CN1020039C - Synthesis of mercerized zeolite with high silicon content - Google Patents
Synthesis of mercerized zeolite with high silicon content Download PDFInfo
- Publication number
- CN1020039C CN1020039C CN 89106793 CN89106793A CN1020039C CN 1020039 C CN1020039 C CN 1020039C CN 89106793 CN89106793 CN 89106793 CN 89106793 A CN89106793 A CN 89106793A CN 1020039 C CN1020039 C CN 1020039C
- Authority
- CN
- China
- Prior art keywords
- mordenite
- crystallization
- high silicon
- sio
- ammonia
- 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.)
- Expired - Lifetime
Links
Images
Landscapes
- Silicates, Zeolites, And Molecular Sieves (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The present invention relates to a synthesis method for high silicon mordenite of which the SiO[2]/Al [2]O[3] is from 15 to 30, which usually uses organic alkali as an additional reagent. The present invention directly synthetizes the mordenite by using industrial raw materials of easily obtain water glass with low cost, inorganic acid, inorganic base, tris aluminum salt or aluminate, etc. without any organic alkali as the additional reagent under the condition with ammonia. The high silicon mordenite prepared according to the present invention has the advantages of low production cost, no environment pollution, easy processing, good product quality, etc. The prepared high silicon mordenite can be used for manufacturing a catalyst generated by the reaction of toluene disproportionation and transalkylati.
Description
The invention belongs to synthesis method of zeolite molecular sieve.
Mordenite is widely used as divided gas flow or liquid mixture adsorption agent.Because it has good catalytic performance, also is usually used in catalytic processs such as catalytic cracking, alkylation, isomerization, disproportionation and transalkylation, reformation, dewaxing pour point depression, methyl alcohol amination.Mordenite is a kind of new catalytic material that paid attention to by people.
Mordenite is no matter be natural mordenite zeolite or general method synthetic mordenite, its SiO
2/ Al
2O
3Molecular ratio mostly is 10-12.And to some reaction process, for example, toluene disproportionation and transalkylation reaction need with higher SiO
2/ Al
2O
3The mordenite of molecular ratio is as catalyzer, because high silicon mordenite presents higher catalytic activity, selectivity and better stable.
Past people mostly adopts with SiO
2/ Al
2O
3Molecular ratio is about 10 mordenite, through 1) acid extraction, 2) roasting-acid extraction, 3) one or more dealumination treatment such as high-temperature water vapor processing-acid extraction are to produce high silicon mordenite, and what obtain is dealuminzation type mordenite.But, dealuminzation operating process more complicated.Afterwards, developed direct method for preparing high silica mordenite, having comprised: 1) high silicon pure aluminium silicate method: use SiO
2/ Al
2O
3It is synthetic that molecular ratio is that the high silicon pure aluminium silicate of 15-30 adds the alkali crystallization; 2) water glass, aluminium salt crystallization in the presence of sodium-chlor is synthetic; 3) silicon sol, sodium aluminate are raw material, and crystallization is synthetic in the presence of organic alkali (as benzyl trimethyl amine or the pyridine of bromination diethyl croak); 4) silica gel method: synthetic with raw material crystallization such as silica gel, aluminium salt, alkali.
About direct method for preparing high silica mordenite, United States Patent (USP) 3,677 973(1972) is introduced, and makes SiO with raw materials such as water glass, aluminium salt, sulfuric acid, ammoniacal liquor through becoming glue, washing, drying
2/ Al
2O
3Molecular ratio is the high silicon pure aluminium silicate of 15-30, then the synthetic SiO of hydro-oxidation sodium crystallization
2/ Al
2O
3Molecular ratio is the high silicon mordenite of 15-30.The disclosure was speciallyyed permit among clear 56-160316 and the clear 58-88119 and was introduced day, and in the presence of sodium-chlor, crystallization is synthesized SiO with raw materials such as water glass, Tai-Ace S 150, sulfuric acid
2/ Al
2O
3Molecular ratio is the high silicon mordenite of 17.4-25.8.The high silicon mordenite that obtains with aforesaid method through the x-diffraction analysis, the spectrum peak of medium tenacity occurs on 23.2 ° of 2 θ and 7.8 ° of positions, illustrate to have stray crystal.Per diem the disclosure is speciallyyed permit clear 58-88118 and European patent 080615(1983) institute's synthetic high silicon mordenite, though above-mentioned two stray crystal peaks do not occur, but need to use organic alkali in the building-up process, compound as benzyl trimethyl amine and the pyridine of bromination diethyl croak and so on is made additive reagent, this class organic alkali is difficult for obtaining, and price is expensive and poisonous.In addition, from Zeolites 6(1), 30(1986) specially permit among the clear 60-118624 with a day disclosure and introduce, add the synthetic method of alkali crystallization, the SiO that raw material feeds intake with water glass and aluminium salt
2/ Al
2O
3Molecular ratio is very high, the product S iO that obtains
2/ Al
2O
3Molecular ratio is but not high, as day the disclosure specially permit among the clear 60-118624 reaction raw materials SiO
2/ Al
2O
3Molecular ratio is up to 98, but gained mordenite SiO
2/ Al
2O
3Molecular ratio has only 16.3.Improved production cost as manufacturing process, inadvisable economically.
More than several method for preparing high silica mordenite, shortcoming such as exist complex process, troublesome poeration, raw material sources are few, price is expensive, toxicity is big, environmental pollution is serious, quality product is low.For this reason, at the existing shortcoming of above-mentioned synthesizing high silicon content mordenite method, the present invention use wide material sources, cheap, technological operation convenient, inorganic ammonia or the ammonia and the sodium-chlor of nontoxic, nonpollution environment, replacement valency height, deleterious organic alkali are as additive reagent, through the directly synthetic SiO of crystallization
2/ Al
2O
3Molecular ratio is the high silicon mordenite of 15-30.The additive reagent ammonia that adds among the present invention or ammonia and sodium-chlor, its effect are in the zeolite synthesis process, promote the formation of mordenite structure, play a part to make " template ", " directed agents ", impel high silicon mordenite to generate, and are unfavorable for α-SiO
2, ZSM-5 and so on stray crystal generates.From Fig. 2 as seen, 23.2 ° of aforesaid 2 θ and 7.8 ° of two stray crystal peaks do not appear in synthetic high silicon mordenite of the present invention.
The main points of high silicon mordenite synthetic method of the present invention are: do not use organic alkali to make additive reagent, also need not high silicon pure aluminium silicate, expensive raw material such as silica gel, silicon sol, and only use water glass, mineral acid (example hydrochloric acid, sulfuric acid or nitric acid), mineral alkali (as liquid caustic soda or sodium hydroxide), aluminium salt (as aluminum chloride, Tai-Ace S 150 or aluminum nitrate) or aluminate (as sodium aluminate) to be raw material, in crystallization, make additive reagent (used ammonia can be ammoniacal liquor or liquefied ammonia), keep the molecular ratio in the reaction mixture to be: NH with ammonia or ammonia and sodium-chlor
3/ Al
2O
3=5-100; Na
2O/Al
2O
3=1-10; SiO
2/ Al
2O
3=15-30; H
2O/Al
2O
3=200-1000, crystallization temperature are 120-250 ℃, and the time of crystallization is 4-480 hour.In the reaction mixture, add the high silicon mordenite that makes by the present invention as crystal seed, can shorten crystallization time, the crystal seed add-on is the 0.5-10%(weight of high silicon mordenite ultimate capacity).Crystallization gained mixture after filtration, washing, drying promptly make SiO
2/ Al
2O
3Molecular ratio is the high silicon mordenite of 15-30.
Use method of the present invention, the molecular ratio of change reaction mixture is regulated other crystallization process condition, can synthesize to have different SiO
2/ Al
2O
3The mordenite series product of molecular ratio, different grain sizes.
The high silicon mordenite that makes as stated above carries out ion-exchange in ammonium chloride solution or ammonium nitrate solution, make zeolite powder through washing, drying again, adds aqueous alumina (α-Al of 20-50% then
2O
3H
2O) or other tackiness agent, mediate, extruded moulding, 110 ℃ dry 12 hours down, 450-580 ℃ following roasting 1-10 hour, make Hydrogen high silicon mordenite catalyzer at last.Prepared catalyzer is white Cylinder, particle diameter 1.6-1.8 millimeter, and long 2-20 millimeter, its main physical and chemical performance: the thing phase composite is that mordenite and aluminum oxide, tap density 0.75 ± 0.1 grams per milliliter, crushing strength are greater than 10 kilograms per centimeter
3, the efflorescence degree is less than or equal to 0.5%(weight).
By the catalyzer that the inventive method makes, it is effective especially to be used for toluene disproportionation and transalkylation production benzene and dimethylbenzene.Under gas phase was faced hydrogen, the Hydrogen high silicon mordenite that uses the inventive method to make was catalyzer as toluene, when liquid volume air speed 0.9
-1, toluene and C9 aromatic weight ratio be 100: 0-60: 40, hydrogen hydrocarbon molecule ratio is that 8: 1, reaction pressure are that 2-3 MPa, temperature of reaction are to react under the 370-490 ℃ of condition, and can present high reactivity, highly selective and good stability: toluene and C9 aromatic transformation efficiency are the 40-45%(mole), benzene and C8 aronmatic selectivity be greater than the 96%(mole), 1 year catalyst regeneration cycle, catalyzer work-ing life is more than 3 years.
Example 1
352.2 gram water glass (SiO
225.50wt%, Na
2O7.30wt%, H
2O67.2wt%, down together) and 28.6 gram liquid caustic soda (Na
2O30wt%, H
2O70wt%) mix.64.5 gram solid sulphuric acid aluminium (Al
2(SO
4)
318H
2O) be dissolved in 139 ml waters, above-mentioned two kinds of solution are added in the container of band whipping appts simultaneously, add 100 gram ammoniacal liquor then and (contain NH
325.5wt%), mix, the gained reaction mixture moves in the stainless steel crystallizing kettle of 2 liter capacities.Crystallizing kettle is airtight, be warming up to 200 ℃, constant temperature 24 hours in 2 hours.Cooling, filtered and recycled solid product then, again through washing, 110 ℃ dry 8 hours down.The x-diffraction analysis is the result conform to data in literature.
The reaction mixture molecular ratio is:
Na
2O∶Al
2O
3∶SiO
2∶H
2O∶NH
3＝2.6∶1∶15∶280∶15
SiO in the product mordenite
2/ Al
2O
3Molecular ratio is 15.0.
Example 2
11.1 gram sodium hydroxide (chemical pure) is dissolved in 17.5 ml waters, with the liquid caustic soda in this solution replacement example 1, all the other are all operated by the step of example 1.The product x-diffraction analysis result of gained conforms to data in literature.
The reaction mixture molecular ratio is:
Na
2O∶Al
2O
3∶SiO
2∶H
2O∶NH
3＝2.6∶1∶15∶280∶15
Product mordenite SiO
2/ Al
2O
3Molecular ratio is 15.0.
Example 3
361.5 gram water glass dilutes with 65 ml waters, gets A solution.51.1 gram solid sulphuric acid al dissolution in 150 gram water, and adds the 2.65 gram vitriol oils (98wt%), mix B solution.Under stirring state, A, B two solution are added in the container simultaneously, be transferred to behind the thorough mixing in 2 liters of crystallizing kettles.Crystallizing kettle is airtight, and bubbling feeds 32.6 gram liquefied ammonia (purity＞99%) in still, intensification crystallization, 180 ℃ of following constant temperature 30 hours.Cooling, filtered and recycled solid product then, again through washing, 110 ℃ dry 12 hours down.The x-diffraction analysis confirms that solid product is a mordenite.
The reaction mixture molecular ratio is:
Na
2O∶Al
2O
3∶SiO
2∶H
2O∶NH
3＝2.5∶1∶20∶350∶25
Product mordenite SiO
2/ Al
2O
3Molecular ratio is 19.8.
Example 4
367.2 gram water glass with 120 gram water dilute A solution, 41.6 gram solid sulphuric acid al dissolutions add the 10.9 gram vitriol oils (98wt%) again in 400 gram water, mix B solution, the step operation of press example 3 then, but the liquefied ammonia of feeding is 53 to restrain.Show that through the x-diffraction analysis product is the mordenite (see figure 2), this zeolite stereoscan photograph (see figure 1).
The reaction mixture molecular ratio is:
Na
2O∶Al
2O
3∶SiO
2∶H
2O∶NH
3＝2.0∶1∶25∶700∶50
Product mordenite SiO
2/ Al
2O
3Molecular ratio is 24.9.
Example 5
371.1 gram water glass with 278 restrain water dilute A solution.35 gram solid sulphuric acid al dissolutions add the 43.7 gram vitriol oils (98wt%) again in 400 gram water, mix B solution.Press the step operation of example 3 then, but the liquefied ammonia that feeds is 89.3 grams.X-diffraction analysis solid product is a mordenite.
The reaction mixture molecular ratio is:
Na
2O∶Al
2O
3∶SiO
2∶H
2O∶NH
3＝3.0∶1∶30∶1000∶100
Product S iO
2/ Al
2O
3Molecular ratio is 28.4.
Example 6
367.2 gram water glass with 95 restrain water dilute A solution.41.6 gram solid sulphuric acid aluminium adds the 14.9 gram vitriol oils (98wt%) then with 200 gram water dilutions, gets B solution.Press later the step operation of example 3, but the liquefied ammonia that feeds is 53 grams, 180 ℃ of crystallization temperatures, constant temperature 96 hours.X-diffraction analysis solid product is a mordenite.
The reaction mixture molecular ratio is:
Na
2O∶Al
2O
3∶SiO
2∶H
2O∶NH
3＝1.5∶1∶25∶500∶50
Product S iO
2/ Al
2O
3Molecular ratio is 24.8.
Example 7
367.2 gram water glass with 95 restrain water dilute A solution.41.6 gram solid sulphuric acid aluminium adds the 10.9 gram vitriol oils (98wt%) again and gets B solution with 200 gram water dissolution, presses the step operation of example 3 again, but the liquefied ammonia that feeds is 53 grams, 185 ℃ of crystallization temperatures, constant temperature 18 hours.The product of gained is a mordenite.
The reaction mixture molecular ratio is:
Na
2O∶Al
2O
3∶SiO
2∶H
2O∶NH
3＝2.0∶1∶25∶500∶50
Product S iO
2/ Al
2O
3Molecular ratio is 24.6.
Example 8
367.2 gram water glass with 120 gram water dilute A solution, 41.6 gram solid sulphuric acid al dissolutions add 10.9 again and restrain the vitriol oils (98wt%) in 400 gram water, mix B solution.Under stirring state, A B two solution are added in the container simultaneously, add example 4 gained high silicon mordenite powder 0.5 gram of the present invention again.Crystallizing kettle is airtight, and bubbling feeds liquefied ammonia 53 grams in still.Be warming up to 180 ℃ of thermostatic crystallizations 24 hours.X-diffraction analysis solid product is a mordenite.Product S iO
2/ Al
2O
3Molecular ratio is 25.0.
Example 9
Sulfuric acid in the example 3 is replaced with nitric acid, and Tai-Ace S 150 replaces with aluminum nitrate, the molecule of reaction mixture when synthesis step and example 3 with.Products therefrom is a mordenite, SiO
2/ Al
2O
3Molecular ratio is 19.6.
Example 10
With the salt acid substitution of the sulfuric acid in the example 3, Tai-Ace S 150 replaces with aluminum chloride, and the molecular ratio of reaction mixture and example 3 add example 4 gained high silicon mordenite powder 10 grams of the present invention together again.180 ℃ of following crystallization 8 hours.Products therefrom is a mordenite, SiO
2/ Al
2O
3 
367.2 gram water glass gets A with 120 gram water dilutions
20.7 the gram sodium-chlor be dissolved in 400 the gram water in, add again 10.9 the gram vitriol oils (98wt%), mix B solution.Press the step operation of example 3 then, but the liquefied ammonia that feeds is 53 grams.Products therefrom is a mordenite, product S iO
2/ Al
2O
3Molecular ratio is 24.9.
Example 12
1650 kg of water glass are A solution.165 kilograms of solid sulphuric acid al dissolutions add 53.1 kilograms of the vitriol oils again in 1350 kg of water, mix B solution.Under stirring state, A, B solution are added in 5000 liters of crystallizing kettles simultaneously, add 2.25 kilograms in gained high silicon mordenite powder of the present invention then, feed 47.7 kilograms in liquefied ammonia again.180 ℃ of following crystallization 28 hours.X-diffraction analysis solid product is a mordenite, its SiO
2/ Al
2O
3Molecular ratio is 24.9.
Example 13
With the high silicon mordenite of example 4 preparations, after ammonium chloride or the exchange of ammonium nitrate solution intermediate ion, with α-Al
2O
3H
2O mixes, through extruded moulding, 110 ℃ of dryings 12 hours, activation is 4 hours in 580 ℃ of air, Hydrogen high silicon mordenite catalyzer.Carry out toluene disproportionation and transalkylation activity with 50 milliliters of catalyzer and investigate, reaction raw materials toluene and C9 aromatic weight ratio are 65: 35, hydrogen/hydrocarbon molecule than 8: 1, reaction pressure 3 MPas, feed liquid volume space velocity 0.9 hour
-1, 390 ℃ of temperature of reaction.Through 100 hours reaction results, toluene and C9 aromatic transformation efficiency were 41.9%, and the selectivity that generates benzene and C8 aronmatic is 97.0%.
Claims (6)
1, a kind of is raw material with water glass, mineral acid, mineral alkali, aluminium salt or aluminate, and method for preparing high silica mordenite is characterized in that in crystallization that with ammonia as additive reagent, the molecular ratio in the reaction mixture is: NH
3/ Al
2O
3=5-100, Na
2O/Al
2O
3=1-10, SiO
2/ Al
2O
3=15-30, H
2O/Al
2O
3=200-1000, crystallization temperature is 120-250 ℃, finishing the required time of crystallization is 4-480 hour, add the high silicon mordenite that makes by the present invention in the reaction mixture as crystal seed, can shorten crystallization time, crystallization gained mixture after filtration, washing, drying is promptly made high silicon mordenite.
2, according to the described method for preparing high silica mordenite of claim 1, it is characterized in that used mineral acid is sulfuric acid, hydrochloric acid or nitric acid, used mineral alkali is a sodium hydroxide.
3, according to the described method for preparing high silica mordenite of claim 1, it is characterized in that used aluminium salt is aluminum chloride, Tai-Ace S 150 or aluminum nitrate, used aluminate is a sodium aluminate.
4,, it is characterized in that the additive reagent ammonia that adds in the crystallization can be ammoniacal liquor or liquefied ammonia according to the described method for preparing high silica mordenite of claim 1.
5, according to the described method for preparing high silica mordenite of claim 1, the add-on that it is characterized in that crystal seed is the 0.5-10%(weight of high silicon mordenite ultimate capacity).
6,, it is characterized in that in the crystallization process except adding ammonia, also can adding sodium-chlor simultaneously as additive reagent according to the described method for preparing high silica mordenite of claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 89106793 CN1020039C (en) | 1989-09-06 | 1989-09-06 | Synthesis of mercerized zeolite with high silicon content |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 89106793 CN1020039C (en) | 1989-09-06 | 1989-09-06 | Synthesis of mercerized zeolite with high silicon content |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1050011A CN1050011A (en) | 1991-03-20 |
| CN1020039C true CN1020039C (en) | 1993-03-10 |
Family
ID=4856869
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 89106793 Expired - Lifetime CN1020039C (en) | 1989-09-06 | 1989-09-06 | Synthesis of mercerized zeolite with high silicon content |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1020039C (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1044868C (en) * | 1994-12-29 | 1999-09-01 | 复旦大学 | C8 aromatic hydrocarbon isomerization catalyst and its preparation method |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1050594C (en) * | 1996-08-20 | 2000-03-22 | 中国石油化工总公司 | Methylbenzene disproportionating and alkyl group transfering process |
| CN1052454C (en) * | 1997-06-06 | 2000-05-17 | 中国石油化工总公司 | Synthesis of mordenite with high silicon aluminum ratio |
| CN1079284C (en) * | 1997-06-06 | 2002-02-20 | 中国石油化工总公司 | Catalyst for toluene disproportionation and alkyl transfer |
| CN1094074C (en) * | 1998-11-18 | 2002-11-13 | 中国石油化工集团公司 | Toluene disproportionation and transalkylation catalyst and its process |
| CN1116229C (en) * | 2000-06-15 | 2003-07-30 | 中国石油化工集团公司 | Synthesis method of high-silicon mordenite |
| CN1164541C (en) | 2001-10-22 | 2004-09-01 | 中国石油化工股份有限公司 | Toluene selective disproportion and toluene and C9 and its above aromatic disproportion and alkyl transfusion method |
| CN102060308B (en) * | 2009-11-18 | 2012-08-22 | 中国科学院大连化学物理研究所 | Synthesis method of nano fibrous mordenite |
| CN103030542A (en) * | 2011-09-29 | 2013-04-10 | 中国石油化工股份有限公司 | Method for preparing 4-hexene-3-ketone by 4-hydroxy-3-hexanone hydration |
| CN110790282B (en) * | 2019-11-20 | 2021-08-06 | 南京沃力化工技术咨询有限公司 | Method for synthesizing mordenite with silicon-aluminium ratio of 20-26 |
-
1989
- 1989-09-06 CN CN 89106793 patent/CN1020039C/en not_active Expired - Lifetime
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1044868C (en) * | 1994-12-29 | 1999-09-01 | 复旦大学 | C8 aromatic hydrocarbon isomerization catalyst and its preparation method |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1050011A (en) | 1991-03-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP0002899B1 (en) | Method for preparing aluminosilicates and their use as catalyst supports and catalysts | |
| US5240892A (en) | Small crystal ZSM-5, as a catalyst | |
| CN100548879C (en) | ZSM-48 crystalline with non-ZSM-48 seeding of heterojunction structure synthesizes | |
| CA2071865C (en) | Zeolite l | |
| CN101717095B (en) | Synthesizing method of small-crystal particle rare earth-ZSM5/ZSM11 co-crystallizing zeolite | |
| EP0002900B1 (en) | Method for producing aluminosilicates and their use as catalysts and supports | |
| CN1020039C (en) | Synthesis of mercerized zeolite with high silicon content | |
| CN102040229A (en) | Synthetic method of MCM-22 (Multiple Chip Module 22) molecular sieve | |
| CN1281494C (en) | Process for preparing small crystal ZSM-5 zeolite | |
| CN1276873C (en) | Processfor preparing mordenite and beta zeolite mixed crystal material | |
| CN1093510C (en) | Process for synthesizing beta-zeolite | |
| CN100341784C (en) | Synthetic method for MCM-22 molecular sieve | |
| CN102050466B (en) | Method for in-suit synthesis of Y-type molecular sieve by taking silicon-aluminum as base material | |
| CA1185953A (en) | Method for manufacture of ams-1b crystalline borosilicate molecular sieve | |
| CN1074388C (en) | Zeolite synthesizing method | |
| CN1083399C (en) | Synthesis of high-silicon mordenite | |
| CN1353087A (en) | Process for preparing ZSM-5 molecular sieve | |
| CN101941718B (en) | Synthesis method of molecular sieve of TON structure | |
| CN1030286C (en) | Preparation of ZSM-5 zeolite/silica-gel composite catalyst material | |
| CA2345637A1 (en) | Process for preparing methylamines using acidic molecular sieve catalysts | |
| CN1137049C (en) | Synthesis of MCM-49 zeolite | |
| CN1689972A (en) | Co-crystallization molecular screen and preparation method and application thereof | |
| CN100408180C (en) | Method for preparing catalyst of para xylene through methylation of toluene | |
| CN1136984C (en) | Zeolite catalyst for direct synthesis of arene with methane and its prepn | |
| CN1490245A (en) | High silicon mordenite and preparing method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C06 | Publication | ||
| PB01 | Publication | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C15 | Extension of patent right duration from 15 to 20 years for appl. with date before 31.12.1992 and still valid on 11.12.2001 (patent law change 1993) | ||
| OR01 | Other related matters | ||
| C17 | Cessation of patent right | ||
| CX01 | Expiry of patent term |
Granted publication date: 19930310 |
|
| DD01 | Delivery of document by public notice |
Addressee: China Petrochemical Corporation Document name: Notification of Expiration of Patent Right Duration |