CN101497041B - Method for preparing palladium-carrying catalyst with nano Pd by suspension polymerization - Google Patents
Method for preparing palladium-carrying catalyst with nano Pd by suspension polymerization Download PDFInfo
- Publication number
- CN101497041B CN101497041B CN2009100088971A CN200910008897A CN101497041B CN 101497041 B CN101497041 B CN 101497041B CN 2009100088971 A CN2009100088971 A CN 2009100088971A CN 200910008897 A CN200910008897 A CN 200910008897A CN 101497041 B CN101497041 B CN 101497041B
- Authority
- CN
- China
- Prior art keywords
- palladium
- dispersant
- nanometer
- polymerization
- water
- 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 - Fee Related
Links
Landscapes
- Catalysts (AREA)
Abstract
The invention discloses a method for preparing a supported palladium catalyst by suspension polymerization with participation of nanometer palladium. The method comprises the following steps: adding a nanometer palladium suspending liquid into polymerization by a standard suspension polymerization process of macroporous styrene type cation exchange resin; obtaining a polymer microsphere (polystyrene-DVE) of which nanometer palladium is evenly distributed inside a frame after polymerization; making the surface of the nanometer palladium and a polymeric monomer chemically or physically adsorbed so as to be firmly combined together; and sulfonating the polystyrene-DVE to produce the supported palladium resin catalyst after hanging, washing and drying. The method has the advantages of simple process, easy operation, low cost, high reaction activity, small pollution, high product yield, high purity and recyclable resin; and the prepared resin catalyst can be applied to gasoline ether hydrogenation and methylisobutylketone synthesis processes.
Description
Technical field
The present invention relates to a kind of preparation technology of ion exchange resin, particularly the preparation technology of a kind of year palladium resin catalyst.
Technical background
The technology of development carried ion exchange resin palladium catalyst has some announcements both at home and abroad, as GB1010260, the disclosed palladium of US3953517/strongly acidic ion-exchange resin catalyst uses palladium nitrate dipping strong-acid ion exchange resin, this resin catalyst is the main catalyst of synthesize methyl-isobutyl ketone, but catalytic activity is lower, and selectivity is lower; CN1457927 has announced a kind of palladium/strongly acidic ion-exchange resin catalyst, adopts the acid solution and the strongly acidic ion-exchange resin catalyst that contain palladium to carry out ion-exchange; CN1883793 has announced a kind of nano Pd catalyst and preparation method thereof, is by water-soluble inorganic palladium salt and the water soluble polymer polymer loaded with nano palladium catalyst that reaction obtains under 60～90 ℃ of conditions in the low-carbon alcohols solvent.
More than invention all needs to carry out ion-exchange or impregnating load process, it is long to have technological process, organic solvent is many, palladium loses shortcomings such as bigger, and has only the active force of physical absorption, palladium to be easy to run off between palladium element after the reduction and carrier, and the present invention is evenly distributed on the nanometer palladium on the skeleton of resin microsphere by molecular separating force in polymerization, palladium is difficult for running off, and this technology has novelty, does not see relevant open report.
Summary of the invention
The present invention adopts the conventional process for suspension polymerization of macropore styrene type cation exchange resin known in the art, in polymerization process, add the nanometer palladium suspension of handling through surface aggregate, obtain the polymer microballoon (also claiming Archon) that skeleton inside is evenly distributed with the nanometer palladium after the polymerization, between nanometer palladium surface and polymerization single polymerization monomer because thereby firm the combining of chemical reaction takes place, Archon is again by sulfonation, through putting into gear, washing obtains described resin catalyst after the drying.The resin catalyst that utilizes said method to make can be applicable to gasoline and faces ether hydrogenation, synthesize methyl-isobutyl ketone technology.
To achieve these goals, the nanometer palladium need be handled through surface aggregate, become lipophile by hydrophily, in macropore styrene type cation exchange resin process for suspension polymerization, add the nanometer palladium of handling through surface aggregate then, make the polymerization Archon by the conventional process for suspension polymerization of macropore styrene type cation exchange resin, through washing, wax is carried in oven dry, carries out sulfonation by the macropore styrene type cation exchange resin process for sulfonation of standard, through putting into gear, washing dries, and obtains product, wherein the macropore styrene type cation exchange resin can be the trade mark general on the market such as D001, D006 etc.
Be not used in that restriction protects, the synthetic of ion exchange resin of the present invention can be realized by following steps:
1). nanometer palladium surface aggregate
The certain amount of nano palladium is distributed in the water, add acrylic ester monomer in following ratio, described acrylic ester monomer is selected from methyl acrylate, ethyl acrylate or butyl acrylate etc., benzoyl peroxide and dispersant, described dispersant is selected from polyvinyl alcohol, gelatin or CMC etc., heats up, 60-90 ℃ of reaction 6-15 hour, promptly obtain nanometer palladium suspension through surface aggregate, centrifugal standby;
Ingredients weight parts
Nanometer palladium 5-15
Acrylic ester monomer 1-10
Benzoyl peroxide 0.1-1
Dispersant 0.1-5
Deionized water 1000
2). suspension polymerisation
2.1. the preparation of water
In the 2000ml there-necked flask, add pure water in following ratio, chemical dispersant, described chemical dispersant is selected from polyvinyl alcohol, gelatin or CMC etc., add a certain amount of inorganic dispersant again, described inorganic dispersant is selected from this area carbonate commonly used, and sulfate stirs;
Ingredients weight parts
Pure water 1000
Chemical dispersant 1-10
Inorganic dispersant 1-10
2.2. the preparation of oil phase
Styrene, divinylbenzene are mixed in beaker by the calculating dosage of the degree of cross linking, add a certain amount of peroxide initiator again, preferably adopt benzoyl peroxide; Good solvents such as a certain amount of toluene, aliphatic alcohols, white oil or paraffin or poor solvent or mixed solvent are done pore-foaming agent, add the nanometer palladium through surface aggregate again, stir;
Wherein:
Ingredients weight parts
Styrene 100
Divinylbenzene 10-40
Peroxide initiator 1-10
Pore-foaming agent 10-40
Nanometer palladium (by butt) 1-5
2.3. reaction
The oil-phase solution for preparing in the beaker is added to is equipped with in the step 2.1 in the there-necked flask of having prepared water, slow earlier fast the stirring in back, react by the conventional process for suspension polymerization of macropore styrene type cation exchange resin known in the art then, reaction finishes the back blowing, 80 ℃ of washing microballoons are limpid to water, get intermediate products 1;
3). carry wax
With intermediate products 1 oven dry, screening is carried wax with gasoline, gets intermediate products 2;
4). sulfonation
Intermediate products 2 are added sulfuric acid and the dichloroethanes of the concentration 90%-102% of following proportioning, heat up gradually, stop reaction when the sample test cross changes capacity to 〉=4.8mmol/g in the middle of getting, obtain intermediate products 3;
Ingredients weight parts
Intermediate products 2 100
Sulfuric acid 300-800
Dichloroethanes 20-100
5). put into gear transition
With intermediate products 3 processing of putting into gear, wherein the first retaining acid is the acid of proportion 1.8, second retaining is the acid of proportion 1.7, successively decrease by retaining, proportion 0.1 falls in each retaining, needs engage a gear 9 times, every retaining was hung 1 hour approximately, after having hung retaining, the water massive laundering, the scope 0.3-2wt% that obtains palladium content carries the palladium resin catalyst.
The beneficial effect of the invention
1). it is effective that year palladium resin catalyst of the present invention's preparation carries palladium, and palladium is difficult for removing, owing to the nanometer palladium is evenly distributed on the skeleton of resin microsphere by molecular separating force in polymerization, palladium is difficult for running off;
2). this resin catalyst intensity is higher, long service life;
3). the organic solvent of consumption is few, and environmental protection pressure is little, and from the practical application angle, this purposes characteristic has important economic value;
4). technology is simple, easy operating, cost is low, and the reactivity height pollutes and lacks, product yield, purity height.
The specific embodiment
Following example only is to further specify the present invention, is not the restriction the scope of protection of the invention.
Embodiment 1:
1. nano-material surface polymerization
With 2.5 gram nanometer palladiums, be distributed in the 500 gram water, add 2 gram butyl acrylates in proportion, 0.2 gram benzoyl peroxide, 0.5 gram PVA heats up, and at 70 ℃ of reaction temperature reaction 8h, promptly obtains the nano inorganic material through surface aggregate, and is centrifugal standby.
2. suspension polymerisation
2.1. the preparation of water
In the 2000ml there-necked flask, add pure water in following ratio, polyvinyl alcohol, magnesium carbonate stirs;
Ingredients weight parts
Pure water 1000
Polyvinyl alcohol 2
Magnesium carbonate 5
2.2. the preparation of oil phase
Styrene, divinylbenzene are mixed in beaker by the calculating dosage of the degree of cross linking, add benzoyl peroxide again, white oil and through the nanometer palladium of surface aggregate stirs;
Wherein:
Ingredients weight parts
Styrene 100
Divinylbenzene 10
Benzoyl peroxide 1
White oil 10
Nanometer palladium (by butt) 1
2.3. reaction
The oil-phase solution for preparing in the beaker is added to is equipped with in the step 2.1 in the there-necked flask of having prepared water, slow earlier fast the stirring in back, then by the conventional process for suspension polymerization reaction of macropore styrene type cation exchange resin known in the art, reaction finishes, blowing, 80 ℃ of washing microballoons are limpid to water, get intermediate products 1.
3. intermediate products 1 oven dry, wax is carried in screening, gets intermediate products 2.
4. sulfonation: intermediate products 2 sulfonating reactions get intermediate products 3
Preparation 500ml concentration is 95% sulfuric acid, dries in the air to room temperature, and with the reactor oven dry, first-class reactor in oil bath pan adds the water seal cover.Weigh up 100g intermediate products 2 (Archon) and add in the reactor, 500ml sulfuric acid is added in the reactor, open stirring, get the 50g dichloroethanes and pour in the reactor with graduated cylinder.Throw material back swelling 2 hours, and be warming up to 80 ℃; Be incubated 6 hours, be warming up to 100 ℃ again, be incubated cooling after 10 hours, obtain intermediate products 3.
5. put into gear transition
With intermediate products 3 processing of putting into gear, wherein the first retaining acid is the acid of proportion 1.8, second retaining is the acid of proportion 1.7, successively decreases by retaining, and proportion 0.1 falls in each retaining, need engage a gear 9 times, every retaining was hung 1 hour approximately, hung the retaining after, the water massive laundering, obtain containing year palladium resin catalyst of palladium percentage by weight 0.3%, production code member A1.
Embodiment 2:
1. nano-material surface polymerization
With 7.5 gram nanometer palladiums, be distributed in the 500 gram water, add 2 gram butyl acrylates in proportion, 0.2 gram benzoyl peroxide, 0.5 gram PVA heats up, and at 70 ℃ of reaction temperature reaction 8h, promptly obtains the nano inorganic material through surface aggregate, and is centrifugal standby
Other technology and embodiment 1 are identical:
Obtain containing year palladium resin catalyst of palladium 0.42%, production code member A2.
Embodiment 3:
1. nano-material surface polymerization
With 5 gram nanometer palladiums, be distributed in the 500 gram water, add 2 gram butyl acrylates in proportion, 0.2 gram benzoyl peroxide, 0.5 gram PVA heats up, and at 70 ℃ of reaction temperature reaction 8h, promptly obtains the nano inorganic material through surface aggregate, and is centrifugal standby
Other technology and embodiment 1 are identical:
Obtain containing year palladium resin catalyst of palladium 0.36%, production code member A3.
Embodiment 4: improve the consumption of nanometer palladium in the preparing process of oil phase, other technology and embodiment 1 are identical:
Styrene, divinylbenzene are mixed in beaker by the calculating dosage of the degree of cross linking, add benzoyl peroxide again, white oil and through the nanometer palladium of surface aggregate stirs;
Wherein:
Ingredients weight parts
Styrene 100
Divinylbenzene 10
Benzoyl peroxide 1
White oil 10
Nanometer palladium (by butt) 5
Obtain containing year palladium resin catalyst of palladium 2%, production code member A4.
Embodiment 4:
The catalyst A 1-A4 that 50ml embodiment 1-4 is made, handle as follows respectively: catalyst is adorned the quartz sand of handling down, and the stainless steel reactor of internal diameter 20mm is put in layering, feeds hydrogen earlier palladium ion is reduced to the palladium atom, behind the 16h, add acetone, air speed 1.4L/h, 120 ℃ of reaction temperatures, pressure 6.0MPa, hydrogen recycles, and records acetone conversion 51%, methyl iso-butyl ketone (MIBK) selectivity 95.3%.
Do not take out catalyst, move above-mentioned hydropyrolysis experiment 20 days continuously, measure catalyst A 1 and contain palladium 0.32%.Record acetone conversion 49%, methyl iso-butyl ketone (MIBK) selectivity 94%.
| Test | Production code member | Reaction temperature ℃ | Reaction pressure MPa | Air speed h -1 | Contain palladium amount %wt | Acetone conversion per pass plug mol/% | MIBK selectivity mol/% |
| Embodiment 1 | A1 | 120 | 6.0 | 1.4 | 0.3 | 31.3 | 96.5 |
| Embodiment 2 | A2 | 120 | 6.0 | 1.4 | 0.42 | 36.2 | 96.1 |
| Embodiment 3 | A3 | 120 | 6.0 | 1.4 | 0.36 | 38.2 | 95.2 |
| Embodiment 4 | A4 | 120 | 6.0 | 1.4 | 2 | 45.3 | 94.6 |
By last explanation, it is effective that year palladium resin catalyst of the present invention's preparation carries palladium, palladium is difficult for removing, illustrate that the present invention has significantly solved year uneven problem of palladium in the prior art, improved the stability of palladium in year palladium resin catalyst, make activity, selectivity and the service life of carrying the palladium resin catalyst all be significantly improved, therefore technical scheme of the present invention possesses outstanding substantive distinguishing features, can use as methyl iso-butyl ketone (MIBK) and other industrial products hydrogenation catalyst.
Claims (5)
1. a nano Pd by suspension polymerization prepares the method for carrying the palladium resin catalyst, comprise: adopt conventional macropore styrene type cation exchange resin process for suspension polymerization, in polymerization process, add the nanometer palladium suspension of handling through surface aggregate, obtain the polymer microballoon that skeleton inside is evenly distributed with the nanometer palladium after the polymerization, nanometer palladium surface and polymerization single polymerization monomer are owing to firm the combining of chemical reaction, polymer microballoon is again by sulfonation, through putting into gear, washing, obtain described year palladium resin catalyst after the drying, wherein, the surface aggregate treatment process of described nanometer palladium suspension is: the certain amount of nano palladium is distributed in the water, adds acrylic ester monomer in following ratio, benzoyl peroxide and dispersant, described acrylic ester monomer is selected from methyl acrylate, ethyl acrylate or butyl acrylate, described dispersant is selected from polyvinyl alcohol, gelatin or CMC heat up, 60-90 ℃ of reaction 6-15 hour, promptly obtain nanometer palladium suspension through surface aggregate, centrifugal standby
Ingredients weight parts
Nanometer palladium 5-15
Acrylic ester monomer 1-10
Benzoyl peroxide 0.1-1
Dispersant 0.1-5
Deionized water 1000.
2. the nano Pd by suspension polymerization of claim 1 prepares the method for carrying the palladium resin catalyst, and wherein: described macropore styrene type cation exchange resin is the resin of trade mark D001 or D006.
3. claim 1 or 2 described nano Pd by suspension polymerization prepare the method for carrying the palladium resin catalysts, may further comprise the steps:
1). nanometer palladium surface aggregate
The certain amount of nano palladium is distributed in the water, add acrylic ester monomer in following ratio, benzoyl peroxide and dispersant, described acrylic ester monomer is selected from methyl acrylate, ethyl acrylate or butyl acrylate, described dispersant is selected from polyvinyl alcohol, gelatin or CMC, heats up, 60-90 ℃ of reaction 6-15 hour, promptly obtain nanometer palladium suspension through surface aggregate, centrifugal standby;
Ingredients weight parts
Nanometer palladium 5-15
Acrylic ester monomer 1-10
Benzoyl peroxide 0.1-1
Dispersant 0.1-5
Deionized water 1000
2). suspension polymerisation
2.1. the preparation of water
In the 2000ml there-necked flask, add pure water in following ratio, chemical dispersant, described chemical dispersant is selected from polyvinyl alcohol, gelatin or CMC, adds a certain amount of inorganic dispersant again, described inorganic dispersant is selected from carbonate or sulfate, stirs;
Ingredients weight parts
Pure water 1000
Chemical dispersant 1-10
Inorganic dispersant 1-10
2.2. the preparation of oil phase
Styrene, divinylbenzene are mixed in beaker by the calculating dosage of the degree of cross linking, add a certain amount of benzoyl peroxide again, with a certain amount of pore-foaming agent, be selected from good solvent or poor solvent or mixed solvent, wherein good solvent is selected from toluene, aliphatic alcohols, white oil or paraffin, add nanometer palladium again, stir through surface aggregate;
Wherein:
Ingredients weight parts
Styrene 100
Divinylbenzene 10-40
Benzoyl peroxide 1-10
Pore-foaming agent 10-40
The nanometer palladium is by butt 1-5
2.3. reaction
The oil-phase solution for preparing in the beaker is added to is equipped with in the step 2.1 in the there-necked flask of having prepared water, slow earlier fast the stirring in back, then by the conventional process for suspension polymerization reaction of macropore styrene type cation exchange resin known in the art, reaction finishes, blowing, 80 ℃ of washing microballoons are limpid to water, get intermediate products 1;
3). carry wax
With intermediate products 1 oven dry, screening is carried wax with gasoline, gets intermediate products 2;
4). sulfonation
The concentration that intermediate products 2 is added following proportioning is sulfuric acid and the dichloroethanes of 90%-102%, heats up gradually, stops reaction when the sample test cross changes capacity to 〉=4.8mmol/g in the middle of getting, and obtains intermediate products 3;
Ingredients weight parts
Intermediate products 2 100
Sulfuric acid 300-800
Dichloroethanes 20-100
5). engage a gear makes the transition
Intermediate products 3 are carried out engage a gear handle, wherein first grade of acid that acid is proportion 1.8, second grade is the acid of proportion 1.7, successively decreases by shelves, and proportion 0.1 falls in each shelves, and engage a gear is 9 times altogether, hung 1 hour for every grade,
After having hung, the water massive laundering obtains carrying the palladium resin catalyst.
4. the arbitrary described method preparation of a claim 1-3 carries the palladium resin catalyst.
5. described year palladium resin catalyst of claim 4 faces application in the ether hydrogenation at synthesize methyl-isobutyl ketone or gasoline.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009100088971A CN101497041B (en) | 2009-02-12 | 2009-02-12 | Method for preparing palladium-carrying catalyst with nano Pd by suspension polymerization |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009100088971A CN101497041B (en) | 2009-02-12 | 2009-02-12 | Method for preparing palladium-carrying catalyst with nano Pd by suspension polymerization |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101497041A CN101497041A (en) | 2009-08-05 |
| CN101497041B true CN101497041B (en) | 2010-11-03 |
Family
ID=40944438
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2009100088971A Expired - Fee Related CN101497041B (en) | 2009-02-12 | 2009-02-12 | Method for preparing palladium-carrying catalyst with nano Pd by suspension polymerization |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101497041B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103571532B (en) * | 2013-11-26 | 2015-05-27 | 凯瑞环保科技股份有限公司 | Pre-etherification reaction method in light petrol etherification technology |
| CN103878030B (en) * | 2014-02-26 | 2015-09-23 | 巨化集团技术中心 | A kind of preparation method of aromatic chlorides Hydrodechlorinating catalyst |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1701847A (en) * | 2005-03-07 | 2005-11-30 | 南开大学 | Method for preparing nano metal palladium/supporter catalyst |
| CN1883793A (en) * | 2005-06-20 | 2006-12-27 | 淮北煤炭师范学院 | Nano Pd catalyst and its preparation and application |
| US20080269533A1 (en) * | 2007-04-26 | 2008-10-30 | Chinese Petroleum Corporation | Method of selectively hydrogenating conjugated diene by using supported ionic liquid nano-pd catalyst |
-
2009
- 2009-02-12 CN CN2009100088971A patent/CN101497041B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1701847A (en) * | 2005-03-07 | 2005-11-30 | 南开大学 | Method for preparing nano metal palladium/supporter catalyst |
| CN1883793A (en) * | 2005-06-20 | 2006-12-27 | 淮北煤炭师范学院 | Nano Pd catalyst and its preparation and application |
| US20080269533A1 (en) * | 2007-04-26 | 2008-10-30 | Chinese Petroleum Corporation | Method of selectively hydrogenating conjugated diene by using supported ionic liquid nano-pd catalyst |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101497041A (en) | 2009-08-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Kong et al. | Dye removal by eco-friendly physically cross-linked double network polymer hydrogel beads and their functionalized composites | |
| CN110743544B (en) | Palladium-carbon catalyst for preparing alpha-phenylethyl alcohol by selective hydrogenation of acetophenone and preparation method and application thereof | |
| CN101773812A (en) | High-specific surface polymer microsphere resin with even particle size and preparation method thereof | |
| CN102909077B (en) | Metal-modified cation exchange resin catalyst, preparation method and application thereof | |
| CN101690885A (en) | 4-vinylpyridine absorbent resin and preparation method thereof | |
| CN102380380A (en) | Mercury-free catalyst system for acetylene hydrochlorination and use thereof | |
| CN105618137A (en) | Porous acidic resin catalyst, preparation method and applications thereof | |
| CN104927063A (en) | Method for adsorbing and recycling phenolic compounds in industrial wastewater and method for manufacturing adsorption materials | |
| CN101721977B (en) | Palladium loaded chelate resin and preparation method thereof | |
| CN101497041B (en) | Method for preparing palladium-carrying catalyst with nano Pd by suspension polymerization | |
| CN109621920A (en) | A kind of pipe/polyhenylethylene nano zero-valent iron composite material and its preparation method and application | |
| CN106589202A (en) | Lysozyme immobilized carrier and preparation method thereof | |
| CN107262054A (en) | A kind of preparation method and applications of magnetic lignin base adsorbent | |
| CN113578383A (en) | Preparation of sulfonic acid modified polystyrene microsphere and method for catalyzing furfuryl alcohol to be converted into ethyl levulinate by using sulfonic acid modified polystyrene microsphere | |
| CN109046382A (en) | A kind of novel biomass carbon-based solid super acids preparation method | |
| CN110773232B (en) | Catalyst for preparing glycol by hydrating alkylene oxide, preparation method and application | |
| CN101439302B (en) | Catalyst for producing vinyl acetate by acetylene method as well as preparation method and use of catalyst | |
| CN107008485A (en) | A kind of nitrogen-doped graphene loads Ru and WO3Catalyst and preparation method and application | |
| CN106824283A (en) | Attapulgite reinforced resin solid acid catalyst and preparation method thereof | |
| CN102909041B (en) | Method for synthesizing methyl sec-butyl ether | |
| CN109012643A (en) | A kind of method of photocatalysis in-situ regeneration active carbon under visible light | |
| CN105295059A (en) | Immobilized cationized beta-cyclodextrin chloromethylated polystyrene polymer and method for adsorbing and recovering phenols in industrial wastewater | |
| CN109134734A (en) | A kind of preparation method of macroporous type strongly acidic styrene system ion exchange resin | |
| CN104531665A (en) | Functionalized active attapulgite enzyme immobilization catalyst preparation method | |
| CN107497490A (en) | A kind of CdS-loaded catalyst preparation of metal organogel and its application in terms of photolysis water hydrogen |
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 | ||
| CP01 | Change in the name or title of a patent holder |
Address after: 062451 industry zone of West Village, Hejian City, Hebei Province Patentee after: Kairui Chemical Co., Ltd. Address before: 062451 industry zone of West Village, Hejian City, Hebei Province Patentee before: Kairui Chemical Co., Ltd. |
|
| C56 | Change in the name or address of the patentee |
Owner name: KAIRUI CHEMICAL PROTECTION TECHNOLOGY CO., LTD. Free format text: FORMER NAME: KAIRUI CHEMICAL CO., LTD. |
|
| CP03 | Change of name, title or address |
Address after: 062451 Hebei Province Hejian City Gu Xian Xiang Xi Liu Zhuang Patentee after: Kai Rui environmental protection Science and Technology Co., Ltd. Address before: 062451 industry zone of West Village, Hejian City, Hebei Province Patentee before: Kairui Chemical Co., Ltd. |
|
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20101103 Termination date: 20200212 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |