CN1715261A - Process for producing high purity 1,2,4-trichlorobenzene and para-dichlorobenzene - Google Patents
Process for producing high purity 1,2,4-trichlorobenzene and para-dichlorobenzene Download PDFInfo
- Publication number
- CN1715261A CN1715261A CN 200410019755 CN200410019755A CN1715261A CN 1715261 A CN1715261 A CN 1715261A CN 200410019755 CN200410019755 CN 200410019755 CN 200410019755 A CN200410019755 A CN 200410019755A CN 1715261 A CN1715261 A CN 1715261A
- Authority
- CN
- China
- Prior art keywords
- dichlorobenzene
- trichlorobenzene
- para
- high purity
- chlorine
- 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.)
- Pending
Links
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 title claims abstract description 45
- PBKONEOXTCPAFI-UHFFFAOYSA-N 1,2,4-trichlorobenzene Chemical compound ClC1=CC=C(Cl)C(Cl)=C1 PBKONEOXTCPAFI-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 238000000034 method Methods 0.000 title claims abstract description 21
- 238000005660 chlorination reaction Methods 0.000 claims abstract description 26
- 229940117389 dichlorobenzene Drugs 0.000 claims abstract description 21
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000006243 chemical reaction Methods 0.000 claims abstract description 15
- 238000005194 fractionation Methods 0.000 claims abstract description 14
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000000460 chlorine Substances 0.000 claims abstract description 13
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 13
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000007788 liquid Substances 0.000 claims abstract description 12
- RELMFMZEBKVZJC-UHFFFAOYSA-N 1,2,3-trichlorobenzene Chemical compound ClC1=CC=CC(Cl)=C1Cl RELMFMZEBKVZJC-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000003054 catalyst Substances 0.000 claims abstract description 9
- 239000000047 product Substances 0.000 claims abstract description 9
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 claims abstract description 3
- 238000010438 heat treatment Methods 0.000 claims abstract 2
- 238000004519 manufacturing process Methods 0.000 claims description 13
- 239000007789 gas Substances 0.000 claims description 11
- 241000282326 Felis catus Species 0.000 claims description 8
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims description 7
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 6
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 6
- GBDZXPJXOMHESU-UHFFFAOYSA-N 1,2,3,4-tetrachlorobenzene Chemical compound ClC1=CC=C(Cl)C(Cl)=C1Cl GBDZXPJXOMHESU-UHFFFAOYSA-N 0.000 claims description 5
- 238000002425 crystallisation Methods 0.000 claims description 4
- CKAPSXZOOQJIBF-UHFFFAOYSA-N hexachlorobenzene Chemical compound ClC1=C(Cl)C(Cl)=C(Cl)C(Cl)=C1Cl CKAPSXZOOQJIBF-UHFFFAOYSA-N 0.000 claims description 4
- 229940007424 antimony trisulfide Drugs 0.000 claims description 3
- NVWBARWTDVQPJD-UHFFFAOYSA-N antimony(3+);trisulfide Chemical compound [S-2].[S-2].[S-2].[Sb+3].[Sb+3] NVWBARWTDVQPJD-UHFFFAOYSA-N 0.000 claims description 3
- 238000009835 boiling Methods 0.000 claims description 3
- 239000006227 byproduct Substances 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- 230000005587 bubbling Effects 0.000 claims description 2
- 239000011552 falling film Substances 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims 1
- 239000011265 semifinished product Substances 0.000 abstract 2
- 238000005516 engineering process Methods 0.000 description 4
- JLYXXMFPNIAWKQ-GNIYUCBRSA-N gamma-hexachlorocyclohexane Chemical compound Cl[C@H]1[C@H](Cl)[C@@H](Cl)[C@@H](Cl)[C@H](Cl)[C@H]1Cl JLYXXMFPNIAWKQ-GNIYUCBRSA-N 0.000 description 3
- JLYXXMFPNIAWKQ-UHFFFAOYSA-N gamma-hexachlorocyclohexane Natural products ClC1C(Cl)C(Cl)C(Cl)C(Cl)C1Cl JLYXXMFPNIAWKQ-UHFFFAOYSA-N 0.000 description 3
- 229960002809 lindane Drugs 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 2
- 230000003327 cancerostatic effect Effects 0.000 description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 238000005904 alkaline hydrolysis reaction Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- CEOCDNVZRAIOQZ-UHFFFAOYSA-N pentachlorobenzene Chemical compound ClC1=CC(Cl)=C(Cl)C(Cl)=C1Cl CEOCDNVZRAIOQZ-UHFFFAOYSA-N 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 230000005180 public health Effects 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
Images
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention relates to oriented chlorination and fractionating process of chlorobenzene to produce high purity 1, 2, 4-trichlorobenzene and para-dichlorobenzene. Chlorobenzene and catalyst are thrown into auxiliary chlorination reactor and reacted with chlorine gas at certain temperature to produce hydrochloric acid gas, after reaction for certain time, the chlorinated liquid is fed to coarse fractionating tower for heating fractionation to fractionate mixed dichlorobenzene, and mixed dichlorobenzene is heated in the dichlorobenzene rectifying tower to fractionate para-dichlorobenzene of 99.5-99.8 % purity. Mixed dichlorobenzene and catalyst are reacted with chlorine inside main chlorinating reactor at certain temperature for certain time, the product is heated and fractionated in coarse fractionating tower to obtain semi-finished product, and the semi-finished product is heated and fractionated in the trichlorobenzene fractionating tower to obtain 1, 2, 4-trichlorobenzene product of 99.5 % purity.
Description
Technical field:
The making method of high purity 1,2 of the present invention, 4-trichlorobenzene and para-dichlorobenzene, relate to mono chloro benzene catalyst oriented chlorination and fractionation and make high purity 1,2,4-trichlorobenzene and para-dichlorobenzene, product application is in producing aspects such as agricultural chemicals, medicine, dyestuff and public health.
Background technology:
The existing trichlorobenzene traditional technology of producing both at home and abroad, the invalid body of employing phenyl-hexachloride carries out alkaline hydrolysis or pyrolysis generates multiple trichlorobenzene and mixtures such as a small amount of dichlorobenzene, tetrachlorobenzene, pentachlorobenzene and Perchlorobenzene, after fractionation, make contain 1,2, low-purity trichlorobenzene that the 4-trichlorobenzene reaches 70%-80%, the fractionation of can re-refining makes high purity 1,2,4 trichlorobenzene, so the very big output in domestic of degree of difficulty seldom, can not satisfy domestic needs far away, the trichlorobenzene that adopts above method to produce in addition wherein contain after testing lindane, polychlorobiphenyl, etc. carcinostatic substance.The clear and definite whole world of WHO stops to produce lindane and uses lindane, thereby has just stopped the raw material of the invalid body production of phenyl-hexachloride trichlorobenzene, has also just stopped this explained hereafter.The production technique of domestic production para-dichlorobenzene has two kinds at present: a kind of is the byproduct of producing mono chloro benzene; Another kind is that purified petroleum benzin oriented chlorination aftercut cold crystallization legal system gets the high purity para-dichlorobenzene, and its technological process of production is long, and produces a large amount of process spent waters, the incompatibility suitability for industrialized production.
Summary of the invention:
The purpose of this invention is to provide a kind of high purity 1,2, the making method of 4-trichlorobenzene and para-dichlorobenzene, adopt mono chloro benzene catalyst oriented chlorination to produce through the vacuum fractionation method, high purity 1,2,4-trichlorobenzene and purify through fractionating process and to produce the production technique of high purity para-dichlorobenzene, it is characterized in that: described catalyst be adopt antimony trisulfide and iron trichloride respectively add-on be the 0.05%-0.1% of mono chloro benzene amount, common secondary chlorination tank and the chlorine reaction that comes out by main chlorination tank of dropping into, temperature of reaction generates hydrogen chloride gas for the 50-80 degree and residue chlorine enters secondary chlorination tank, react 5-7 hour chlorated liquid and reach best composition, chlorated liquid is sent into topping still and heated fractionation under reduced pressure with well heater with high temperature heat conductive oil 180-220 degree, and cat head fractionates out mixed dichlorobenzene.As produce para-dichlorobenzene mixed dichlorobenzene is sent into the dichlorobenzene rectifying tower, heater via heats fractionation under reduced pressure with high temperature heat conductive oil 180-220 degree, and cat head fractionates out the high purity para-dichlorobenzene.Produce 1,2, the 4-trichlorobenzene, the mixed dichlorobenzene that topping still is fractionated out drops in the main chlorination tank after metering, and adding accounts for the 0.05-0.1% iron trichloride of mixed dichlorobenzene amount, feed chlorine reaction 4-6 hour of optimum flow for the 50-80 degree in temperature, the generation chlorated liquid is sent into topping still and is operated as stated above, topping still fractionates out 68-73%1,2, the 4-trichlorobenzene, send into trichlorobenzene rectifying tower heater via and heat fractionation under reduced pressure with high temperature heat conductive oil 200-220 degree, cat head fractionates out 1,2,4-trichlorobenzene finished product, tower bottoms reaches definite composition and emits high boiling material, the rectifying tower still is returned in the liquid extracting behind the crystallisation by cooling, recyclable tetrachlorobenzene of its crystallisate or production Perchlorobenzene.
Description of drawings:
Fig. 1 is the Production Flow Chart synoptic diagram of the making method of high purity 1,2,4-trichlorobenzene and para-dichlorobenzene.Following examples are 1 described in conjunction with the accompanying drawings.
Embodiment:
Mono chloro benzene 1.8-2.3 ton is dropped in the secondary chlorination tank, add antimony trisulfide and iron trichloride respectively and respectively account for the 0.04-0.12% of mono chloro benzene amount, the chlorine reaction that comes out with main chlorination tank, generate hydrogen chloride gas during the reaction of temperature 50-80 degree and isolate the mono chloro benzene recovery of carrying secretly through cooling separator, hydrogen chloride gas absorbs, absorbs, absorbs, absorbs through circulation and make 28-30% concentration by-product hydrochloric acid, rare gas element emptying through water-jet exhauster again through the falling-film tower circulation again through bubbling water.Secondary again chlorination tank internal reaction such as above-mentioned mono chloro benzene was put into main chlorination tank in 4-6 hour.Liquid chlorine is through being vaporized into gas chlorine, is that the 20-24 cubic meter drops into the reactant that main chlorination tank and secondary chlorination tank enter main chlorination tank and reacts with flow per hour, generates hydrogen chloride gas and residue chlorine enters secondary chlorination tank when temperature of reaction 50-80 spends.5-7 hour chlorated liquid of main chlorination tank reaction reaches best and forms: to being dichlorobenzene 65-70%, and 1,2,4 trichlorobenzene 28-32%, tetrachlorobenzene 2.5% is sent in the topping still after emission gases.Topping still chlorated liquid constituent heater via heats fractionation under reduced pressure with high temperature heat conductive oil 180-200 degree, and cat head fractionates out mixed dichlorobenzene, santochlor 97-98% wherein, orthodichlorobenzene 1%, mono chloro benzene 1%, trichlorobenzene 1%.If coproduction para-dichlorobenzene, mixed dichlorobenzene is sent into dichlorobenzene rectifying tower heater via heat fractionation under reduced pressure with high temperature heat conductive oil 180-200 degree, cat head fractionates out the high purity para-dichlorobenzene, and its molten mass is 99.5-99.8 para-dichlorobenzene finished product through shaper at 0-5 degree water cooling compacted under.Produce 1,2, the 4-trichlorobenzene drops into main chlorination tank with mixed dichlorobenzene through metering, and input accounts for the iron trichloride catalyst of mixed dichlorobenzene amount 0.05-0.1%, feed the chlorine reaction of optimum flow at temperature 50-80 degree, reaction in 4-6 hour finishes, make chlorated liquid reach best the composition, send into topping still, operating the tower bottoms that fractionates out best composition as stated above is: 1,2, the 4-trichlorobenzene 68-75% send the trichlorobenzene rectifying tower, heater via heats fractionation under reduced pressure with high temperature heat conductive oil 200-220 degree, and cat head fractionates out high purity 1,2,4-trichlorobenzene 99.5% finished product.Tower bottoms reaches definite composition and emits high boiling material, and rectifying tower is returned in the liquid extracting behind the crystallisation by cooling, recyclable tetrachlorobenzene of its crystallisate or production Perchlorobenzene.
The making method of high purity 1,2,4 trichlorobenzene of the present invention and para-dichlorobenzene, quality product satisfies the users at home and abroad requirement, and do not contain polychlorobiphenyl through organic element institute of Nankai University testing product, Deng carcinostatic substance, compare with traditional technology, have following advantage, eliminated the invalid body of phenyl-hexachloride decompose produce to operator's poisonous pollution and a large amount of pollutent and sewage.Production Flow Chart of the present invention is short, equipment is simple, eliminate the technology pollution substance, is fit to suitability for industrialized production, guarantees operator's health.
Claims (5)
1, a kind of with mono chloro benzene catalyst oriented chlorination and fractionation production high purity 1,2, the making method of 4-trichlorobenzene and para-dichlorobenzene, it is characterized in that: described catalyst be antimony trisulfide and iron trichloride respectively add-on be the 0.05-0.1% of mono chloro benzene amount, the chlorine reaction that common secondary chlorination tank of input and main chlorination tank come out, temperature of reaction is that 50-80 puts into main chlorination tank after 4-6 hour when spending, liquid chlorine feeds main chlorination tank reaction after metering through being vaporized into gas chlorine, temperature 50-80 degree generates hydrogen chloride gas and residue chlorine enters secondary chlorination tank, react and chlorated liquid sent into topping still and heat fractionation under reduced pressure with high temperature heat conductive oil 180-220 degree with well heater in 5-7 hour, cat head fractionates out mixed dichlorobenzene.
2, according to the making method of the described high purity 1,2 of claim 1,4-trichlorobenzene and para-dichlorobenzene, it is characterized in that: mixed dichlorobenzene is sent into dichlorobenzene rectifying tower heater via heat fractionation under reduced pressure with high temperature heat conductive oil 180-220 degree, cat head fractionates out the high purity para-dichlorobenzene.
3, according to the described high purity 1 of claim 1,2, the making method of 4-trichlorobenzene and para-dichlorobenzene, it is characterized in that: the mixed dichlorobenzene that topping still is gone out drops in the main chlorination tank after metering, and adding accounts for the 0.05-0.1% iron trichloride of mixed dichlorobenzene amount, reacted jointly 4-6 hour for the 50-80 degree feeds a certain amount of chlorine in temperature, rise into chlorated liquid and send into topping still and by the operation of the described method of claim 1, topping still fractionates out work in-process 1,2, the 4-trichlorobenzene is sent into trichlorobenzene separation column heater via and is under reduced pressure fractionated out 1 with the heating of high temperature heat conductive oil 200-220 degree, 2,4-trichlorobenzene product.
4, according to the making method of claim 1,3 described high purities 1,2,4-trichlorobenzene and para-dichlorobenzene, it is characterized in that: tower bottoms reaches definite composition and emits high boiling material, rectifying tower is returned in the liquid extracting behind the crystallisation by cooling, recyclable tetrachlorobenzene of its crystallisate or production Perchlorobenzene.
5, according to the making method of the described high purity 1,2 of claim 1,4-trichlorobenzene and para-dichlorobenzene, it is characterized in that: generate hydrogen chloride gas when mono chloro benzene catalyst chlorine reaction temperature 50-80 spends, reclaim through cooling and isolating the mono chloro benzene of carrying secretly, hydrogen chloride gas absorbs through bubbling water again and absorbs through the falling-film tower circulation, absorbs through water-jet exhauster to can be made into 28-30% concentration by-product hydrochloric acid again.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200410019755 CN1715261A (en) | 2004-06-28 | 2004-06-28 | Process for producing high purity 1,2,4-trichlorobenzene and para-dichlorobenzene |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200410019755 CN1715261A (en) | 2004-06-28 | 2004-06-28 | Process for producing high purity 1,2,4-trichlorobenzene and para-dichlorobenzene |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1715261A true CN1715261A (en) | 2006-01-04 |
Family
ID=35821463
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 200410019755 Pending CN1715261A (en) | 2004-06-28 | 2004-06-28 | Process for producing high purity 1,2,4-trichlorobenzene and para-dichlorobenzene |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1715261A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102126958A (en) * | 2010-12-30 | 2011-07-20 | 江苏淮河化工有限公司 | Device and method for preparing high purity m/p-nitrotoluene by coupling rectification and crystallization |
| CN102197010A (en) * | 2008-10-24 | 2011-09-21 | 东曹株式会社 | Process for producing p-dichlorobenzene |
| CN105801334A (en) * | 2016-05-03 | 2016-07-27 | 四川福思达生物技术开发有限责任公司 | Synthetic method of 2,5-dichlorophenol |
-
2004
- 2004-06-28 CN CN 200410019755 patent/CN1715261A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102197010A (en) * | 2008-10-24 | 2011-09-21 | 东曹株式会社 | Process for producing p-dichlorobenzene |
| CN102197010B (en) * | 2008-10-24 | 2013-12-04 | 东曹株式会社 | Process for producing p-dichlorobenzene |
| CN102126958A (en) * | 2010-12-30 | 2011-07-20 | 江苏淮河化工有限公司 | Device and method for preparing high purity m/p-nitrotoluene by coupling rectification and crystallization |
| CN102126958B (en) * | 2010-12-30 | 2013-12-04 | 江苏淮河化工有限公司 | Device and method for preparing high purity m/p-nitrotoluene by coupling rectification and crystallization |
| CN105801334A (en) * | 2016-05-03 | 2016-07-27 | 四川福思达生物技术开发有限责任公司 | Synthetic method of 2,5-dichlorophenol |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US6887448B2 (en) | Method for production of high purity silicon | |
| CN106748632B (en) | A kind of clean preparation method synthesizing chloromethanes | |
| CN102874817B (en) | Method for preparing silane by disproportionating dichlorosilane | |
| CN104817110A (en) | Method for producing high-purity zirconium oxychloride and co-producing silicon tetrachloride through zircon sand boiling chlorination method | |
| EP1411027A1 (en) | Method of chlorine purification and process for producing 1,2−dichloroethane | |
| CN110589838B (en) | Method for treating chlorosilane residual liquid | |
| CA2707503C (en) | Gecl4 and/or sicl4 recovery process from optical fibers or glassy residues and process for producing sicl4 from sio2 rich materials | |
| CN1412114A (en) | New process for preparing anhydrous magnesium chloride | |
| CN106946286A (en) | A kind of crude titanic chloride is except the chemical reaction equipment and method of vanadium | |
| CN100532339C (en) | A method for producing benzylidene dichloride or chlorobenzylidene dichloride | |
| CN108569700A (en) | A kind of technique of recycling chlorosilane dreg slurry | |
| CN103570760B (en) | Hydroxy ethylene diphosphonic acid production unit and method thereof | |
| CN1715261A (en) | Process for producing high purity 1,2,4-trichlorobenzene and para-dichlorobenzene | |
| CN104909489B (en) | A kind of process for producing of trichloro-isocyanuric acid sewage water treatment method | |
| CN101462943B (en) | Method for preparing oxalate with co-production products oxalic acid and dihydric phosphate by continuous dehydrogenation of formate | |
| CN101759187A (en) | Preparation method and device for solar-grade polycrystalline silicon | |
| CN117105759B (en) | Method for continuously preparing 2-chloro-1- (1-chlorocyclopropyl) ethanone | |
| CN102556989A (en) | Production of phosphoric acid and multi-trace element potassium dihydrogen phosphate through using waste phosphorus mud | |
| RU2280010C1 (en) | Method of production 0f trichlorosilane | |
| CN104556054A (en) | Method and device for recycling light components in trichlorosilane synthetic compost | |
| CN106829989B (en) | Production method and device of high-purity boron tribromide | |
| CN110627069A (en) | System for handle chlorosilane raffinate | |
| CN110981687A (en) | Method for producing dichloroalkane compound and production device thereof | |
| CN117843441A (en) | High-boiling-point substance treatment method and device in trichloroethylene production | |
| CN112573991B (en) | Method for preparing vinyl chloride by using tail gas FTrPSA (fluorine-doped plasma-enhanced pressure swing adsorption) in growth process of vinyl-containing chlorine-based CVD (chemical vapor deposition) crystal film |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| AD01 | Patent right deemed abandoned | ||
| C20 | Patent right or utility model deemed to be abandoned or is abandoned |