CN102249201B - Method and device for producing electronic grade phosphorus oxychloride - Google Patents
Method and device for producing electronic grade phosphorus oxychloride Download PDFInfo
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- CN102249201B CN102249201B CN 201110158443 CN201110158443A CN102249201B CN 102249201 B CN102249201 B CN 102249201B CN 201110158443 CN201110158443 CN 201110158443 CN 201110158443 A CN201110158443 A CN 201110158443A CN 102249201 B CN102249201 B CN 102249201B
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- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 title claims abstract description 136
- 238000000034 method Methods 0.000 title claims abstract description 60
- 238000009835 boiling Methods 0.000 claims abstract description 54
- 238000004821 distillation Methods 0.000 claims abstract description 46
- 239000007788 liquid Substances 0.000 claims abstract description 13
- 239000012535 impurity Substances 0.000 claims abstract description 11
- 238000010992 reflux Methods 0.000 claims abstract description 10
- 239000000654 additive Substances 0.000 claims abstract description 8
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 claims abstract description 8
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims abstract description 4
- 238000003756 stirring Methods 0.000 claims abstract description 4
- 238000003860 storage Methods 0.000 claims description 40
- 238000000746 purification Methods 0.000 claims description 26
- 239000007800 oxidant agent Substances 0.000 claims description 16
- 230000008676 import Effects 0.000 claims description 15
- 239000000463 material Substances 0.000 claims description 14
- 238000007254 oxidation reaction Methods 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 9
- 230000003647 oxidation Effects 0.000 claims description 9
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 claims description 9
- 239000002994 raw material Substances 0.000 claims description 8
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 6
- 229910001447 ferric ion Inorganic materials 0.000 claims description 6
- 229910001448 ferrous ion Inorganic materials 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- 239000001301 oxygen Substances 0.000 claims description 6
- 239000012286 potassium permanganate Substances 0.000 claims description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 3
- XEFQLINVKFYRCS-UHFFFAOYSA-N Triclosan Chemical compound OC1=CC(Cl)=CC=C1OC1=CC=C(Cl)C=C1Cl XEFQLINVKFYRCS-UHFFFAOYSA-N 0.000 claims description 3
- -1 ferric ion compound Chemical class 0.000 claims description 3
- GYCHYNMREWYSKH-UHFFFAOYSA-L iron(ii) bromide Chemical compound [Fe+2].[Br-].[Br-] GYCHYNMREWYSKH-UHFFFAOYSA-L 0.000 claims description 3
- 229910052698 phosphorus Inorganic materials 0.000 claims description 3
- 239000011574 phosphorus Substances 0.000 claims description 3
- 229960003500 triclosan Drugs 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- 238000006424 Flood reaction Methods 0.000 claims description 2
- 230000000996 additive effect Effects 0.000 abstract description 4
- 238000000926 separation method Methods 0.000 abstract description 3
- 230000001590 oxidative effect Effects 0.000 abstract description 2
- 230000007547 defect Effects 0.000 abstract 1
- 238000001914 filtration Methods 0.000 abstract 1
- 239000000203 mixture Substances 0.000 abstract 1
- 238000004519 manufacturing process Methods 0.000 description 7
- 239000000126 substance Substances 0.000 description 5
- 229910021576 Iron(III) bromide Inorganic materials 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- FEONEKOZSGPOFN-UHFFFAOYSA-K tribromoiron Chemical compound Br[Fe](Br)Br FEONEKOZSGPOFN-UHFFFAOYSA-K 0.000 description 4
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 230000007812 deficiency Effects 0.000 description 3
- 229910052785 arsenic Inorganic materials 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- JYGXADMDTFJGBT-VWUMJDOOSA-N hydrocortisone Chemical compound O=C1CC[C@]2(C)[C@H]3[C@@H](O)C[C@](C)([C@@](CC4)(O)C(=O)CO)[C@@H]4[C@@H]3CCC2=C1 JYGXADMDTFJGBT-VWUMJDOOSA-N 0.000 description 2
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 2
- TVEXGJYMHHTVKP-UHFFFAOYSA-N 6-oxabicyclo[3.2.1]oct-3-en-7-one Chemical compound C1C2C(=O)OC1C=CC2 TVEXGJYMHHTVKP-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 229910000975 Carbon steel Inorganic materials 0.000 description 1
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- 239000010962 carbon steel Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005194 fractionation Methods 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 229960000890 hydrocortisone Drugs 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 150000002500 ions Chemical group 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 239000011133 lead Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910001425 magnesium ion Inorganic materials 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 238000000918 plasma mass spectrometry Methods 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000011175 product filtration Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- 230000003319 supportive effect Effects 0.000 description 1
- OBSZRRSYVTXPNB-UHFFFAOYSA-N tetraphosphorus Chemical compound P12P3P1P32 OBSZRRSYVTXPNB-UHFFFAOYSA-N 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 230000003245 working effect Effects 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
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Abstract
The invention discloses a method and device for producing electronic grade phosphorus oxychloride. The method comprises the following steps of: (1) putting technical grade phosphorus oxychloride into a container, adding a sodium bromide or hexadecyl trimethyl ammonium bromide additive into the container, uniformly stirring and conveying the mixture into a high-position storing tank through a conveying pump; (2) introducing the phosphorus oxychloride in the high-position storing tank into a sub-boiling distiller for performing sub-boiling distillation; (3) introducing a distilled product obtained in the step (2) into a half-finished product storing tank; (4) introducing the half-finished product in the storing tank into a rectifying tower; (5) boiling the half-finished product in the rectifying tower in the step (4) and performing total reflux, wherein high-boiling-point impurities are left in the rectifying tower; (6) introducing a phosphorus oxychloride cut fraction into a finished product storing tank, oxidizing, reflowing into the rectifying tower, and performing complete gas-liquid mass transfer separation; and (7) introducing the phosphorus oxychloride product in the finished product storing tank into a filter in a clean room for filtering to obtain the colorless and transparent electronic grade phosphorus oxychloride. According to the method and the device, the defects of the prior art can be overcome.
Description
Technical field
The present invention relates to high-purity chemical materials that microelectronic industry and photovoltaic industry use, is that a kind of purity is method of purification and the device thereof of a kind of electronic grade phosphorus oxychloride of 99.99999%.
Background technology
Electronic grade phosphorus oxychloride is a kind of extra pure regent and ultra-pure material.It is the supportive material of large-scale integrated circuit and photovoltaic solar cell.In recent years along with the manufacturing very fast development of solar cell, the consumption of electronic grade phosphorus oxychloride is increased year by year.Because the production method of present widely used electronic grade phosphorus oxychloride is chlorinolysis, this method is easier to grasp with respect to other method ratio, so domestic each enterprise substantially all uses the same method.But, the deficiency of this chlorinolysis is comparatively obvious: operational path is longer, and belong to batch production, environmental pollution is heavier, particularly there is more serious pollution in the cleaning section of yellow phosphorus, also exists simultaneously and produce dangerous higher deficiency, production efficiency is relatively low, cause its price higher, the present Economic Development Status requirement of difficult adaptation.
Summary of the invention
The method of purification and the device thereof that the purpose of this invention is to provide a kind of electronic grade phosphorus oxychloride make it solve the deficiencies in the prior art.
The present invention is achieved through the following technical solutions for achieving the above object: a kind of method of purification of electronic grade phosphorus oxychloride may further comprise the steps:
1. getting the technical grade phosphoryl chloride inserts in the container, then in container according to ten thousand of phosphoryl chloride total amount/to 3/10000ths adding potassium permanganate oxidants, adding Sodium Bromide or cetyl trimethylammonium bromide additives according to the thousandth to thousand of phosphoryl chloride total amount/three, be delivered in the high-order storage tank by transferpump after stirring;
2. the phosphoryl chloride in the high-order storage tank is imported in the sub-boiling distillation device and carry out the I and II sub-boiling distillation, the one-level sub-boiling distillation is got 80-104.2 ℃ of phosphoryl chloride cut, and the secondary sub-boiling distillation is got 82.5-104.1 ℃ of phosphoryl chloride cut;
3. with step 2. in the gained distillation product importing work in-process storage tank;
4. the work in-process in the work in-process storage tank are imported in the rectifying tower reactor, heating tube is installed in the rectifying tower reactor, and after the liquid level in the rectifying tower reactor flooded heating tube, opening power heated, voltage control is at 100-200V, and the flow that work in-process flow in the rectifying tower reactor is 5-10kg/h;
5. 4. step carried out total reflux 30-60 minute after the interior work in-process boiling of middle rectifying tower reactor, ferrous ion is fully changed into lower boiling ferric ion compound become the easily iron bromide of distillation, be removed simultaneously, then with control of reflux ratio at 2-6, high-boiling-point impurity is stayed in the rectifying tower reactor;
6. the phosphoryl chloride cut of getting 101-105 ℃ imports in the finished product storage tank, the low-boiling point material phosphorus trichloride imports in the oxidizer and passes into purity oxygen, the flow of the purity oxygen that passes into is 200-350L/h, carries out being back to after the oxidation carrying out abundant vapour-liquid mass in the rectifying tower reactor again and separating;
7. the strainer that the triclosan oxidation phosphorus product in the finished product storage tank is imported in the clean room filters, and is 99.99999% electronic grade phosphorus oxychloride thereby obtain water white transparency and purity.The phosphoryl chloride of step described in 2. imports in the one-level sub-boiling distillation device and the liquid level in the secondary sub-boiling distillation device all is lower than more than the heating tube 30mm.
The device that uses in the method for purification of a kind of electronic grade phosphorus oxychloride of the present invention, splendid attire industry phosphoryl chloride container is connected with transferpump, transferpump is connected with the high-order storage tank of raw material, the outlet of the high-order storage tank of raw material is connected with one-level sub-boiling distillation device entrance by pipeline, on the one-level sub-boiling distillation device the first fractional column is set, the first fractional column is connected by the import of prolong with secondary sub-boiling distillation device, on the secondary sub-boiling distillation device after-fractionating post is set, the after-fractionating post is connected with work in-process storage tank entrance by prolong, simultaneously, the outlet of work in-process storage tank is connected with the import of rectifying tower reactor by pipeline, on the rectifying tower reactor king-post is set, return line is set on the king-post, above the return line of king-post one side, pipe connecting is set, king-post top to the height H of pipe connecting is the 800-1500 millimeter, the king-post top is connected with the second prolong by pipeline, the second prolong is connected with the oxidizer entrance, the oxidizer outlet is connected with the rectifying tower reactor, pipe connecting is connected with tower head, and tower head is connected with the first prolong, and the first prolong is connected with divider, divider is connected with finished product storage tank, simultaneously, return line is connected with divider by pipeline, and finished product storage tank connects by pipe-and-filter.King-post top to the height H of pipe connecting is the 850-1500 millimeter; The height of the first fractional column and after-fractionating post is 300mm-1000mm.Angle [alpha] between pipe connecting and the king-post is 15o-60o.Angle [alpha] between pipe connecting and the king-post is 45o.3 opening for feeds are set on the rectifying tower reactor.
Method of purification of the present invention and device are totally-enclosed production, product does not contact with atmosphere, further guaranteed quality product, thoroughly having solved technique that electronic grade phosphorus oxychloride purifies can not the quantity-produced difficulty, realize the continuous production that electronic grade phosphorus oxychloride is purified, production efficiency is significantly improved, reduced many middle-chains, flow process is short, has reduced to greatest extent the generation of waste; Environmental pollution is down to extremely low; Whole technique and plant investment are few, low production cost, and have the raw material advantage such as effective that is easy to get, refluxes; Product colourity of the present invention is less than 5APHA, and the metallic impurity total content is less than 100ppb, and the individual event metallic impurity are no more than 10ppb.
Description of drawings
Accompanying drawing 1 is method of purification technique of the present invention and each operation device syndeton synoptic diagram.
Embodiment
The present invention will be further described for the contrast drawings and Examples.
Method of purification of the present invention only needs a rectifying can reach fabulous separating-purifying effect, is different from the multiple rectification and purification method of prior art fully.Raw material of the present invention is the industrial phosphoryl chloride of content 〉=98.5%.
Concrete preparation method of the present invention and device are as follows: the method for purification of electronic grade phosphorus oxychloride of the present invention may further comprise the steps:
1. getting industrial phosphoryl chloride inserts in the container, then in container according to ten thousand of phosphoryl chloride total amount/to 3/10000ths adding potassium permanganate oxidants, adding Sodium Bromide or cetyl trimethylammonium bromide additives according to the thousandth to thousand of phosphoryl chloride total amount/three, be delivered in the high-order storage tank 2 by transferpump 1 after stirring; Add herein potassium permanganate oxidant ten thousand/, 2/10000ths or 3/10000ths all can, oxygenant is used for making the ferrous ion of phosphoryl chloride fully be oxidized to ferric ion.The additive thousandth, 2/1000ths or 3/1000ths that adds all can, additive is used for and the ferric ion reaction generates lower boiling or the easy compound F 17-hydroxy-corticosterone eBr of distillation
3Additive also can with material in arsenic, calcium, magnesium ion and heavy metal ion form high boiling compound or complex compound, thereby make the separation purpose that reaches fabulous in the rectifying afterwards, make the colourity of product less than 5APHA, the resultant metal content of impurities is less than 100ppb, the individual event metallic impurity are no more than 10ppb etc., and the oxygenant of selecting and the purity of additive are the above purity of analytical pure.
2. the phosphoryl chloride in the high-order storage tank 2 is imported in the sub-boiling distillation device and carry out the I and II sub-boiling distillation, the one-level sub-boiling distillation is got 80-104.2 ℃ of phosphoryl chloride cut, and the secondary sub-boiling distillation is got 82.5-104.1 ℃ of phosphoryl chloride cut; This process can make the ferrous ion of 30-55% change into ferric ion, and the ferrous ion of complete oxidation does not continue oxidation again at rectification working process.It is further preferred version that the one-level sub-boiling distillation is got 94.2-102 ℃ of phosphoryl chloride cut, and it is further preferred version that the secondary sub-boiling distillation is got 95-101 ℃ of phosphoryl chloride cut.
3. with step 2. in the gained distillation product importing work in-process storage tank 5;
4. the work in-process in the work in-process storage tank 5 are imported in the rectifying tower reactor 6, rectifying tower reactor 6 interior installation heating tubes, after the liquid level in the rectifying tower reactor 6 floods heating tube, opening power heats, voltage control is at 100-200V, the flows that work in-process flow in the rectifying tower reactor 6 are 5-10kg/h, voltage control 100,110,120,130,140,150,160,170,180,190 or 200V all can, preferred 150-180V; Work in-process flow into flows in the rectifying tower reactor 6 be 5,6,7,8,9 or 10kg/h all can, preferred 7-10kg/h;
5. 4. step carried out total reflux 30-60 minute after the middle rectifying tower reactor 6 interior work in-process boilings, that is: backflow all could in 30,35,40,45,50,55 or 60 minutes, ferrous ion is fully changed into lower boiling ferric ion compound become the easily iron bromide of distillation, be removed simultaneously, then with control of reflux ratio at 2-6, high-boiling-point impurity is stayed in the rectifying tower reactor 6, and reflux ratio is 2,3,4,5 or 6 all can;
6. the phosphoryl chloride cut of getting 101-105 ℃ imports in the finished product storage tank 14, the low-boiling point material phosphorus trichloride imports in the oxidizer 13 and passes into purity oxygen, the flow of the purity oxygen that passes into is 200-350L/h, carry out being back in the rectifying tower reactor 6 after the oxidation, carry out again the vapour-liquid mass exchange, impurity is fully separated, can obtain the electronic grade phosphorus oxychloride of 7N;
7. the strainer 15 that the triclosan oxidation phosphorus products in the finished product storage tank 14 is imported in the clean room filters, and is 99.99999% electronic grade phosphorus oxychloride thereby obtain water white transparency and purity.
The FeBr3 that has minute quantity in the whole continuous purification process of the present invention produces, because FeBr3, easily distillation, so FeBr3 that produces in the production process, enter into oxidizer 13 with the low-boiling-point substance phosphorus trichloride with same principle, phosphorus trichloride is being carried out in the oxidation reaction process, making simultaneously easy sublimate FeBr3, playing exhaust treatment system with tail gas one and dispose.
Product filtration of the present invention, detection and can are all carried out under the environment purification of whole thousand grades of local laminar flows.
The phosphoryl chloride of method of purification step of the present invention described in 2. import in the one-level sub-boiling distillation device 3 and in the secondary sub-boiling distillation device 4 liquid level all be lower than more than the heating tube 30mm, be convenient to better reach the Asia state that boils.
Product of the present invention is colourless transparent liquid, with inductivity coupled plasma mass spectrometry (ICP-MS) detection Al, As, Ba, Bi, Ca, Cr, Co, Cu, Ga, Au, Fe, Pb, Mg, Mn, Hg, Ni, K, Ag, Na, Sr, Sn, Ti, Zn, Cd, Li content wherein, result such as following table:
Resultant metal ionic impurity total content is less than 100ppb, and individual event impurity metal ion content is less than or equal to 10ppb.
The device that uses in the method for purification of a kind of electronic grade phosphorus oxychloride of the present invention, splendid attire industry phosphoryl chloride container is connected with transferpump 1, transferpump 1 is connected with the high-order storage tank 2 of raw material, the outlet of the high-order storage tank 2 of raw material is connected with one-level sub-boiling distillation device 3 entrances by pipeline, the first fractional column 16 is set on the one-level sub-boiling distillation device 3, the first fractional column 16 is connected by the import of prolong with secondary sub-boiling distillation device 4, on the secondary sub-boiling distillation device 4 after-fractionating post 17 is set, after-fractionating post 17 is connected with work in-process storage tank 5 entrances by prolong, simultaneously, 5 outlets of work in-process storage tank are connected with 6 imports of rectifying tower reactor by pipeline, king-post 7 is set on the rectifying tower reactor 6, return line 8 is set on the king-post 7, above the return line 8 of king-post 7 one sides, pipe connecting 9 is set, king-post 7 tops to the height H of pipe connecting 9 is the 800-1500 millimeter, king-post 7 tops are connected with the second prolong 18 by pipeline, the second prolong 18 is connected with oxidizer 13 entrances, oxidizer 13 outlets are connected with rectifying tower reactor 6, pipe connecting 9 is connected with tower head 10, tower head 10 is connected with the first prolong 11, the first prolong 11 is connected with divider 12, divider 12 is connected with finished product storage tank 14, simultaneously, return line 8 is connected with divider 12 by pipeline, and finished product storage tank 14 connects by pipe-and-filter 15.
In the device of method of purification of the present invention, king-post 7 tops to the height H of pipe connecting 9 is that the 850-1500 millimeter is preferred version.That is: the boiling point of low-boiling-point substance phosphorus trichloride is lower than phosphoryl chloride, this section height can make material again carry out the vapour-liquid mass separation, herein, low-boiling-point substance phosphorus trichloride proportion is little, boiling point is low, so phosphorus trichloride can be from king-post 7 top fractionation to oxidizer 13, the about generation more than 99% of the heavy phosphoryl chloride of high boiling point refluxed, thereby more phosphoryl chloride is flowed from tower head 10 parts.
In the device of method of purification of the present invention, 3 opening for feeds are set on the rectifying tower reactor 6.3 opening for feeds are respectively applied to: opening for feed 1 is used for cleaning rectifying tower, can prolong the work-ing life of rectifying tower.Opening for feed 2 enters rectifying tower reactor 6 as the material in the work in-process storage tank 5 or the opening for feed of the complete material of oxidizer 13 interior oxidations continuously according to setting flow velocity; Opening for feed 3 is that the products in the finished product storage tank 14 detect through ICP-MS and flow in the rectifying tower reactor 6 again purification processes after defective.
On the one-level sub-boiling distillation device 3 that uses in method of purification of the present invention and the device and the secondary sub-boiling distillation device 4 fractional column is set all, the height of the first fractional column 16, after-fractionating post 17 is at 300-1000 millimeters, the preferred 600-900 millimeter of the height of the first fractional column 16, after-fractionating post 17; This fractional column and highly be used for carrying out again the vapour-liquid mass process one time by the phosphoryl chloride material of sub-boiling distillation makes sub-boiling distillation equipment herein that a little rectifying be arranged in sub-boiling distillation, thereby reaches better separating-purifying effect.
Linkage section between linkage section between return line 8 of the present invention and the divider 12 and divider 12 and the finished product storage tank 14 arranges respectively variable valve, is used for the control reflux ratio.
Equipment used of the present invention is pure quartz glass or liner polytetrafluoro metal vessel; Transport pipe is high purity quartz pipe or high-purity tetrafluoroethylene pipeline; Storage tank is pure quartz glass or metal vessel (carbon steel, 304,316 or the metallic substance such as 316L) the high-purity tetrafluoroethylene material of liner.
Filter device therefor 15 of the present invention is that high-purity polytetrafluoro material of 0.01-0.05 micron is made.
Equipment used of the present invention does not describe part in detail and is known technology.
Claims (8)
1. the method for purification of an electronic grade phosphorus oxychloride is characterized in that: may further comprise the steps:
1. getting the technical grade phosphoryl chloride inserts in the container, then in container according to ten thousand of phosphoryl chloride total amount/to 3/10000ths adding potassium permanganate oxidants, adding Sodium Bromide or cetyl trimethylammonium bromide additives according to the thousandth to thousand of phosphoryl chloride total amount/three, be delivered in the high-order storage tank (2) by transferpump (1) after stirring;
2. the phosphoryl chloride in the high-order storage tank (2) is imported in the sub-boiling distillation device and carry out the I and II sub-boiling distillation, the one-level sub-boiling distillation is got 80-104.2 ℃ of phosphoryl chloride cut, and the secondary sub-boiling distillation is got 82.5-104.1 ℃ of phosphoryl chloride cut;
3. with step 2. in the gained distillation product importing work in-process storage tanks (5);
4. the work in-process in the work in-process storage tank (5) are imported in the rectifying tower reactor (6), heating tube is installed in the rectifying tower reactor (6), after the liquid level in the rectifying tower reactor (6) floods heating tube, opening power heats, voltage control is at 100-200V, and the flow that work in-process flow in the rectifying tower reactor (6) is 5-10kg/h;
5. 4. step carried out total reflux 30-60 minute after the interior work in-process boiling of middle rectifying tower reactor (6), ferrous ion is fully changed into lower boiling ferric ion compound become the easily iron bromide of distillation, be removed simultaneously, then with control of reflux ratio at 2-6, high-boiling-point impurity is stayed in the rectifying tower reactor (6);
6. the phosphoryl chloride cut of getting 101-105 ℃ imports in the finished product storage tank (14), the low-boiling point material phosphorus trichloride imports in the oxidizer (13) and passes into purity oxygen, the flow of the purity oxygen that passes into is 200-350L/h, carries out being back to after the oxidation carrying out abundant vapour-liquid mass in the rectifying tower reactor (6) again and separating;
7. the strainer (15) that the triclosan oxidation phosphorus product in the finished product storage tank (14) is imported in the clean room filters, and is 99.99999% electronic grade phosphorus oxychloride thereby obtain water white transparency and purity.
2. the method for purification of a kind of electronic grade phosphorus oxychloride according to claim 1 is characterized in that: the phosphoryl chloride of step described in 2. imports in the one-level sub-boiling distillation device (3) and the liquid level in the secondary sub-boiling distillation device (4) all is lower than more than the heating tube 30mm.
3. the device that uses in the method for purification of a kind of electronic grade phosphorus oxychloride according to claim 1, it is characterized in that: splendid attire industry phosphoryl chloride container is connected with transferpump (1), transferpump (1) is connected with the high-order storage tank of raw material (2), the outlet of the high-order storage tank of raw material (2) is connected with one-level sub-boiling distillation device (3) entrance by pipeline, the first fractional column (16) is set on the one-level sub-boiling distillation device (3), the first fractional column (16) is connected by the import of prolong with secondary sub-boiling distillation device (4), after-fractionating post (17) is set on the secondary sub-boiling distillation device (4), after-fractionating post (17) is connected with work in-process storage tank (5) entrance by prolong, simultaneously, work in-process storage tank (5) outlet is connected with rectifying tower reactor (6) import by pipeline, king-post (7) is set on the rectifying tower reactor (6), return line (8) is set on the king-post (7), return line (8) top in king-post (7) one sides arranges pipe connecting (9), king-post (7) top to the height H of pipe connecting (9) is the 800-1500 millimeter, king-post (7) top is connected with the second prolong (18) by pipeline, the second prolong (18) is connected with oxidizer (13) entrance, oxidizer (13) outlet is connected with rectifying tower reactor (6), pipe connecting (9) is connected with tower head (10), tower head (10) is connected with the first prolong (11), the first prolong (11) is connected with divider (12), divider (12) is connected with finished product storage tank (14), simultaneously, return line (8) is connected with divider (12) by pipeline, and finished product storage tank (14) connects by pipe-and-filter (15).
4. the device that uses in the method for purification of a kind of electronic grade phosphorus oxychloride according to claim 3 is characterized in that: king-post (7) top to the height H of pipe connecting (9) is the 850-1500 millimeter.
5. the device that uses in the method for purification of described a kind of electronic grade phosphorus oxychloride according to claim 3, it is characterized in that: the height of the first fractional column (16) and after-fractionating post (17) is 300mm-1000mm.
6. the device that uses in the method for purification of described a kind of electronic grade phosphorus oxychloride according to claim 3, it is characterized in that: the angle [alpha] between pipe connecting (9) and the king-post (7) is 15o-60o.
7. the device that uses in the method for purification of described a kind of electronic grade phosphorus oxychloride according to claim 3, it is characterized in that: the angle [alpha] between pipe connecting (9) and the king-post (7) is 45o.
8. the device that uses in the method for purification of a kind of electronic grade phosphorus oxychloride according to claim 3 is characterized in that: 3 opening for feeds are set on the rectifying tower reactor (6).
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201110158443 CN102249201B (en) | 2011-06-14 | 2011-06-14 | Method and device for producing electronic grade phosphorus oxychloride |
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| CN 201110158443 CN102249201B (en) | 2011-06-14 | 2011-06-14 | Method and device for producing electronic grade phosphorus oxychloride |
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| CN102249201B true CN102249201B (en) | 2013-04-24 |
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| CN104891462B (en) * | 2015-05-28 | 2017-05-10 | 云南省化工研究院 | Method for synthesising phosphorus oxychloride by virtue of micro-reaction |
| CN108821254B (en) * | 2018-09-11 | 2021-11-26 | 安徽东至广信农化有限公司 | Method for removing inorganic and organic impurities in phosphorus trichloride synthesis process |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US4178353A (en) * | 1971-10-08 | 1979-12-11 | Monsanto Company | Preparation and purification of phosphoryl chloride |
| JPH08259207A (en) * | 1995-03-24 | 1996-10-08 | Nippon Soda Co Ltd | Method for purifying phosphorus oxychloride |
| DE19730224A1 (en) * | 1997-07-15 | 1999-01-21 | Bayer Ag | Process for cleaning phosphorus oxychloride |
| CN1290762C (en) * | 2004-11-10 | 2006-12-20 | 贵州威顿晶磷电子材料有限公司 | Production of phosphorus oxychloride with purity of 99.99999% |
| CN101570323A (en) * | 2009-06-10 | 2009-11-04 | 向东 | Method for producing phosphorus oxychloride with purity of 99.99999 percent and device thereof |
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