CN1169620C - High active long-acting fluorating catalyst and its producing method - Google Patents
High active long-acting fluorating catalyst and its producing method Download PDFInfo
- Publication number
- CN1169620C CN1169620C CNB011419709A CN01141970A CN1169620C CN 1169620 C CN1169620 C CN 1169620C CN B011419709 A CNB011419709 A CN B011419709A CN 01141970 A CN01141970 A CN 01141970A CN 1169620 C CN1169620 C CN 1169620C
- Authority
- CN
- China
- Prior art keywords
- catalyst
- activity
- reaction
- acting
- pore volume
- 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
Abstract
The present invention relates to a high-activity long-acting fluorinating catalyst and a manufacturing method thereof. The purpose of the fluorinating catalyst is to solve the problems of lower activity and short service life of a fluorinating catalyst. The fluorinating catalyst adopts two metal bases having the cooperation and assistance effects besides a chromium base, the metal bases mutually inhibit the crystal formation, a catalyst precursor is accelerated at the lower temperature of 200 to 400 DEG C, and acceleration and activating treatment adopt reducibility hydrogen; therefore, the sintering is avoided, and the specific area and the pore volume are enlarged. The catalyst of the present invention is used for a two-step reaction which uses trichloroethylene and anhydrous hydrogen fluoride as raw materials to be fluorinated and synthesized into HFC-134a by a gas phase, and has the characteristics of high activity, good stability, long service life, etc.
Description
Technical field
The present invention is a kind of high active long-acting fluorating catalyst (abbreviation catalyst) and manufacture method thereof, and it belongs to fluorination catalyst, is mainly used in halogenated hydrocarbons and hydrofluoric fluorine halogen exchange reaction.
Background technology
In recent years, the problem of destroying ozone layer in the atmosphere owing to the CFC that contains the chlorine atom becomes increasingly conspicuous, and 1,1,1,2-HFC-134a (being called for short HFC-134a) compound has just in time solved this problem.This compound is a chromium-based catalysts by the catalyst majority that trichloro-ethylene and hydrogen fluoride react synthetic, used in gas phase.The catalyst based activity of Cr is good, but easily coking, the synthetic patent of early stage HFC-134a is many to feed O in the reaction gas
2Gas keeps activity of such catalysts and life-span, but has increased accessory substance and equipment corrosion.Cr is catalyst based can be divided into infusion process, wet chemistry method, blending method, thermal decomposition method etc. according to the preparation method.Infusion process is many with γ-AlF
3, partially fluorinated γ-Al
2O
3, activated carbon, γ-Al
2O
3Deng being carrier, be active component with Cr etc.Since restrictions such as the stand under load surface area per unit volume is long-pending, pore volume, the content of main active component Cr generally lower (＜10%), activity is restricted, and general space-time yield is lower.Trichloro-ethylene is directly fluoridized, only can be obtained yield and be 3% HFC-134a, activity of such catalysts decays rapidly in addition, needs often regenerate, change catalyst, and this obviously is unfavorable for suitability for industrialized production.Chinese patent 95115476.1 has been reported the yield that " a kind of fluorination catalyst of fluorination of halogenated hydrocarbon " improved product HFC-134a, has slowed down the catalyst activity decay.But along with the expansion of suitability for industrialized production scale, activity of such catalysts and service life still can not satisfy the demand, and especially the speed that descends along with the rising of material air speed and reaction temperature of catalyst activity is accelerated, and has influenced service life.
Chinese patent 94115127.1 has been reported " fluorination process of a kind of chromium-based fluorination catalyst and production method thereof and this catalyst of use " and pointed out: the heat-treat condition when the preparation catalyst has very big influence to the performance of catalyst, but also find, by in the presence of hydrogen, in 350～500 ℃ of roastings or heat a kind of material of mainly forming by the hydroxide of chromium (III), the precursor of preparation catalyst, and the chromium-based fluorination catalyst that partially fluorinated this catalyst precarsor is produced in the air-flow of fluorinated hydrogen, on selectivity and activity, all be better than traditional fluorination catalyst.Find out that from above-mentioned patent heat-treat condition has a significant impact catalyst performance, but the way of head it off only is to set about from extraneous heat-treat condition, fails to set about solving the problem, so the effect that obtains is limited from the catalyst itself that is produced.Catalyst precarsor is confined to a kind of chromium base in addition, if adopt carrier, the advantageous effects of its invention can maybe can not obtain for a short time.Chinese patent 96121696.6 has been reported " a kind of is amorphous catalyst of base with chromium oxide; its preparation method and its application in the halogenated hydrocarbons fluorination reaction " and has been pointed out: chromium oxide or chromium and may another kind of at least catalytically active metal oxides, fluorination catalyst specific area＞25m that it is fluorine-containing
2/ g.Is the catalyst that the catalyst of base can obtain to improve reactivity by a kind of supercritical fluid drying with armorphous chromium oxide, has improved the rate of fluoridizing significantly, and self can be limited in the formation of water in the industrial reactor by it.Though this invention has improved active to a certain extent and fluoridized rate, the fluorination catalyst specific area is on the low side, and service life is shorter.
Summary of the invention
Purpose of the present invention is exactly in order to overcome disadvantages of background technology, designs that a kind of activity is high, armorphous, the Catalysts and its preparation method of long service life.
Design of the present invention: to achieve these goals, obtain that a kind of activity is high, armorphous, the catalyst of long service life, the essential two big technical barriers that solve, exothermic effect was easy to generate sintering phenomenon too when the first will solve in the roasting process and to decompose heat release hot-spot generation sintering phenomenon and catalyst precarsor and carry out fluorination treatment, can both reduce the specific area of catalyst greatly, influence activity of such catalysts.It two is that catalyst crystalline phases transforms especially single chromium base and is easy to generate crystal structure or microcrystalline texture, and the stability that the existence of crystal influences catalyst has promptly influenced catalyst service life, so armorphous the changing into of catalyst is key problem in technology.Obtain armorphous fluorination catalyst, must except the chromium base, add two kinds of Metal Substrate that play collaborative and booster action in addition, it three is that metallic compound does not preferably belong to same crystallographic system, the speed of growth of crystal has nothing in common with each other, so just destroy the formation of " dot matrix " in the crystal growing process, all suppressed crystal formation between three kinds of metallic compounds mutually; Prevent the sintering of catalyst, the first step prevents the catalyst precarsor sintering, at first to overcome the chromium based hybroxide and produce hot-spot 405 ℃ of fierce decomposition, its way is in adding two kinds of Metal Substrate, select the lower Metal Substrate of a kind of Metal Substrate hydroxide decomposition temperature, can generate the active hydrogen oxygen radical when utilizing the lower Metal Substrate hydroxide of decomposition temperature to decompose and act on the chromium based hybroxide, chromium based hybroxide decomposition activation energy is reduced, use TA, among Fig. 1 that the DSC2910 instrument is measured, the strong exothermic peak of Cr based hybroxide disappears in Fig. 2, has illustrated at a lower temperature slowly to decompose.Second step prevented that sintering of catalyst from adopting inert gas to water down, increase lentamente and control outside the temperature, with nascent state, hydrogen under super-dry and laser irradiation feeds as inert gas, hydrogen produces the free radical of a small amount of hydrogen under the laser irradiation, have reproducibility, can reduce and fluoridize activation energy, also reduce the strong exothermic effect of fluorination reaction, avoided the micropore sintered of catalyst.
Catalyst of the present invention is characterized in being made up of many Metal Substrate, oxygen and fluorine, and its combined type is as follows:
CrX
0.005～0.5Y
0.005～0.3O
0.1～1.0F
1.0～3.0
X is Mn in the formula, Co or Zn; Y is Mg or Ni.
Another characteristics of the present invention are that Cr, Mn, Mg, O and F form, and its combined type is CrMn
0.05～0.4Mg
0.05～0.2O
0.5～1.0F
1.0～2.5
Another characteristics of the present invention are that combined type is CrMn
0.3Mg
0.1O
0.5F
2.0
Manufacture method of the present invention, comprising many Metal Substrate soluble-salt is dissolved, 20～100 ℃ of following and precipitating reagent reactions, between 6.5～9.5PH value, stir, precipitate, filter, and drying becomes catalyst precarsor with roasting under 100～200 ℃, be characterized in catalyst precarsor in 200～400 ℃ of following roastings of lower temperature, in wherein roasting, the activation processing process, feed N
2, H
2Mist, H wherein
2It is nascent state and through super-dry, laser treatment with irradiation.
Advantage of the present invention is as follows:
1. activity of such catalysts height, good stability, the space-time yield of first step reaction are greater than 290g/Lh, and the space-time yield of second step reaction is greater than 180g/Lh.Catalyst continuous evaluation in service life is after 1000 hours, and activity remains unchanged.
2. utilize the coprecipitation preparation process simple, good reproducibility, specific area and pore volume are bigger, and the catalyst precarsor specific area is greater than 200m
2/ g, pore volume are greater than 0.3ml/g, and specific surface area of catalyst is greater than 60m
2/ g, pore volume is greater than 0.15ml/g.
3. many Metal Substrate are collaborative mutually, auxiliary catalysis and inhibition crystal formation produce and improved catalyst precarsor stability, avoided that crystal produces in curing and the activation process, and it is armorphous that catalyst precarsor and catalyst are, and plays a key effect to increasing the service life.
4. in curing, activation process, prevented the sintering phenomenon appearance, greatly increasing specific surface area and pore volume thereby catalyst activity height.
Description of drawings
Description of drawings of the present invention is as follows:
Fig. 1 is Cr (OH)
3Differential thermal analysis curve
Fig. 2 is Cr (OH)
3, Mn (OH)
2And Mg (OH)
2Differential thermal analysis curve
Fig. 3 is the XRD figure spectrum of catalyst
Fig. 4 is the catalyst life Test Drawing
The specific embodiment
1. manufacture method of the present invention is implemented with reference to following combined type:
CrMn
0.3Mg
0.1O
0.5F
2.0
1.1 catalyst precarsor preparation
Active component soluble-salt (can be nitrate, sulfate, chloride etc.) is mixed with certain density solution, 20～100 ℃ down and precipitating reagent (can be NaOH, KOH, (NH
4)
2CO
3, ammoniacal liquor etc.) reaction, control final pH value between 6.5～9.5, carry out strong agitation therebetween, active component is fully precipitated, filter then, with deionized water or methanol wash to neutral, again with filter cake 100～200 ℃ dry down, make specific area greater than 200m
2g
-1, pore volume is greater than 0.3mlg
-1The amorphous catalyst precursor.
1.2 curing, activation processing
Precursor is added compressing tablet moulding such as graphite, pack into then and under 200～400 ℃, fully solidify in the reactor with inert gas, feed inert gas and hydrofluoric gaseous mixture again 200～400 ℃ of activation down, feed pure hydrogen fluoride at last and make catalyst reach certain degree of fluorination, make the oxyfluoride amorphous catalyst.In activation process, the strong exothermic effects of fluorination reaction can make the micropore sintered of catalyst, can cause catalyst tight burning inactivation when serious.So the ratio of necessary strict control hydrogen fluoride and inert gas is carried out activation processing under relatively mild condition.The temperature rise of control fluorination reaction is less than 50 ℃.Inert gas is N
2, H
2Mist, N
2: H
2=1: 0.1-1.0, wherein H
2Be nascent state through super-dry, laser treatment with irradiation.
Because the reaction of synthetic HFC-134a is carried out in the HF medium, so catalyst is that form with fluoride exists.Precursor obtains in the process of catalyst in activation processing, and in order to prevent the sintering inactivation, the ratio and the reaction temperature of hydrogen fluoride and inert gas controlled in necessary strictness, and fluorination reaction is carried out under comparatively gentle condition, and the higher catalyst of degree of fluorination has higher activity.
Table 1 catalyst degree of fluorination is to the influence of reactivity
Numbering F/Cr O/Cr HFC-134a productive rate, %
1 2.32 1.01 25.4
2 1.66 0.49 24.3
3 1.58 0.96 23.6
4 0.43 1.48 8.5
Reaction condition: HF: HCFC-133a=4: 1,350 ℃ of temperature, air speed 1320/h
-1
1.3 the reactivity worth of catalyst
Above-mentioned catalyst 50ml (10-18 order) is packed in Φ 19 * 2 nickel pipe reactors of fused salt heating, carry out following two reactions, the result is shown in table 2 and table 3.
TCE AHF HCFC-133a
HCFC-133a HFC-134a
Activity of such catalysts in table 2 reaction (1)
Numbering reaction temperature/℃ HF/TCE GHSV/h
-1The HCFC-133a productive rate, %
1 280 10∶1 1320 95.1
2 280 10∶1 1320 94.3
Activity of such catalysts in table 3 reaction (2)
Numbering reaction temperature/℃ HF/HCFC133a GHSV/h
-1The HFC-134a productive rate, %
1 350 4.5∶1 1320 22.6
2 350 4.5∶1 1650 22.8
3 350 4.5∶1 1980 20.6
4 350 4.6∶1 1344 21.3
1.4 catalyst performance test
1.4.1 armorphous mensuration
The XRD characterization result shows that the catalyst of coprecipitation preparation is armorphous, and its crystal phase structure does not change before and after fluorination reaction, and is shown in Figure 3 as what measure with the D/MAX-2400 instrument.
1.4.2 the mensuration of specific area, pore volume
Measured specific area, pore volume, the pore-size distribution of catalyst with the BET physical adsorption appearance, test result: specific area is greater than 60m
2G
-1, pore volume is greater than 0.15mlg
-1The time reactivity preferably arranged, and increase with the augmenting response of specific area and pore volume is active.
Measured result:
Specific area pore volume reaction (1) space-time yield reaction (2) space-time yield
m
2·g
-1 ml·g
-1 g·L
-1·h
-1 g·L
-1·h
-1
63 0.17 302 184
Reaction (1) condition: 280 ℃, HF/TCE=10: 1, GHSV1320h
-1
Reaction (2) condition: 350 ℃, HF/HCFC133a=4: 1, GHSV1320h
-1
1.4.3 reinforcing life test
Select the reaction of HCFC-133a and HF, at 350 ℃, HF: HCFC133a=4: 1, air speed 1320h
-1Under the condition, the catalyst that screens has been carried out life test still had activity preferably as a result more than the 1000h, as shown in Figure 4.
1.5 catalyst application test
The catalyst long-play in the 200t/aHFC-134a commerical test device of packing into, catalyst presents good anti-coking and recyclability.
2 manufacture methods of the present invention are implemented with reference to following combined type:
CrCo
0.1Mg
0.7O
0.6F
1.0
Manufacturing process is identical with embodiment 1, and performance is basic identical, test results such as specific area, pore volume:
Specific area pore volume reaction (1) space-time yield reaction (2) space-time yield
m
2·g
-1 ml·g
-1 g·L
-1·h
-1 g·L
-1·h
-1
65 0.16 299 182
Reaction condition is with embodiment 1.
3 manufacture methods of the present invention, implement with reference to following combined type:
CrZn
0.2Mg
0.9O
0.7F
1.2
Manufacturing process is identical with embodiment 1, and performance is basic identical, test results such as specific area, pore volume:
Specific area pore volume reaction (1) space-time yield reaction (2) space-time yield
m
2·g
-1 ml·g
-1 g·L
-1·h
-1 g·L
-1·h
-1
61 0.19 304 194
Reaction condition is with embodiment 1.
4 manufacture methods of the present invention, implement with reference to following combined type:
CrMn
0.4Ni
0.12O
1.0F
1.4
Manufacturing process is identical with embodiment 1, and performance is basic identical, test results such as specific area, pore volume:
Specific area pore volume reaction (1) space-time yield reaction (2) space-time yield
m
2·g
-1 ml·g
-1 g·L
-1·h
-1 g·L
-1·h
-1
65 0.18 302 189
Reaction condition is with embodiment 1.
5 manufacture methods of the present invention, implement with reference to following combined type:
CrCo
0.05Ni
0.16O
0.8F
1.6
Manufacturing process is identical with embodiment 1, and performance is basic identical, test results such as specific area, pore volume:
Specific area pore volume reaction (1) space-time yield reaction (2) space-time yield
m
2·g
-1 ml·g
-1 g·L
-1·h
-1 g·L
-1·h
-1
64 0.19 311 198
Reaction condition is with embodiment 1.
6 manufacture methods of the present invention, implement with reference to following combined type:
CrZn
0.08Ni
0.2O
0.9F
1.8
Manufacturing process is identical with embodiment 1, and performance and embodiment 5 are approaching.
Claims (4)
1. a high active long-acting fluorating catalyst is characterized in that being made up of many Metal Substrate, oxygen and fluorine, and its combined type is as follows:
CrX
0.005～0.5Y
0.005～0.3O
0.1～1.0F
1.0～3.0
X is Mn, Co or Zn in the formula; Y is Mg or Ni.
2. catalyst according to claim 1 is characterized in that being made up of Cr, Mn, Mg, O and F, and its combined type is CrMn
0.05～0.4Mg
0.05～0.2O
0.5～1.0F
1.0～2.5
3. catalyst according to claim 2 is characterized in that combined type is CrMn
0.3Mg
0.1O
0.5F
2.0
4. the manufacture method of the high active long-acting fluorating catalyst of a claim 1, comprising many Metal Substrate soluble-salt is dissolved, 20～100 ℃ of following and precipitating reagent reactions, between 6.5～9.5PH value, stir, precipitate, filter, and drying becomes catalyst precarsor with roasting under 100～200 ℃, be characterized in catalyst precarsor in 200～400 ℃ of following roastings of lower temperature, in wherein roasting, the activation processing process, feed N
2, H
2Mist, H wherein
2It is nascent state and through super-dry, laser treatment with irradiation.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011419709A CN1169620C (en) | 2001-09-26 | 2001-09-26 | High active long-acting fluorating catalyst and its producing method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011419709A CN1169620C (en) | 2001-09-26 | 2001-09-26 | High active long-acting fluorating catalyst and its producing method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1408476A CN1408476A (en) | 2003-04-09 |
| CN1169620C true CN1169620C (en) | 2004-10-06 |
Family
ID=4676523
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB011419709A Expired - Lifetime CN1169620C (en) | 2001-09-26 | 2001-09-26 | High active long-acting fluorating catalyst and its producing method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1169620C (en) |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1911512B (en) * | 2005-07-07 | 2011-12-07 | 独立行政法人产业技术综合研究所 | Fluorination catalysts, method for their preparation, and method for producing fluorinated compounds using the catalysts |
| CN1308072C (en) * | 2005-09-30 | 2007-04-04 | 山东东岳化工有限公司 | Iron series chromium base catalyst for 1,1,1,2-tetrafluoro ethane |
| CN101041132B (en) * | 2007-04-23 | 2010-05-26 | 浙江师范大学 | Vapor-phase fluorination catalysts for producing HFC-134a and the preparing method |
| CN102001912A (en) * | 2010-10-24 | 2011-04-06 | 浙江衢化氟化学有限公司 | Method for synthesizing 3,3,3-trifluoropropene |
| CN102989489B (en) * | 2011-09-14 | 2015-04-22 | 中化蓝天集团有限公司 | 2,3,3,3-tetrafluoropropylene preparation method |
| CN103143344B (en) * | 2011-12-06 | 2015-10-14 | 中化蓝天集团有限公司 | A kind of high than table chromium-based fluorination catalyst and preparation method thereof |
| CN103880589B (en) | 2012-12-19 | 2015-07-29 | 中化蓝天集团有限公司 | The technique of HFO-1234ze and HFC-245fa is prepared in a kind of coproduction |
| CN104707631A (en) | 2013-12-12 | 2015-06-17 | 西安近代化学研究所 | Chromium-free gas phase fluorination catalyst and use thereof |
| CN103896721B (en) * | 2014-04-11 | 2015-04-15 | 太仓中化环保化工有限公司 | Preparation method of 1,1,1,2-tetrafluoroethane |
| CN105344365A (en) * | 2015-11-23 | 2016-02-24 | 山东东岳化工有限公司 | Method for preparing fluorinated catalyst by homogeneous precipitation method |
-
2001
- 2001-09-26 CN CNB011419709A patent/CN1169620C/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| CN1408476A (en) | 2003-04-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1035320C (en) | Process for producing hydrogen peroxide | |
| CN1008088B (en) | Alcohols production by hydrogenation of carboxylic acids | |
| CN109174085A (en) | Atom level disperses palladium base Nano diamond/graphene composite material catalyst and its preparation method and application | |
| CN1103632C (en) | Shell catalyst for producing acetic acid by gas phase oxidation of unsaturated C4 hydrocarbons | |
| CN1169620C (en) | High active long-acting fluorating catalyst and its producing method | |
| CN104428273B (en) | Method for manufacturing Fluorine containing olefine | |
| CN1235561A (en) | Improved process for production of supported palladium-gold catalysts | |
| CN1681587A (en) | Catalyst and method for decomposition of perfluoro-compound in waste gas | |
| CN1764500A (en) | Catalyst for partial oxidation and preparation method thereof | |
| CN1422693A (en) | Preparation of ruthenium/iron catalyst loaded onto carbon | |
| CN107413366B (en) | Preparation method of phenol hydrogenation catalyst | |
| CN1188213C (en) | Metal oxide catalyst for synthesizing methyl carbonate by urea process and its prepn | |
| CN1859972A (en) | Catalyst for gaseous partial oxidation of propylene and its preparing method | |
| CN1239945A (en) | Process for producing aromatic amines by gaseous phase hydrogenation | |
| CN111875546A (en) | Echinoid cobalt-based photocatalyst for converting CO2Application of synthesizing benzazepine | |
| CN1164363C (en) | Catalyst in oxychlorination reaction as well as its preparation method and application | |
| CN107098790A (en) | A kind of method for preparing high-purity octafluoropropane | |
| CN1947839A (en) | Fluorination catalyst, its prepn. method and use | |
| CN1197651C (en) | Benzene selection noncrystalline catalyst with hydrogen added and containing ruthenium, boron as well as its preparing method | |
| CN1954911A (en) | Solid catalyst and its preparation and method of catalytic preparation epoxy propane hexafluoride | |
| CN1008973B (en) | The preparation method of syngas conversion catalyst | |
| CN1232720A (en) | Catalyst for self-heating oxidation and reforming of natural gas to produce synthetic gas and its preparation process | |
| Li et al. | Readily-fabricated supported MgO catalysts for efficient and green synthesis of diethyl carbonate from ethyl carbamate and ethanol | |
| CN113398912B (en) | Catalyst for synthesizing dimethyl carbonate by alcoholysis of methyl carbamate | |
| CN1133493C (en) | Efficient catalyst for synthesizing ammonia and its preparing process |
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 | ||
| C56 | Change in the name or address of the patentee |
Owner name: CHIAN CHEMICAL MODERN ENVIRONMENTAL PROTECTION CHE Free format text: FORMER NAME OR ADDRESS: JINZHU MODERN CHEMICAL CO., LTD., XI'AN |
|
| CP03 | Change of name, title or address |
Address after: 710201 Shaanxi city of Xi'an province Gaoling Jinghe Industrial Park Patentee after: Sinochem Modern Environmental Chemical Industrial ( Xi 'an)Co., Ltd. Address before: 710201 Shaanxi city of Xi'an province Gaoling Jinghe Industrial Park Patentee before: Jinzhu Modern Chemical Co., Ltd., Xi'an |
|
| EE01 | Entry into force of recordation of patent licensing contract |
Assignee: Sinochem Taicang Environmental Protection Chemical Co., Ltd. Assignor: Sinochem Modern Environmental Protection Chemicals (Xi'an) Co., Ltd. Contract record no.: 2012320010044 Denomination of invention: High active long-acting fluorating catalyst and its producing method Granted publication date: 20041006 License type: Exclusive License Open date: 20030409 Record date: 20120322 |
|
| CX01 | Expiry of patent term |
Granted publication date: 20041006 |
|
| CX01 | Expiry of patent term |