CN1623662A - Mixed molecular sieve catalyst and its preparation process - Google Patents
Mixed molecular sieve catalyst and its preparation process Download PDFInfo
- Publication number
- CN1623662A CN1623662A CNA2004100645046A CN200410064504A CN1623662A CN 1623662 A CN1623662 A CN 1623662A CN A2004100645046 A CNA2004100645046 A CN A2004100645046A CN 200410064504 A CN200410064504 A CN 200410064504A CN 1623662 A CN1623662 A CN 1623662A
- Authority
- CN
- China
- Prior art keywords
- molecular sieve
- mixed molecular
- mixed
- catalyst
- catalyzer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- 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
Landscapes
- Catalysts (AREA)
Abstract
A mixed molecular sieve catalyst is prepared through proportionally mixing the mixed molecular sieve, adhesive and solution of diluted nitric acid, extruding out to become strips, baking, calcining, crushing, immersing in the solution of inorganic acid for 8-12 hr, baking at 100-120 deg.C and calcining at 300-350 deg.C for 3-6 hr. Its advantages are high strength, cyclic use and high hydrothermal stability.
Description
Technical field
The invention belongs to a kind of molecular sieve catalyst and preparation method, relate in particular to a kind of mixed molecular sieve catalyst and preparation method who is used for by carbon four following alkene or superimposed preparation nonene of its mixture and laurylene.
Background technology
Unsaturated hydrocarbons superimposed is one of reaction outstanding in the organic chemistry, is used for producing liquid fuel, plastics, medicine, dyestuff, resin, washing composition, lubricating oil and additive etc. widely.So-called alkene oligomerization reaction is meant certain olefinic monomer (C
2-C
14) under catalyst action polymerization generate the reaction process of the compound that one or more tectonic elements repeat to link to each other.
Basic identical by the superimposed production tripolymer of propylene, the most used technology of tetramer technology, all adopt solid phosphoric acid-diatomite catalyzer.Nonene and laurylene are to make important chemical intermediate, and nonyl phenol is field of fine chemical important material and intermediate, carries out alkylated reaction by phenol and nonene and makes.Laurylene can be used to produce isomery alcohol, tensio-active agent and petroleum additive etc.(reference: petrochemical complex, 1994, Vol.23, No3, P149)
It is comparatively extensive to be used for alkene oligomerization catalyst for reaction system, the catalyzer that is adopted under the industrialized condition is essentially solid phosphoric acid-diatomite catalyzer at present, this catalyzer is to be made by the tripolite loading solid phosphoric acid, and the acidity of catalyzer is by free P on the catalyzer
2O
5With the water-content decision, when reaction was carried out, the phosphoric acid silicon hydrolysis on the catalyzer was constantly carried out, and can impel the crystalline structure of catalyzer to be destroyed, and also was that the argillization of catalyzer is constantly carried out, and the pressure of reactor is improved, and was difficult to carry out until reaction.Process conditions control strictness in the reaction process, complicated operation, and the non-renewable use repeatedly of catalyzer,
Summary of the invention
The purpose of this invention is to provide a kind of renewablely use repeatedly, simple to operate, and reactive behavior high be used for mixed molecular sieve catalyst and preparation method by carbon four following alkene or superimposed preparation nonene of its mixture and laurylene.
Molecular sieve is the silico-aluminate system that a class has the molecular size aperture, in the alkene oligomerization reaction, have an effect with the protonic acid form, one of its typical feature is the pore passage structure of its uniqueness, present sieving capacity to organic molecule, adopt contain HZSM-5 and HY molecular sieve mixture and load thereof PO
4 3-, SO
4 =Or Cl
-The molecular sieve catalyst of making owing to the synergy of mixed molecular sieve total acid content and loaded article, has been strengthened the generation and the selectivity of product of building-up reactions, not only has high reaction activity and high but also has the renewable advantage of using repeatedly of molecular sieve catalyst.
Catalyst weight ratio of the present invention consists of:
Mixed molecular sieve: binding agent: load component mineral acid=1: 0.30-0.45: 4 * 10
-3-0.15.
Described mixed molecular sieve is homogeneously crystallized mixture molecular sieve or uniform powder mixture molecular sieve.Be made up of HZSM-5 and HY molecular sieve, its weight ratio is that HZSM-5: HY is 1: 0.3-3.0,
Described load group is divided into and contains PO
4 3-, SO
4 =Or Cl
-The mineral acid of negative ion
Described binding agent is boehmite, diatomite or gama-alumina.
Preparation of catalysts process of the present invention comprises the steps:
Form mixed molecular sieve by the catalyst weight ratio: binding agent: load component mineral acid=1: 0.30-0.45: 4 * 10
-3-0.15, the dilute nitric acid solution that adds binding agent and 2-4wt% in mixed molecular sieve evenly is extruded into strip, the add-on of its dilute nitric acid solution is mixed molecular sieve and binding agent to be mixed pinch slivering to be as the criterion, in 100-120 ℃ of baking oven, keep oven dry in 6-8 hour, in 500-540 ℃ of following roasting 3-6 hour, be broken for the 10-80 order after the roasting again; Adopt equi-volume impregnating through the active constituent inorganic acid solution of 0.1-1.0mol/l dipping 8-12 hour, after 100-120 ℃ of oven dry, 300-350 ℃ roasting 3-6 hour, obtain mixed molecular sieve catalyst then.
Used two kinds of molecular sieves of the present invention and binding agent, mineral acid, deionized water etc. all is selected from commercially available
Advantage of the present invention:
1, this catalyst strength height, operating restraint broad.
2, because catalyst substrates adopts is molecular sieve, therefore has the advantage that iterative regenerable uses.
3, no argillization phenomenon in the catalyst reaction process, good hydrothermal stability.
Embodiment
Embodiment 1
Accurately take by weighing HZSM-5 molecular sieve 4.2 grams and HY molecular sieve 21.0 grams, diatomite 9.0 grams, put into mortar, mix, the salpeter solution that drips 3wt% mixes and pinches evenly, is squeezed into strip with the spiral banded extruder of manual type, in 120 ℃ of baking ovens, keep oven dry, put into stoving oven then 540 ℃ of roastings 4 hours; Be crushed to the 20-40 order again, catalyzer after the fragmentation is measured 15ml put into crucible, measuring the 0.5mol/l sulphuric acid soln that 15ml disposed with graduated cylinder again adds in the crucible, stir with glass stick, flooded at room temperature 8 hours, insert oven dry in about 5 hours in 120 ℃ of baking ovens then, in the process of oven dry, will stir once, at last the catalyzer of complete drying is put into stoving oven and obtained catalyzer after 3 hours in 300 ℃ of following roastings every 30 minutes.This catalyst weight ratio of components is a mixed molecular sieve: diatomite: SO
4 ==1: 0.36: 0.07.The NH of catalyzer
3The acid matter of-TPD sees Table 2.
Embodiment 2
Accurately take by weighing HZSM-5 molecular sieve 9.0 grams and HY molecular sieve 13.5 grams, boehmite 7.5 grams, put into mortar, mix, dropping 2 (wt) % salpeter solution mixes and pinches evenly, is squeezed into strip with the spiral banded extruder of manual type, in 110 ℃ of baking ovens, keep oven dry in about 3 hours, put into stoving oven then temperature is risen to 500 ℃ of roastings 5 hours; Again that roasting is good catalyst breakage is to the 20-60 order, measure 20ml with graduated cylinder and put into crucible, adding the 0.1mol/l phosphoric acid solution that 20ml has configured, stir with glass stick, flooded 10 hours, insert oven dry in about 6 hours in 120 ℃ of baking ovens then, in the process of oven dry, will stir once, at last the catalyzer of complete drying is put into stoving oven and obtained catalyzer after 5 hours in 320 ℃ of following roastings every 30 minutes.This catalyzer proportion of composing is a mixed molecular sieve: boehmite: PO
4 -3=1: 0.33: 0.01.The NH of catalyzer
3The acid matter of-TPD sees Table 2.
Embodiment 3
Accurately take by weighing HZSM-5 molecular sieve 12.6 grams and HY molecular sieve 8.4 grams, gama-alumina 9.0 grams, put into mortar, mix, dropping 3 (wt) % nitric acid mixes to be pinched evenly, be squeezed into strip with the spiral banded extruder of manual type, in 100 ℃ of baking ovens, keep oven dry in about 3 hours, put into stoving oven then temperature is risen to 520 ℃ of roastings 6 hours, again that roasting is good catalyst breakage is to the 20-40 order, measure 20ml with graduated cylinder and put into crucible, adding the 0.1mol/l hydrochloric acid soln that 20ml has configured, stir with glass stick, flooded 10 hours, insert oven dry in about 6 hours in 120 ℃ of baking ovens then, in the process of oven dry, to stir once, at last the catalyzer of complete drying be put into stoving oven and obtained catalyzer after 8 hours in 340 ℃ of following roastings every 30 minutes.This catalyzer proportion of composing is a mixed molecular sieve: gama-alumina: Cl
-=1: 0.43: 6.5 * 10
-3The NH of catalyzer
3The acid matter of-TPD sees Table 2.
Embodiment 4
Accurately take by weighing HZSM-5 molecular sieve 16.8 grams and HY molecular sieve 4.0 grams, boehmite 9.0 grams, put into mortar, mix, dropping 3 (wt) % nitric acid mixes to be pinched evenly, be squeezed into strip with the spiral banded extruder of manual type, in 100 ℃ of baking ovens, keep oven dry in about 3 hours, put into stoving oven then temperature is risen to 520 ℃ of roastings 6 hours, again that roasting is good catalyst breakage is to the 20-40 order, measure 20ml with graduated cylinder and put into crucible, adding the 0.5mol/l phosphoric acid solution that 20ml has configured, stir with glass stick, flooded 10 hours, insert oven dry in about 6 hours in 120 ℃ of baking ovens then, in the process of oven dry, to stir once, at last the catalyzer of complete drying be put into stoving oven and obtained catalyzer after 6 hours in 320 ℃ of following roastings every 30 minutes.This catalyzer proportion of composing is a mixed molecular sieve: boehmite: PO
4 3-=1: 0.43: 0.08.The NH of catalyzer
3The acid matter of-TPD sees Table 2.
Embodiment 5
The method for making of present embodiment is with embodiment 3, just changes steeping fluid the phosphoric acid solution of 1.0mol/l into by the 0.1mol/l hydrochloric acid soln, and all the other method for makings are identical.This catalyzer proportion of composing is a mixed molecular sieve: gama-alumina: PO
4 3-=1: 0.43: 0.09, the NH of catalyzer
3The acid matter of-TPD sees Table 2.
Comparative Examples 1
Accurately take by weighing HY molecular sieve 21.0 grams, boehmite 9.0 grams, put into mortar, mix, dropping 3 (wt) % nitric acid mixes to be pinched evenly, be squeezed into strip with the spiral banded extruder of manual type, in 100 ℃ of baking ovens, keep oven dry in about 3 hours, put into stoving oven then temperature is risen to 520 ℃ of roastings 6 hours, again that roasting is good catalyst breakage is to the 20-40 order, measure 20ml with graduated cylinder and put into crucible, adding the 1.0mol/l sulphuric acid soln that 20ml has configured, stir with glass stick, flooded 10 hours, insert oven dry in about 6 hours in 120 ℃ of baking ovens then, in the process of oven dry, to stir once, at last the catalyzer of complete drying be put into stoving oven and obtained catalyzer after 5 hours in 320 ℃ of following roastings every 30 minutes.This catalyst weight proportion of composing is the HY molecular sieve: boehmite: SO
4 ==1: 0.43: 0.09.The NH of catalyzer
3The acid matter of-TPD sees Table 2.
Comparative Examples 2
Accurately take by weighing HZSM-5 molecular sieve 18.0 grams, gama-alumina 10.0 grams, put into mortar, mix, dropping 3 (wt) % nitric acid mixes to be pinched evenly, be squeezed into strip with the spiral banded extruder of manual type, in 100 ℃ of baking ovens, keep oven dry in about 3 hours, put into stoving oven then temperature is risen to 520 ℃ of roastings 6 hours, again that roasting is good catalyst breakage is to the 20-40 order, measure 20ml with graduated cylinder and put into crucible, adding the 0.1mol/l phosphoric acid solution that 20ml has configured, stir with glass stick, flooded 10 hours, insert oven dry in about 6 hours in 120 ℃ of baking ovens then, in the process of oven dry, to stir once, at last the catalyzer of complete drying be put into stoving oven and obtained catalyzer after 5 hours in 350 ℃ of following roastings every 30 minutes.This catalyst weight proportion of composing is the HZSM-5 molecular sieve: gama-alumina: PO
4 3-=1: 55.62: 0.02.The NH of catalyzer
3The acid matter of-TPD sees Table 2.
The reactivity worth of catalyzer adopts following method to estimate:
Feed olefin can contain the 2-6 carbon atom, preferred 2-4 carbon atom.This reaction raw materials is a propylene, reaction unit adopts continuous flow pressurization static bed, the catalyzer that the 5ml that packs in the reactor constant temperature zone makes, temperature of reaction is controlled by the controllable type electrical heater, raw material pumps into single cylinder plunger tpe compression pump, and system pressure adopts high pure nitrogen or argon gas to regulate by the level pressure system.Its condition is as follows: temperature of reaction T=210 ℃; Reaction pressure P=4.0Mpa; Liquid air speed LHSW=1.5H
-1, reaction result sees Table 1
Table 1
| Embodiment | Olefin conversion (wt) % | Selectivity of product % | |||
| ??C 6 | ??C 9 | ??C 12 | ??C 15 + | ||
| Embodiment 1 | ??97.5 | ??20.12 | ??40.32 | ??35.15 | ??4.41 |
| Embodiment 2 | ??98.3 | ??22.32 | ??38.96 | ??34.28 | ??4.44 |
| Embodiment 3 | ??98.2 | ??21.68 | ??42.35 | ??30.29 | ??5.68 |
| Embodiment 4 | ??97.5 | ??22.58 | ??39.61 | ??32.96 | ??4.85 |
| Embodiment 5 | ??98.3 | ??23.52 | ??41.38 | ??30.15 | ??4.95 |
| Comparative Examples 1 | ??98.1 | ??35.28 | ??30.25 | ??23.24 | ??13.23 |
| Comparative Examples 2 | ??97.6 | ??41.22 | ??20.15 | ??24.32 | ??14.31 |
Table 2
| The catalyzer numbering | Strong acid amount mmol/ restrains catalyzer | Weak acid amount mmol/ restrains catalyzer | Total acid content mmol/ restrains catalyzer |
| Embodiment 1 | ????0.53 | ????0.46 | ????0.99 |
| Embodiment 2 | ????0.61 | ????0.51 | ????1.12 |
| Embodiment 3 | ????0.56 | ????0.49 | ????1.05 |
| Embodiment 4 | ????0.52 | ????0.51 | ????1.03 |
| Comparative Examples 1 | ????0.46 | ????0.45 | ????0.91 |
| Comparative Examples 2 | ????0.45 | ????0.43 | ????0.88 |
Claims (6)
1, a kind of mixed molecular sieve catalyst is characterized in that the catalyst weight ratio consists of:
Mixed molecular sieve: binding agent: load component mineral acid=1: 0.30-0.45: 4 * 10
-3-0.15.
2, a kind of mixed molecular sieve catalyst as claimed in claim 1 is characterized in that described mixed molecular sieve is homogeneously crystallized mixture molecular sieve or uniform powder mixture molecular sieve.
3, a kind of mixed molecular sieve catalyst as claimed in claim 1, the mixed molecular sieve that it is characterized in that is made up of HZSM-5 and HY molecular sieve, and its weight ratio is that HZSM-5: HY is 1: 0.3-3.0.
4, a kind of mixed molecular sieve catalyst as claimed in claim 1 is characterized in that described load component mineral acid is for containing PO
4 3-, SO
4 =Or Cl
-The mineral acid of negative ion.
5, a kind of mixed molecular sieve catalyst as claimed in claim 1 is characterized in that described binding agent is boehmite, diatomite or gama-alumina.
6,, it is characterized in that comprising the steps: as the preparation method of each described a kind of mixed molecular sieve catalyst of claim 1-5
Form mixed molecular sieve by the catalyst weight ratio: binding agent: load component mineral acid=1: 0.30-0.45: 4 * 10
-3-0.15, the dilute nitric acid solution that adds binding agent and 2-4wt% in mixed molecular sieve evenly is extruded into strip, the add-on of its dilute nitric acid solution is mixed molecular sieve and binding agent to be mixed pinch slivering to be as the criterion, in 100-120 ℃ of baking oven, keep oven dry in 6-8 hour, in 500-540 ℃ of following roasting 3-6 hour, be broken for the 10-80 order after the roasting again; Adopt equi-volume impregnating through the active constituent inorganic acid solution of 0.1-1.0mol/l dipping 8-12 hour, after 100-120 ℃ of oven dry, 300-350 ℃ roasting 3-6 hour, obtain mixed molecular sieve catalyst then.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100645046A CN100528355C (en) | 2004-10-18 | 2004-10-18 | Mixed molecular sieve catalyst and its preparation process |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100645046A CN100528355C (en) | 2004-10-18 | 2004-10-18 | Mixed molecular sieve catalyst and its preparation process |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1623662A true CN1623662A (en) | 2005-06-08 |
| CN100528355C CN100528355C (en) | 2009-08-19 |
Family
ID=34764522
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2004100645046A Active CN100528355C (en) | 2004-10-18 | 2004-10-18 | Mixed molecular sieve catalyst and its preparation process |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100528355C (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105566033A (en) * | 2014-10-14 | 2016-05-11 | 中国石油化工股份有限公司 | Method for non-hydrogenation olefin removal of pentane oil |
| CN108273543A (en) * | 2018-01-23 | 2018-07-13 | 西南化工研究设计院有限公司 | A kind of preparation method of oligomerization of propene nonene catalyst |
| CN108554440A (en) * | 2018-01-04 | 2018-09-21 | 西南化工研究设计院有限公司 | The preparation method and molecular sieve catalyst of molecular sieve catalyst for oligomerization of propene |
| CN110327967A (en) * | 2019-07-26 | 2019-10-15 | 山东达民化工股份有限公司 | The peaceful production. art of the isopropanol of catalyst and preparation method and application catalyst |
| CN112316974A (en) * | 2020-11-06 | 2021-02-05 | 东华工程科技股份有限公司 | Bifunctional catalyst and preparation method and application thereof |
| CN114192185A (en) * | 2021-11-22 | 2022-03-18 | 泰兴市凌飞化学科技有限公司 | Catalyst for preparing nonyl phenol by transalkylation and preparation method thereof |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4828679A (en) * | 1984-03-12 | 1989-05-09 | Mobil Oil Corporation | Octane improvement with large size ZSM-5 catalytic cracking |
| CN1042201C (en) * | 1993-08-28 | 1999-02-24 | 中国石油化工总公司石油化工科学研究院 | Cracking catalyst of rich producing olefines |
| CN1136983C (en) * | 1999-02-04 | 2004-02-04 | 中国石化集团齐鲁石油化工公司 | Composite molecular sieve catalyst and preparing process thereof |
| CN1162325C (en) * | 2001-06-29 | 2004-08-18 | 中国石油天然气股份有限公司 | Step crystallizing process for synthesizing composite mesaporous and microporous molecular sieve composition |
| CN1171788C (en) * | 2001-06-29 | 2004-10-20 | 中国石油天然气股份有限公司 | Process for synthesizing composite mesaporous-microporous molecular sieve composition |
-
2004
- 2004-10-18 CN CNB2004100645046A patent/CN100528355C/en active Active
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105566033A (en) * | 2014-10-14 | 2016-05-11 | 中国石油化工股份有限公司 | Method for non-hydrogenation olefin removal of pentane oil |
| CN108554440A (en) * | 2018-01-04 | 2018-09-21 | 西南化工研究设计院有限公司 | The preparation method and molecular sieve catalyst of molecular sieve catalyst for oligomerization of propene |
| CN108554440B (en) * | 2018-01-04 | 2020-06-09 | 西南化工研究设计院有限公司 | Preparation method of molecular sieve catalyst for propylene oligomerization and molecular sieve catalyst |
| CN108273543A (en) * | 2018-01-23 | 2018-07-13 | 西南化工研究设计院有限公司 | A kind of preparation method of oligomerization of propene nonene catalyst |
| CN108273543B (en) * | 2018-01-23 | 2020-04-24 | 西南化工研究设计院有限公司 | Preparation method of catalyst for preparing nonene by oligomerization of propylene |
| CN110327967A (en) * | 2019-07-26 | 2019-10-15 | 山东达民化工股份有限公司 | The peaceful production. art of the isopropanol of catalyst and preparation method and application catalyst |
| CN112316974A (en) * | 2020-11-06 | 2021-02-05 | 东华工程科技股份有限公司 | Bifunctional catalyst and preparation method and application thereof |
| CN114192185A (en) * | 2021-11-22 | 2022-03-18 | 泰兴市凌飞化学科技有限公司 | Catalyst for preparing nonyl phenol by transalkylation and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN100528355C (en) | 2009-08-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP2772307B1 (en) | Method for preparing a catalyst for preparing vinyl chloride | |
| CN1342719A (en) | Rare-earth catalyst system and its catalytic bis polymerizing process for butadiene | |
| CN1623662A (en) | Mixed molecular sieve catalyst and its preparation process | |
| US9314781B2 (en) | Catalyst for selective paraffin isomerization and preparation method and use thereof | |
| CN1618832A (en) | Manufacturing method of low melting point polyester | |
| CN102351970A (en) | Method for preparing poly-1,3-pentadiene | |
| CN1340601A (en) | Aromatizing catalyst for light hydrocarbon and its preparing process | |
| CN1043313C (en) | Catalyst for synthesizing diphenylamine from phenylamine and preparing process thereof | |
| CN1718596A (en) | Method of preparing nano-polyethylene fiber by normal pressure extrusion polymerization | |
| DE1049582B (en) | Process for the polymerization of tetrafluoroethylene. 23.'2. 56th V. St. America | |
| CN1035774C (en) | Hydrocarbon dearsenicating catalyst | |
| CN1353168A (en) | Hydrorefining catalyst and its preparing process | |
| CN1117620C (en) | Multiphase Rh-Li metal catalyst for methanol carbonylation and its prepn | |
| CN1944483A (en) | Aluminum trichloride/nucleophilic reagent composite catalystic system and its use in synthesizing petroleum resin | |
| CN1175933C (en) | Bimetal reforming catalyst and its preparing process | |
| KR101948799B1 (en) | Catalyst for oligomerization reaction of light olefins, method for preparing the same and use thereof | |
| CN101186662B (en) | Initiator for ultra-low Mooney fluororubber production and polymerization, and preparation method thereof | |
| CN1123389C (en) | Preparation of catalyst for preparing low-carbon alcohol by low-carbon oleffine hydration and its application | |
| CN105111344A (en) | Carbon nano tube/polyisoprene composite material and preparation method thereof | |
| CN101045209A (en) | Catalyst for synthesizing iso-propylbenzene | |
| CN1189497C (en) | Method for preparing polyurea polybasic alcohol | |
| CN102728336B (en) | Preparation method of boron-containing alumina carrier | |
| CN1544151A (en) | Molecular sieve catalyst and preparation method thereof | |
| CN113694944B (en) | Palladium selective hydrogenation catalyst for pyrolysis gasoline and preparation method and application thereof | |
| CN113663699B (en) | Alumina carrier and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |