion aid, after stirring, use the banded extruder extrusion;
D, to step C extrusion gained catalyst semi-finished product dried overnight in blast dry oven, place the Muffle furnace roasting then, get 20～40 order particles through crushing and screening, make required catalyst.
Preferred 110 ℃ of the temperature of dried overnight in the blast dry oven wherein; Place preferred 450 ℃ of the temperature of Muffle furnace roasting then, the time is 4 hours.
In above-mentioned arbitrary technical scheme, being defined as of silica alumina ratio is known in this field, is sial ratio of components in the structure cell, and promptly mol ratio can be represented with Si/Al, perhaps SiO
2/ Al
2O
3Expression.
In above-mentioned arbitrary technical scheme, soluble compound generally speaking, does not have specified otherwise, all is meant water-soluble compound.
The producing ethylene from dehydration of ethanol reaction belongs to the reaction under the acid catalysis, and its reactivity worth receives the acid catalysis Effect on Performance.The present invention reduces the acidic site density of molecular sieve through introducing the strong acidic site that assorted element ion partly covers molecular sieve, effectively suppresses the generation of hydrogen migration, increases selectivity of ethylene, improves the anti-coking performance of molecular sieve; The interpolation of binding agent increases the interparticle caking property of raw material in shaping of catalyst, reach to improve catalyst strength and the effect that improves physico-chemical properties such as catalyst pores structure.The effect when helping the catalyst raw material smoothly through forming operation that is added with of auxiliary agent also changes and improve the function of physico-chemical properties such as acidic zeolite simultaneously.The catalyst of method for preparing has that preparation is simple, intensity is good, is used for the producing ethylene with ethyl alcohol course of reaction, at 20%～100% concentration of alcohol, 0.5 h
-1～2.5h
-1Reach under 220 ℃～300 ℃ reaction conditions, ethanol conversion and ethylene selectivity are not less than 99%, and the catalyst regeneration cycle, technique effect was obvious greater than 2000 h, had certain prospects for commercial application.
Through instance the present invention is done further elaboration below, but do not limit content of the present invention.
The specific embodiment
Disclosed arbitrary characteristic in this specification is only if special narration all can be replaced by other equivalences or the alternative features with similar purpose.That is, only if special narration, each characteristic is an example in a series of equivalences or the similar characteristics.
Fixed bed reactors are adopted in the activity of such catalysts evaluation among the present invention, are that raw material, water are diluent, normal pressure with ethanol.Hereinafter " part " among comparative example and the embodiment all is meant " weight portion ".The weight portion of assorted element modifier is all in the weight of this element among the present invention.
Comparative example 1
A kind of preparation method of catalyst for ethanol delydration to ethylene may further comprise the steps:
A, be that 50 HZMS-5 molecular sieve powder adds in the entry, obtain homogeneous slurry 85 parts of silica alumina ratios;
B, in the slurries that steps A obtains, under agitation slowly to add 2 parts of mass fractions be 85% phosphoric acid solution (in P), obtains homogeneous slurry;
C, in the slurries that step B obtains, add sesbania powder, 5 parts of citric acids of 10 parts, after stirring, use the banded extruder extrusion;
D, place 110 ℃ blast dry oven dried overnight, place Muffle furnace then, get 20～40 order particles, make required catalyst through crushing and screening in 450 ℃ of following roastings 4 hours to step C extrusion gained catalyst semi-finished product.Table 1 is seen in this activity of such catalysts evaluation.
Comparative example 2
A kind of preparation method of catalyst for ethanol delydration to ethylene may further comprise the steps:
A, be that 50 HZMS-5 molecular sieve powder adds in the entry, obtain homogeneous slurry 90 parts of silica alumina ratios;
B, in the slurries that steps A obtains, under agitation slowly add 2 parts of cerous nitrates (in Ce), obtain homogeneous slurry;
C, in the slurries that step B obtains, add kaolin, 4 parts of oxalic acid of 10 parts, after stirring, use the banded extruder extrusion;
D, place 110 ℃ blast dry oven dried overnight, place Muffle furnace then, get 20～40 order particles, make required catalyst through crushing and screening in 450 ℃ of following roastings 4 hours to step C extrusion gained catalyst semi-finished product.Table 1 is seen in this activity of such catalysts evaluation.
Instance 1
A kind of preparation method of catalyst for ethanol delydration to ethylene may further comprise the steps:
A, be that 25 HZMS-5 molecular sieve powder adds in the entry, obtain homogeneous slurry 90 parts of silica alumina ratios;
B, in the slurries that steps A obtains, under agitation slowly to add 2 parts of mass fractions be 85% phosphoric acid solution (in P), 1.5 parts of lanthanum nitrates (in La), 0.5 part of strontium nitrate (in Sr), obtains homogeneous slurry;
C, in the slurries that step B obtains, add 10 parts boehmite, 3 parts citric acid, after stirring, use the banded extruder extrusion;
D, place 110 ℃ blast dry oven dried overnight, place Muffle furnace then, get 20～40 order particles, make required catalyst through crushing and screening in 450 ℃ of following roastings 4 hours to step C extrusion gained catalyst semi-finished product.Table 1 is seen in this activity of such catalysts evaluation.
Instance 2
A kind of preparation method of catalyst for ethanol delydration to ethylene may further comprise the steps:
A, be that 30 HZMS-5 molecular sieve powder adds in the entry, obtain homogeneous slurry 95 parts of silica alumina ratios;
B, in the slurries that steps A obtains, under agitation slowly to add 1.5 parts of mass fractions be 85% phosphoric acid solution (in P), 1.5 parts of ferric nitrates (in Fe), 1 part of magnesium nitrate (in Mg), obtains homogeneous slurry;
C, in the slurries that step B obtains, add sesbania powder, 5 parts of methylcellulose of 15 parts, after stirring, use the banded extruder extrusion;
D, place 110 ℃ blast dry oven dried overnight, place Muffle furnace then, get 20～40 order particles, make required catalyst through crushing and screening in 450 ℃ of following roastings 4 hours to step C extrusion gained catalyst semi-finished product.Table 1 is seen in this activity of such catalysts evaluation.
Instance 3
A kind of preparation method of catalyst for ethanol delydration to ethylene may further comprise the steps:
A, be that 25 HZMS-5 molecular sieve powder adds in the entry, obtain homogeneous slurry 90 parts of silica alumina ratios;
B, in the slurries that steps A obtains, under agitation slowly to add 1.0 parts of mass fractions be 85% phosphoric acid solution (in P), 2 parts of ferric nitrates (in Fe), 0.01 part of strontium nitrate (in Sr), 1 part of manganese nitrate (in Mn), obtains homogeneous slurry;
C, in the slurries that step B obtains, add Xuyong china clay, 1 part of oxalic acid, 6 parts of polyvinyl alcohol of 10 parts, after stirring, use the banded extruder extrusion;
D, place 110 ℃ blast dry oven dried overnight, place Muffle furnace then, get 20～40 order particles, make required catalyst through crushing and screening in 450 ℃ of following roastings 4 hours to step C extrusion gained catalyst semi-finished product.Table 1 is seen in this activity of such catalysts evaluation.
Instance 4
A kind of preparation method of catalyst for ethanol delydration to ethylene may further comprise the steps:
A, be that 50 HZMS-5 molecular sieve powder adds in the entry, obtain homogeneous slurry 95 parts of silica alumina ratios;
B, in the slurries that steps A obtains, under agitation slowly add 2 parts of cerous nitrates (in Ce), 0.5 part of potassium nitrate (in K), 1.5 parts of manganese nitrates (in Mn), obtain homogeneous slurry;
C, in the slurries that step B obtains, add kaolin, 8 parts of polyvinyl alcohol of 8 parts, after stirring, use the banded extruder extrusion;
D, place 110 ℃ blast dry oven dried overnight, place Muffle furnace then, get 20～40 order particles, make required catalyst through crushing and screening in 450 ℃ of following roastings 4 hours to step C extrusion gained catalyst semi-finished product.Table 1 is seen in this activity of such catalysts evaluation.
Instance 5
A kind of preparation method of catalyst for ethanol delydration to ethylene may further comprise the steps:
A, be that 40 HZMS-5 molecular sieve powder adds in the entry, obtain homogeneous slurry 95 parts of silica alumina ratios;
B, add slowly under agitation in the slurries that steps A obtains that 1.5 parts of mass fractions are 85% phosphoric acid solution (in P), 2. part cerous nitrate (in Ce), 0.3 part of strontium nitrate (in Sr) obtain homogeneous slurry;
C, in the slurries that step B obtains, add sesbania powder, 10 parts of polyvinyl alcohol of 15 parts, after stirring, use the banded extruder extrusion;
D, place 110 ℃ blast dry oven dried overnight, place Muffle furnace then, get 20～40 order particles, make required catalyst through crushing and screening in 450 ℃ of following roastings 4 hours to step C extrusion gained catalyst semi-finished product.Table 1 is seen in this activity of such catalysts evaluation.
Instance 6
A kind of preparation method of catalyst for ethanol delydration to ethylene may further comprise the steps:
A, be that 50 HZMS-5 molecular sieve powder adds in the entry, obtain homogeneous slurry 100 parts of silica alumina ratios;
B, in the slurries that steps A obtains, under agitation slowly to add 1.5 parts of mass fractions be 85% phosphoric acid solution (in P), 1.0 parts of ferric nitrates (in Fe), 0.05 part of strontium nitrate (in Sr), 0.5 part of nitric acid molybdenum (in Mo), obtains homogeneous slurry;
C, in the slurries that step B obtains, add boehmite, 10 parts of polyvinyl alcohol, 5 parts of oxalic acid of 5 parts, after stirring, use the banded extruder extrusion;
D, place 110 ℃ blast dry oven dried overnight, place Muffle furnace then, get 20～40 order particles, make required catalyst through crushing and screening in 450 ℃ of following roastings 4 hours to step C extrusion gained catalyst semi-finished product.Table 1 is seen in this activity of such catalysts evaluation.
Instance 7
A kind of preparation method of catalyst for ethanol delydration to ethylene may further comprise the steps:
A, be that 75 HZMS-5 molecular sieve powder adds in the entry, obtain homogeneous slurry 95 parts of silica alumina ratios;
B, in the slurries that steps A obtains, under agitation slowly to add 1.0 parts of mass fractions be 85% phosphoric acid solution (in P), 2.0 parts of zinc nitrates (in Zn), 2.0 parts of magnesium nitrates (in Mg), obtains homogeneous slurry;
C, in the slurries that step B obtains, add clay, 6 parts of polyvinyl alcohol, 5 parts of citric acids of 12 parts, after stirring, use the banded extruder extrusion;
D, place 110 ℃ blast dry oven dried overnight, place Muffle furnace then, get 20～40 order particles, make required catalyst through crushing and screening in 450 ℃ of following roastings 4 hours to step C extrusion gained catalyst semi-finished product.Table 1 is seen in this activity of such catalysts evaluation.
Instance 8
A kind of preparation method of catalyst for ethanol delydration to ethylene may further comprise the steps:
A, be that 100 HZMS-5 molecular sieve powder adds in the entry, obtain homogeneous slurry 70 parts of silica alumina ratios;
B, in the slurries that steps A obtains, under agitation slowly add 8 parts of magnesium nitrates (in Mg), 1.5 parts of cerous nitrates (in Ce), 0.5 part of manganese nitrate (in Mn), obtain homogeneous slurry;
C, in the slurries that step B obtains, add kaolin, 5 parts of polyvinyl alcohol, 5 parts of oxalic acid of 5 parts, after stirring, use the banded extruder extrusion;
D, place 110 ℃ blast dry oven dried overnight, place Muffle furnace then, get 20～40 order particles, make required catalyst through crushing and screening in 450 ℃ of following roastings 4 hours to step C extrusion gained catalyst semi-finished product.Table 1 is seen in this activity of such catalysts evaluation.
Instance 9
A kind of preparation method of catalyst for ethanol delydration to ethylene may further comprise the steps:
A, be that 50 HZMS-5 molecular sieve powder adds in the entry, obtain homogeneous slurry 96 parts of silica alumina ratios;
B, in the slurries that steps A obtains, under agitation slowly to add 2.0 parts of mass fractions be 85% phosphoric acid solution (in P), 2.0 parts of ferric nitrates (in Fe), 1.5 parts of cerous nitrates (in Ce), obtains homogeneous slurry;
C, in the slurries that step B obtains, add boehmite, 4 parts of kaolin, 12 parts of polyvinyl alcohol of 1 part, after stirring, use the banded extruder extrusion;
D, place 110 ℃ blast dry oven dried overnight, place Muffle furnace then, get 20～40 order particles, make required catalyst through crushing and screening in 450 ℃ of following roastings 4 hours to step C extrusion gained catalyst semi-finished product.Table 1 is seen in this activity of such catalysts evaluation.
Instance 10
A kind of preparation method of catalyst for ethanol delydration to ethylene may further comprise the steps:
A, be that 200 HZMS-5 molecular sieve powder adds in the entry, obtain homogeneous slurry 97 parts of silica alumina ratios;
B, in the slurries that steps A obtains, under agitation slowly add 0.02 part of magnesium nitrate (in Mg), 0.02 part of cerous nitrate (in Ce), 0.01 part potassium nitrate (in K) obtains homogeneous slurry;
C, in the slurries that step B obtains, add sesbania powder, 5 parts of boehmites, 1 part of oxalic acid of 15 parts, after stirring, use the banded extruder extrusion;
D, place 110 ℃ blast dry oven dried overnight, place Muffle furnace then, get 20～40 order particles, make required catalyst through crushing and screening in 450 ℃ of following roastings 4 hours to step C extrusion gained catalyst semi-finished product.Table 1 is seen in this activity of such catalysts evaluation.
The present invention is not limited to the aforesaid specific embodiment.The present invention expands to any new feature or any new combination that discloses in this manual, and the arbitrary new method that discloses or step or any new combination of process.
The activity rating table of table 1 catalyst for ethanol delydration to ethylene
| Title | Catalyst radial crushing strength N (3mm strip) | Reaction temperature | Air speed h -1 | Ethanol conversion % | Ethylene selectivity % |
| Comparative example 1 | 22 | 280 | 1.5 | 85.8 | 76.5 |
| Comparative example 2 | 55 | 220 | 1.5 | 63.2 | 65.3 |
| Embodiment 1 | 61 | 280 | 2.5 | 99.2 | 99.1 |
| Embodiment 2 | 41 | 250 | 1.1 | 99.5 | 96.5 |
| Embodiment 3 | 60 | 260 | 1.5 | 99.6 | 98.2 |
| Embodiment 4 | 56 | 270 | 1.2 | 99.3 | 93.2 |
| Embodiment 5 | 45 | 280 | 1.5 | 99.8 | 99.7 |
| Embodiment 6 | 48 | 260 | 1.2 | 99.2 | 99.6 |
| Embodiment 7 | 65 | 290 | 1.2 | 99.3 | 99.1 |
| Embodiment 8 | 42 | 220 | 2.5 | 75.2 | 66.3 |
| Embodiment 9 | 52 | 260 | 1.5 | 93.2 | 95.9 |
| Embodiment 10 | 48 | 300 | 1.2 | 95.3 | 90.2 |
Visible by last table, technical scheme of the present invention is superior to comparative example in the data aspect ethanol conversion, the ethylene selectivity.
Claims (10)
1. the catalyst by ethanol conversion system ethene is characterized in that comprising following component: the HZSM-5 molecular sieve of 70～100 weight portions, 1-30 parts by weight of adhesive, the extrusion aid of 1-15 weight portion, the assorted element modifier of 0.01-10 weight portion.
2. the catalyst by ethanol conversion system ethene according to claim 1, the silica alumina ratio that it is characterized in that said HZSM-5 molecular sieve is 25-200.
3. the catalyst by ethanol conversion system ethene according to claim 1 and 2 is characterized in that said binding agent is selected from one or more in sesbania powder, Xuyong china clay, aluminium hydroxide, boehmite, kaolin or the clay.
4. according to any described catalyst among the claim 1-3, it is characterized in that said extrusion aid is selected from one or more in oxalic acid, citric acid, polyvinyl alcohol, starch or the methylcellulose by ethanol conversion system ethene.
5. according to any described catalyst among the claim 1-4, it is characterized in that said assorted element modifier is the mixture that contains the soluble compound of P, Fe, Zn, K, Ce, La, Sr, Ba, Ca, Mg, Mo or Mn element more than three kinds or three kinds by ethanol conversion system ethene.
6. according to any described catalyst among the claim 1-5, it is characterized in that the silica alumina ratio of said HZSM-5 molecular screening below crystal grain 5 μ m is 25～100 HZSM-5 molecular sieve by ethanol conversion system ethene.
7. according to any described catalyst among the claim 1-6, it is characterized in that said binding agent is selected from one or more in sesbania powder, Xuyong china clay or the clay by ethanol conversion system ethene.
8. according to any described catalyst among the claim 1-7, it is characterized in that said extrusion aid is selected from citric acid, polyvinyl alcohol or the methylcellulose one or more by ethanol conversion system ethene.
9. according to any described catalyst among the claim 1-8, it is characterized in that said assorted element modifier is the mixture that contains the soluble compound of P, Fe, Ce, K, Sr, Mg or Zn element more than three kinds or three kinds by ethanol conversion system ethene.
10. according to any described Preparation of catalysts method among the claim 1-9, it is characterized in that comprising the steps: by ethanol conversion system ethene
A, the HZMS-5 molecular sieve powder is added in the entry, obtain homogeneous slurry;
B, in the slurries that steps A obtains, under agitation slowly add assorted element modifier, obtain homogeneous slurry;
C, in the slurries that step B obtains, add binding agent and extrusion aid, after stirring, use the banded extruder extrusion;
D, to step C extrusion gained catalyst semi-finished product dried overnight in blast dry oven, place the Muffle furnace roasting then, get 20～40 order particles through crushing and screening, make required catalyst.
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|---|---|---|---|
| CN2012102859932A CN102806101A (en) | 2012-08-13 | 2012-08-13 | Catalyst for preparing ethylene by conversion of ethanol and preparation method of catalyst |
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| CN2012102859932A CN102806101A (en) | 2012-08-13 | 2012-08-13 | Catalyst for preparing ethylene by conversion of ethanol and preparation method of catalyst |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107694544A (en) * | 2017-10-12 | 2018-02-16 | 江西萍乡市成宇陶瓷有限责任公司 | The preparation method of ethene efficient molecular sieve |
| CN108636448A (en) * | 2018-04-18 | 2018-10-12 | 佛山市飞程信息技术有限公司 | A kind of catalyst for producing ethylene from dehydration of ethanol |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4698452A (en) * | 1986-10-02 | 1987-10-06 | Institut Nationale De La Recherche Scientifique | Ethylene light olefins from ethanol |
| CN102527426A (en) * | 2011-12-15 | 2012-07-04 | 西南化工研究设计院 | Preparation method for catalyst for preparing ethylene by dehydrating ethanol |
-
2012
- 2012-08-13 CN CN2012102859932A patent/CN102806101A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4698452A (en) * | 1986-10-02 | 1987-10-06 | Institut Nationale De La Recherche Scientifique | Ethylene light olefins from ethanol |
| CN102527426A (en) * | 2011-12-15 | 2012-07-04 | 西南化工研究设计院 | Preparation method for catalyst for preparing ethylene by dehydrating ethanol |
Non-Patent Citations (1)
| Title |
|---|
| KANAPARTHI RAMESH, ET AL.: "Structure and reactivity of phosphorous modified H-ZSM-5 catalysts for ethanol dehydration", 《CATALYSIS COMMUNICATIONS》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107694544A (en) * | 2017-10-12 | 2018-02-16 | 江西萍乡市成宇陶瓷有限责任公司 | The preparation method of ethene efficient molecular sieve |
| CN108636448A (en) * | 2018-04-18 | 2018-10-12 | 佛山市飞程信息技术有限公司 | A kind of catalyst for producing ethylene from dehydration of ethanol |
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Application publication date: 20121205 |