CN104190256A - Construction method based on technology for producing boron isotope by anisole-boron trifluoride - Google Patents
Construction method based on technology for producing boron isotope by anisole-boron trifluoride Download PDFInfo
- Publication number
- CN104190256A CN104190256A CN201410414342.8A CN201410414342A CN104190256A CN 104190256 A CN104190256 A CN 104190256A CN 201410414342 A CN201410414342 A CN 201410414342A CN 104190256 A CN104190256 A CN 104190256A
- Authority
- CN
- China
- Prior art keywords
- tower
- methyl phenyl
- phenyl ethers
- ethers anisole
- boron
- 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.)
- Granted
Links
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 title claims abstract description 43
- 229910052796 boron Inorganic materials 0.000 title claims abstract description 43
- 238000005516 engineering process Methods 0.000 title abstract description 5
- ADKFPZYATUZKCR-UHFFFAOYSA-N anisole;trifluoroborane Chemical compound FB(F)F.COC1=CC=CC=C1 ADKFPZYATUZKCR-UHFFFAOYSA-N 0.000 title abstract 4
- 238000010276 construction Methods 0.000 title abstract 3
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 claims abstract description 355
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 117
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 claims abstract description 117
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 claims abstract description 87
- 239000007789 gas Substances 0.000 claims abstract description 78
- 239000007788 liquid Substances 0.000 claims abstract description 59
- 238000000034 method Methods 0.000 claims abstract description 31
- 229910015900 BF3 Inorganic materials 0.000 claims abstract description 22
- ZOXJGFHDIHLPTG-BJUDXGSMSA-N Boron-10 Chemical compound [10B] ZOXJGFHDIHLPTG-BJUDXGSMSA-N 0.000 claims abstract description 13
- ZOXJGFHDIHLPTG-IGMARMGPSA-N boron-11 atom Chemical compound [11B] ZOXJGFHDIHLPTG-IGMARMGPSA-N 0.000 claims abstract description 12
- 239000002994 raw material Substances 0.000 claims abstract description 11
- 238000005336 cracking Methods 0.000 claims abstract description 7
- 238000004519 manufacturing process Methods 0.000 claims abstract description 7
- 238000001035 drying Methods 0.000 claims description 62
- 229910052757 nitrogen Inorganic materials 0.000 claims description 59
- -1 methyl phenyl ethers anisole-boron trifluoride Chemical class 0.000 claims description 41
- 239000012535 impurity Substances 0.000 claims description 37
- 150000001875 compounds Chemical class 0.000 claims description 33
- 238000003860 storage Methods 0.000 claims description 30
- 230000000536 complexating effect Effects 0.000 claims description 27
- 238000003776 cleavage reaction Methods 0.000 claims description 26
- 230000007017 scission Effects 0.000 claims description 26
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 18
- 238000007599 discharging Methods 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 238000000746 purification Methods 0.000 claims description 15
- 238000000926 separation method Methods 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 10
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 claims description 6
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 6
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 6
- 230000006835 compression Effects 0.000 claims description 6
- 238000007906 compression Methods 0.000 claims description 6
- 239000000945 filler Substances 0.000 claims description 6
- 239000007791 liquid phase Substances 0.000 claims description 6
- 239000012071 phase Substances 0.000 claims description 6
- 238000005086 pumping Methods 0.000 claims description 6
- 238000010926 purge Methods 0.000 claims description 6
- 239000007921 spray Substances 0.000 claims description 6
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 3
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 claims description 3
- HMFWLRTYRNNDGP-UHFFFAOYSA-N [N].COC1=CC=CC=C1 Chemical compound [N].COC1=CC=CC=C1 HMFWLRTYRNNDGP-UHFFFAOYSA-N 0.000 claims description 3
- 238000007664 blowing Methods 0.000 claims description 3
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 3
- 239000001110 calcium chloride Substances 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 150000002500 ions Chemical class 0.000 claims description 3
- 239000002808 molecular sieve Substances 0.000 claims description 3
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 3
- 238000012856 packing Methods 0.000 claims description 3
- 238000004080 punching Methods 0.000 claims description 3
- 238000010992 reflux Methods 0.000 claims description 3
- 230000008929 regeneration Effects 0.000 claims description 3
- 238000011069 regeneration method Methods 0.000 claims description 3
- 239000011347 resin Substances 0.000 claims description 3
- 229920005989 resin Polymers 0.000 claims description 3
- 230000000630 rising effect Effects 0.000 claims description 3
- 239000000741 silica gel Substances 0.000 claims description 3
- 229910002027 silica gel Inorganic materials 0.000 claims description 3
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 238000005507 spraying Methods 0.000 claims description 3
- 238000005372 isotope separation Methods 0.000 abstract description 2
- 229910001873 dinitrogen Inorganic materials 0.000 abstract 2
- 238000010668 complexation reaction Methods 0.000 abstract 1
- 239000000126 substance Substances 0.000 description 3
- FSQBHIPIGPYBCB-UHFFFAOYSA-N anisole;boron Chemical compound [B].COC1=CC=CC=C1 FSQBHIPIGPYBCB-UHFFFAOYSA-N 0.000 description 2
- 230000006837 decompression Effects 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 1
- 238000005094 computer simulation Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- KTPWETRNSUKEME-UHFFFAOYSA-N methoxymethane;trifluoroborane Chemical compound COC.FB(F)F KTPWETRNSUKEME-UHFFFAOYSA-N 0.000 description 1
- 239000010813 municipal solid waste Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a construction method based on a technology for producing boron isotope by anisole-boron trifluoride, which belongs to the field of isotope separation, and mainly aims at solving the problems such as low yield of boron-10 and incapability of obtaining qualified boron-11 products at the same time in the existing construction method based on the technology for producing boron isotope by anisole-boron trifluoride. The method disclosed by the invention comprises the following steps: continuously purifying raw materials, namely boron trifluoride gas and an anisole liquid, as well as an anisole-boron trifluoride complex before entering a cracking tower, nitrogen gas coming out of the top of a complex gas stripping tower, boron trifluoride gas after cracking, and gas coming out of the top of a first exchange rectifying tower; adding the purified nitrogen gas into a second exchange rectifying tower; adding fresh boron trifluoride gas into the first exchange rectifying tower, wherein boron-10 is not discharged out from the top of the cracking tower and boron-11 is not discharged out from the top of a complexation tower; and after performing system rectification balance for 72-148 hours, converting to the normal production mode. The method has the advantage that the two qualified products, namely boron trifluoride-10 and boron trifluoride-11 can be produced at the same time.
Description
Technical field:
The invention belongs to isotopic separation field, specifically relate to a kind of start-up method of methyl phenyl ethers anisole-boron trifluoride complex chemical reaction rectifying Separation of boron isotopes production process.
Background technology:
Boron has two kinds of stable isotopes, boron-10 and boron-11, and natural abundance is respectively 19.3% and 80.7%.Boron-10 pair neutron has very strong absorbability, increasingly extensive in the application of the aspects such as nuclear power, modern industry, military equipment and medicine.Boron-11st, a kind of potential thermonuclear reaction material, adds the steel of boron-11 and can significantly improve the performances such as high temperature resistant, radiation hardness.At present, the high abundance boron istope product that China is used mainly relies on import.The method of industrial production boron istope mainly contains three kinds in the world: ether-boron trifluoride decompression exchange distillation, methyl ether-boron trifluoride decompression exchange distillation and methyl phenyl ethers anisole-boron trifluoride chemical exchange reaction rectification method.Wherein methyl phenyl ethers anisole-boron trifluoride chemical exchange reaction rectification method is the main method of producing in the world boron istope at present.
Because the separation of boron istope is very little, need for a long time from being dosed into rectifying balance, conventionally several days consuming time to twenties days not etc.How restart up is key subjects.The Zhang Weijiang of University Of Tianjin etc. with computer simulation start-up process, and proposed the strategy that goes into operation of " cascade charging, not discharging of tower bottom; become gas speed, keep impurities removal ", but the method boron-10 yield is low, boron-11, as trash discharge, can not be obtained to boron-11 qualified products simultaneously.
Summary of the invention:
The technical problem of all solutions of the present invention is to provide that a kind of time of driving is short, boron-10 yield is high, and can obtain a kind of start-up method of producing boron istope technique based on the rectifying of methyl phenyl ethers anisole-boron trifluoride complex Chemical Exchange of boron-11 qualified products simultaneously.
Above-mentioned purpose is achieved in that used raw material is for boron triflouride gas (natural abundance, boron-10 abundance is 19.3%) and methyl phenyl ethers anisole liquid, and the mol ratio of described boron triflouride gas and methyl phenyl ethers anisole liquid is 1: 1; The equipment using comprises complexing tower, the first exchange rectifying column, the second exchange rectifying column, complex compound stripping tower, complex compound cleavage column, methyl phenyl ethers anisole rectifying removal of impurities tower, methyl phenyl ethers anisole drying tower, ice chest etc.;
Method is: system is replaced with nitrogen blowing, not residual moisture.Initialization system pressure is 5Kpa (G)-85Kpa (G), and suitable pressure is 10Kpa (G), nitrogen punching press pressurize for system.Low-pressure nitrogen positive seals protection for all storage tanks, prevents that humid air from scurrying into.
Raw material boron triflouride gas and methyl phenyl ethers anisole liquid are carried out respectively to purified treatment:
1, with Deep Cooling Method purified treatment boron triflouride gas, remove HF, CH wherein
3the impurity such as F; Processing procedure is: raw material boron triflouride gas is removed solid matter by deduster, then enters compressor and boosts to 0.2Mpa-1.6Mpa, then enter ice chest, is cooled to-85 DEG C--95 DEG C are carried out cryogenic separation, make HF, CH
3the high-boiling-point impurities such as F are condensed into liquid, and boron trifluoride still exists with gas; Separate and remove residual HF and water through cyclone separator, boron triflouride gas from cyclone separator top out, enters unstrpped gas spherical tank, then enters exchange rectification working process.
2, benzene feedstock methyl ether liquid is carried out removal of impurities, dehydrates processing.Method is: methyl phenyl ethers anisole liquid is sent into methyl phenyl ethers anisole rectifying removal of impurities tower and carry out rectifying, the impurity such as phenol are discharged from tower reactor, phenol content is less than 0.002% methyl phenyl ethers anisole liquid from tower top out, enter the top of methyl phenyl ethers anisole drying tower, filler, carry out counter current contacting with the nitrogen entering from methyl phenyl ethers anisole drying tower tower reactor, by air lift, the moisture in methyl phenyl ethers anisole is reduced to 0.002%-0.004%, dried methyl phenyl ethers anisole from drying tower tower reactor with being pumped to methyl phenyl ethers anisole storage tank; Dry from methyl phenyl ethers anisole drying tower tower top moisture nitrogen out denitrification gas dryer after compressor compression, dried nitrogen is got back to methyl phenyl ethers anisole drying tower tower reactor and is recycled, and the drier in nitrogen drying device continues to use after regeneration; Described nitrogen is 3 with the molal weight ratio of methyl phenyl ethers anisole liquid: 1-7: 1, and methyl phenyl ethers anisole drying tower pressure is 5Kpa (G)-85Kpa (G), temperature is 20 DEG C-60 DEG C; In nitrogen drying device, can adopt sodium metal, calcium chloride, molecular sieve, active carbon, silica gel, ion to hand over resin to equal drying prescription; Methyl phenyl ethers anisole drying tower can be packed tower, plate column, valve tower or miscellaneous equipment form; Described methyl phenyl ethers anisole nitrogen drying, dewaters with drier from methyl phenyl ethers anisole drying tower tower top moisture nitrogen out, and after compressor compression, nitrogen returns methyl phenyl ethers anisole drying tower to be continued to recycle;
From methyl phenyl ethers anisole storage tank by purify methyl phenyl ethers anisole liquid pumping to complexing top of tower, by interim pipeline, by the boron triflouride gas of natural abundance, (boron-10 abundance is 19.3%, boron-11 abundance is 80.7%) deliver to complexing tower bottom, from top to bottom spray methyl phenyl ethers anisole liquid with to lower and on boron triflouride gas counter current contacting in filler, produce methyl phenyl ethers anisole-boron trifluoride complex and enter complexing tower tower reactor, complex reaction temperature is 6 DEG C-12 DEG C, and the methyl phenyl ethers anisole-boron trifluoride complex of complexing tower tower reactor is through being pumped to complex compound storage tank;
By methyl phenyl ethers anisole-boron trifluoride complex from complex compound storage tank with being pumped to the first exchange rectifying column tower top, in tower, spray, when tower reactor liquid level reaches 50%, start still liquid pump reinforced to the second exchange rectifying column tower top, in the time that the second exchange tower bottom of rectifying tower liquid level reaches 50%, start the second exchange tower bottom of rectifying tower still liquid pump,, set up from the Matter Transfer of methyl phenyl ethers anisole-boron trifluoride complex storage tank-the first exchange rectifying column-the second exchange rectifying column to the discharging of methyl phenyl ethers anisole-boron trifluoride complex storage tank by interim pipeline;
By interim pipeline, methyl phenyl ethers anisole liquid is injected to complex compound cleavage column and methyl phenyl ethers anisole purification and impurity removal tower, start the reboiler of cleavage column and methyl phenyl ethers anisole purification and impurity removal tower, set up infinite reflux at two towers respectively, benzene feedstock methyl ether is added to purification and impurity removal tower, from removal of impurities column overhead to the discharging of methyl phenyl ethers anisole drying tower, drying nitrogen is introduced to methyl phenyl ethers anisole drying tower tower reactor, start methyl phenyl ethers anisole drying tower, dried methyl phenyl ethers anisole is by being pumped to methyl phenyl ethers anisole storage tank;
Boron triflouride gas after treatment is added from the first exchange rectifying tower bottom, by the second exchange rectifying tower reactor liquid pump, methyl phenyl ethers anisole-boron trifluoride complex is delivered to complex compound stripping tower top, close the second exchange rectifying tower reactor simultaneously and go the interim pipeline valve of methyl phenyl ethers anisole-boron trifluoride complex storage tank;
Nitrogen is passed into complex compound stripping tower bottom, methyl phenyl ethers anisole-boron trifluoride complex is carried out to air lift purified treatment, nitrogen from complex compound stripping tower top out, after compressor is compressed to 0.2Mpa (G)-1.6Mpa (G), enters in ice chest and be cooled to-85 DEG C--95 DEG C are carried out cryogenic separation, HF, CH
3f and water are condensed, and nitrogen and boron trifluoride are still gas, remove residual HF, CH through cyclone separator
3f and water, boron triflouride gas and nitrogen remove the second exchange rectifying column; Methyl phenyl ethers anisole-boron trifluoride complex after purification removes cleavage column from the pumping of complex compound stripping tower tower reactor;
In cleavage column, there is cracking in methyl phenyl ethers anisole-boron trifluoride complex, boron triflouride gas from cleavage column tower top out, after compressor is compressed to 0.2Mpa (G)-1.6Mpa (G), enters in ice chest and be cooled to-85 DEG C--95 DEG C are carried out cryogenic separation, HF, CH
3f and water are condensed, and boron trifluoride is still gas, remove residual HF, CH in cyclone separator
3f and water, boron triflouride gas is all back to the second exchange rectifying column, keeps not discharging; Methyl phenyl ethers anisole from cleavage column tower reactor out, goes methyl phenyl ethers anisole purification and impurity removal tower and methyl phenyl ethers anisole drying tower to carry out purge drying processing, and the methyl phenyl ethers anisole liquid after purge drying removes methyl phenyl ethers anisole storage tank;
Eject next gas and contain boron trifluoride, nitrogen and hydrofluoric acid etc. from the first exchange rectifying tower, be cooled to-85 DEG C through ice chest--95 DEG C are carried out cryogenic separation, HF, CH
3f etc. are condensed into liquid, and boron trifluoride and nitrogen are still gas, enter out in cyclone separator, remove residual HF, CH from ice chest
3f etc., still for boron trifluoride and the nitrogen of gaseous state enter complexing tower tower reactor, in complexing tower packing there is complex reaction with the methyl phenyl ethers anisole liquid spraying downwards in the boron triflouride gas of rising, generates methyl phenyl ethers anisole-boron trifluoride complex;
Add continuously fresh boron triflouride gas to the first exchange rectifying column, along with boron trifluoride-10 are by transferring to gradually in liquid phase in gas phase, boron trifluoride-11 are item by transferring to gradually in gas phase in liquid phase, last boron trifluoride-10 at the bottom of the second exchange rectifying tower slowly enrichment get up, and boron trifluoride-11 the first exchange rectifying column tower top slowly enrichment get up;
The not discharging of boron-10 of cleavage column tower top, also not discharging of complexing column overhead boron-11 (by increasing methyl phenyl ethers anisole quantity, make boron trifluoride-11 in complexing tower become methyl phenyl ethers anisole-boron trifluoride-11 complex compound and realize);
Through total system circulation in 72-148 hour, exchange rectifying column reached rectifying balance, and boron trifluoride-10 and boron trifluoride-11 abundance reach after designing requirement, can transfer smoothly normal production model to, simultaneously output boron trifluoride-10 and boron trifluoride-11 two kind of product
Advantage of the present invention is: the driving time is short, after 72-148 hour system rectifying balance, just can transfer smoothly normal production model to, and can while output boron trifluoride-10 and boron trifluoride-11 two kind of qualified products.In whole start-up process, all the time to raw material boron triflouride gas and methyl phenyl ethers anisole liquid, to entering the methyl phenyl ethers anisole-boron trifluoride complex before complex compound cleavage column, complex compound stripping tower tower top nitrogen out, boron triflouride gas after cracking, the first exchange rectifying tower ejects the gas coming and carries out continuous purified treatment, remove water wherein, the impurity such as HF, guarantee that the total impurities in system is on a declining curve, making production process be able to continous-stable carries out, adopt the original creation technology that adds nitrogen to exchange rectifying column, can effectively improve the separative efficiency of exchange rectifying column, restart up.
Brief description of the drawings:
Accompanying drawing is process chart of the present invention, and in figure, 1 is complexing tower, and 2 is first exchange rectifying columns, and 3 is second exchange rectifying columns, the 4th, and complex compound stripping tower, the 5th, complex compound cleavage column, the 6th, methyl phenyl ethers anisole rectifying removal of impurities tower, the 7th, methyl phenyl ethers anisole drying tower, the 8th, ice chest.
Detailed description of the invention:
The raw material using is boron triflouride gas (natural abundance, boron-10 abundance is 19.3%) and methyl phenyl ethers anisole liquid, and the mol ratio of described boron triflouride gas and methyl phenyl ethers anisole liquid is 1: 1;
With reference to accompanying drawing, the equipment using comprises complexing tower 1, the first exchange rectifying column 2, the second exchange rectifying column 3, complex compound stripping tower 4, complex compound cleavage column 5, methyl phenyl ethers anisole rectifying removal of impurities tower 6, methyl phenyl ethers anisole drying tower 7, ice chest 8 etc.;
Method is: system is replaced with nitrogen blowing, not residual moisture.Initialization system pressure is 5Kpa (G) or 10Kpa (G) or 20Kpa (G) or 35Kpa (G) or 50Kpa (G) or 70Kpa (G) or 85Kpa (G), suitable pressure is 10Kpa (G), nitrogen punching press pressurize for system.Low-pressure nitrogen positive seals protection for all storage tanks, prevents that humid air from scurrying into.
Raw material boron triflouride gas and methyl phenyl ethers anisole liquid are carried out respectively to purified treatment:
1, with Deep Cooling Method purified treatment boron triflouride gas, remove HF, CH wherein
3the impurity such as F; Processing procedure is: raw material boron triflouride gas is removed solid matter by deduster, then enters compressor and boosts to 0.2Mpa or 0.8Mpa or 1.2Mpa or 1.6Mpa, then enter ice chest, is cooled to-85 DEG C or-90 DEG C or-95 DEG C and carries out cryogenic separation, makes HF, CH
3the high-boiling-point impurities such as F are condensed into liquid, and boron trifluoride still exists with gas; Separate and remove residual HF and water through cyclone separator, boron triflouride gas from cyclone separator top out, enters unstrpped gas spherical tank, then enters exchange rectification working process.
2, benzene feedstock methyl ether liquid is carried out removal of impurities, dehydrates processing.Method is: methyl phenyl ethers anisole liquid is sent into methyl phenyl ethers anisole rectifying removal of impurities tower and carry out rectifying, the impurity such as phenol are discharged from tower reactor, phenol content is less than 0.002% methyl phenyl ethers anisole liquid from tower top out, enter the top of methyl phenyl ethers anisole drying tower, filler, carry out counter current contacting with the nitrogen entering from methyl phenyl ethers anisole drying tower tower reactor, by air lift, the moisture in methyl phenyl ethers anisole is reduced to 0.002% or 0.003% or 0.004%, dried methyl phenyl ethers anisole from drying tower tower reactor with being pumped to methyl phenyl ethers anisole storage tank; Dry from methyl phenyl ethers anisole drying tower tower top moisture nitrogen out denitrification gas dryer after compressor compression, dried nitrogen is got back to methyl phenyl ethers anisole drying tower tower reactor and is recycled, and the drier in nitrogen drying device continues to use after regeneration; Described nitrogen is 3: 1 or 5: 1 or 7: 1 with the molal weight ratio of methyl phenyl ethers anisole liquid, methyl phenyl ethers anisole drying tower pressure is 5Kpa (G) or 20Kpa (G) or 35Kpa (G) or 50Kpa (G) or 70Kpa (G) or 85Kpa (G), and temperature is 20 DEG C or 40 DEG C or 60 DEG C; In nitrogen drying device, can adopt sodium metal, calcium chloride, molecular sieve, active carbon, silica gel, ion to hand over the drier such as resin; Methyl phenyl ethers anisole drying tower can be packed tower, plate column, valve tower or miscellaneous equipment form; Described methyl phenyl ethers anisole nitrogen drying, dewaters with drier from methyl phenyl ethers anisole drying tower tower top moisture nitrogen out, and after compressor compression, nitrogen returns methyl phenyl ethers anisole drying tower to be continued to recycle;
From methyl phenyl ethers anisole storage tank by purify methyl phenyl ethers anisole liquid pumping to complexing top of tower, by interim pipeline, by the boron triflouride gas of natural abundance, (boron-10 abundance is 19.3%, boron-11 abundance is 80.7%) deliver to complexing tower bottom, from top to bottom spray methyl phenyl ethers anisole liquid with to lower and on boron triflouride gas counter current contacting in filler, generate methyl phenyl ethers anisole-boron trifluoride complex and enter complexing tower tower reactor, complex reaction temperature is 6 DEG C or 9 DEG C or 12 DEG C, and the methyl phenyl ethers anisole-boron trifluoride complex of complexing tower tower reactor is through being pumped to complex compound storage tank;
By methyl phenyl ethers anisole-boron trifluoride complex from complex compound storage tank with being pumped to the first exchange rectifying column tower top, in tower, spray, when tower reactor liquid level reaches 50%, start still liquid pump reinforced to the second exchange rectifying column tower top, in the time that the second exchange tower bottom of rectifying tower liquid level reaches 50%, start the second exchange tower bottom of rectifying tower still liquid pump,, set up from the Matter Transfer of methyl phenyl ethers anisole-boron trifluoride complex storage tank-the first exchange rectifying column-the second exchange rectifying column to the discharging of methyl phenyl ethers anisole-boron trifluoride complex storage tank by interim pipeline;
By interim pipeline, methyl phenyl ethers anisole liquid is injected to complex compound cleavage column and methyl phenyl ethers anisole purification and impurity removal tower, start the reboiler of cleavage column and methyl phenyl ethers anisole purification and impurity removal tower, set up infinite reflux at two towers respectively, benzene feedstock methyl ether is added to purification and impurity removal tower, from removal of impurities column overhead to the discharging of methyl phenyl ethers anisole drying tower, drying nitrogen is introduced to methyl phenyl ethers anisole drying tower tower reactor, start methyl phenyl ethers anisole drying tower, dried methyl phenyl ethers anisole is by being pumped to methyl phenyl ethers anisole storage tank;
Boron triflouride gas after treatment is added from the first exchange rectifying tower bottom, by the second exchange rectifying tower reactor liquid pump, methyl phenyl ethers anisole-boron trifluoride complex is delivered to complex compound stripping tower top, close the second exchange rectifying tower reactor simultaneously and go the interim pipeline valve of methyl phenyl ethers anisole-boron trifluoride complex storage tank;
Nitrogen is passed into complex compound stripping tower bottom, methyl phenyl ethers anisole-boron trifluoride complex is carried out to air lift purified treatment, nitrogen from complex compound stripping tower top out, after compressor is compressed to 0.2Mpa (G) or 0.6Mpa (G) or 1.0Mpa (G) or 1.3Mpa (G) or 1.6Mpa (G), enter in ice chest and be cooled to-85 DEG C or-90 DEG C or-95 DEG C and carry out cryogenic separation, HF, CH
3f and water are condensed, and nitrogen and boron trifluoride are still gas, remove residual HF, CH through cyclone separator
3f and water, boron triflouride gas and nitrogen remove the second exchange rectifying column; Methyl phenyl ethers anisole-boron trifluoride complex after purification removes cleavage column from the pumping of complex compound stripping tower tower reactor;
In cleavage column, there is cracking in methyl phenyl ethers anisole-boron trifluoride complex, boron triflouride gas from cleavage column tower top out, after compressor is compressed to 0.2Mpa (G) or 0.6Mpa (G) or 1.0Mpa (G) or 1.3Mpa (G) or 1.6Mpa (G), enter in ice chest and be cooled to-85 DEG C or-90 DEG C or-95 DEG C and carry out cryogenic separation, HF, CH
3f and water are condensed, and boron trifluoride is still gas, remove residual HF, CH in cyclone separator
3f and water, boron triflouride gas is all back to the second exchange rectifying column, keeps not discharging; Methyl phenyl ethers anisole from cleavage column tower reactor out, goes methyl phenyl ethers anisole purification and impurity removal tower and methyl phenyl ethers anisole drying tower to carry out purge drying processing, and the methyl phenyl ethers anisole liquid after purge drying removes methyl phenyl ethers anisole storage tank;
Eject next gas and contain boron trifluoride, nitrogen and hydrofluoric acid etc. from the first exchange rectifying tower, being cooled to-85 DEG C or-90 DEG C or-95 DEG C through ice chest carries out cryogenic separation, HF, CH
3f etc. are condensed into liquid, and boron trifluoride and nitrogen are still gas, enter out in cyclone separator, remove residual HF, CH from ice chest
3f etc., still for boron trifluoride and the nitrogen of gaseous state enter complexing tower tower reactor, in complexing tower packing there is complex reaction with the methyl phenyl ethers anisole liquid spraying downwards in the boron triflouride gas of rising, produces methyl phenyl ethers anisole-boron trifluoride complex;
Add continuously fresh boron triflouride gas to the first exchange rectifying column, along with boron trifluoride-10 are by transferring to gradually in liquid phase in gas phase, boron trifluoride-11 are item by transferring to gradually in gas phase in liquid phase, last boron trifluoride-10 at the bottom of the second exchange rectifying tower slowly enrichment get up, and boron trifluoride-11 the first exchange rectifying column tower top slowly enrichment get up;
The not discharging of boron-10 of cleavage column tower top, also not discharging of complexing column overhead boron-11 (by increasing methyl phenyl ethers anisole quantity, make boron trifluoride-11 in complexing tower become methyl phenyl ethers anisole-boron trifluoride-11 complex compound and realize);
Through 72 hours or 92 hours or 115 hours or total system circulation in 148 hours, exchange rectifying column reaches rectifying balance, boron trifluoride-10 and boron trifluoride-11 abundance reach after designing requirement, can transfer smoothly normal production model to, simultaneously output boron trifluoride-10 and boron trifluoride-11 two kind of qualified products.
Claims (2)
1. a start-up method of producing boron istope technique based on methyl phenyl ethers anisole-boron trifluoride, is characterized in that: the raw material using for boron triflouride gas and methyl phenyl ethers anisole liquid, the mol ratio of described boron triflouride gas and methyl phenyl ethers anisole liquid be 1: 1; The equipment using comprises complexing tower (1), the first exchange rectifying column (2), the first exchange rectifying column (3), complex compound stripping tower (4), complex compound cleavage column (5), methyl phenyl ethers anisole rectifying removal of impurities tower (6), methyl phenyl ethers anisole drying tower (7), ice chest (8) etc.;
Method is: system is replaced with nitrogen blowing, not residual moisture; Initialization system pressure is 5Kpa (G)-85Kpa (G), nitrogen punching press pressurize for system; Low-pressure nitrogen positive seals protection for all storage tanks, prevents that humid air from scurrying into;
Raw material boron triflouride gas and methyl phenyl ethers anisole liquid are carried out respectively to purified treatment:
With Deep Cooling Method purified treatment boron triflouride gas, remove HF, CH wherein
3the impurity such as F; Processing procedure is: raw material boron triflouride gas is removed solid matter by deduster, then enters compressor and boosts to 0.2Mpa-1.6Mpa, then enter ice chest, is cooled to-85 DEG C--95 DEG C are carried out cryogenic separation, make HF, CH
3the high-boiling-point impurities such as F are condensed into liquid, and boron trifluoride still exists with gas; Separate and remove residual HF and water through cyclone separator, boron triflouride gas from cyclone separator top out, enters unstrpped gas spherical tank, then enters exchange rectification working process;
Benzene feedstock methyl ether liquid is carried out removal of impurities, dehydrates processing, method is: methyl phenyl ethers anisole liquid is sent into methyl phenyl ethers anisole rectifying removal of impurities tower and carry out rectifying, the impurity such as phenol are discharged from tower reactor, phenol content is less than 0.002% methyl phenyl ethers anisole liquid from tower top out, enter the top of methyl phenyl ethers anisole drying tower, filler, carry out counter current contacting with the nitrogen entering from methyl phenyl ethers anisole drying tower tower reactor, by air lift, the moisture in methyl phenyl ethers anisole is reduced to 0.002%-0.004%, dried methyl phenyl ethers anisole from drying tower tower reactor with being pumped to methyl phenyl ethers anisole storage tank; Dry from methyl phenyl ethers anisole drying tower tower top moisture nitrogen out denitrification gas dryer after compressor compression, dried nitrogen is got back to methyl phenyl ethers anisole drying tower tower reactor and is recycled, and the drier in nitrogen drying device continues to use after regeneration; Described nitrogen is 3 with the molal weight ratio of methyl phenyl ethers anisole liquid: 1-7: 1, and methyl phenyl ethers anisole drying tower pressure is 5Kpa (G)-85Kpa (G), temperature is 20 DEG C-60 DEG C; Described methyl phenyl ethers anisole nitrogen drying, dewaters with drier from methyl phenyl ethers anisole drying tower tower top moisture nitrogen out, and after compressor compression, nitrogen returns methyl phenyl ethers anisole drying tower to be continued to recycle;
From methyl phenyl ethers anisole storage tank by purify methyl phenyl ethers anisole liquid pumping to complexing top of tower, by interim pipeline, the boron triflouride gas of natural abundance is delivered to complexing tower bottom, from top to bottom spray methyl phenyl ethers anisole liquid with to lower and on boron triflouride gas counter current contacting in filler, generate methyl phenyl ethers anisole-boron trifluoride complex and enter complexing tower tower reactor, complex reaction temperature is 6 DEG C-12 DEG C, and the methyl phenyl ethers anisole-boron trifluoride complex of complexing tower tower reactor is through being pumped to complex compound storage tank;
By methyl phenyl ethers anisole-boron trifluoride complex from complex compound storage tank with being pumped to the first exchange rectifying column tower top, in tower, spray, when tower reactor liquid level reaches 50%, start still liquid pump reinforced to the second exchange rectifying column tower top, in the time that the second exchange tower bottom of rectifying tower liquid level reaches 50%, start the second exchange tower bottom of rectifying tower still liquid pump,, set up from the Matter Transfer of methyl phenyl ethers anisole-boron trifluoride complex storage tank-the first exchange rectifying column-the second exchange rectifying column to the discharging of methyl phenyl ethers anisole-boron trifluoride complex storage tank by interim pipeline;
By interim pipeline, methyl phenyl ethers anisole liquid is injected to complex compound cleavage column and methyl phenyl ethers anisole purification and impurity removal tower, start the reboiler of cleavage column and methyl phenyl ethers anisole purification and impurity removal tower, set up infinite reflux at two towers respectively, benzene feedstock methyl ether is added to purification and impurity removal tower, from removal of impurities column overhead to the discharging of methyl phenyl ethers anisole drying tower, drying nitrogen is introduced to methyl phenyl ethers anisole drying tower tower reactor, start methyl phenyl ethers anisole drying tower, dried methyl phenyl ethers anisole is by being pumped to methyl phenyl ethers anisole storage tank;
Boron triflouride gas after treatment is added from the first exchange rectifying tower bottom, by the second exchange rectifying tower reactor liquid pump, methyl phenyl ethers anisole-boron trifluoride complex is delivered to complex compound stripping tower top, close the second exchange rectifying tower reactor simultaneously and go the interim pipeline valve of methyl phenyl ethers anisole-boron trifluoride complex storage tank;
Nitrogen is passed into complex compound stripping tower bottom, methyl phenyl ethers anisole-boron trifluoride complex is carried out to air lift purified treatment, nitrogen from complex compound stripping tower top out, after compressor is compressed to 0.2Mpa (G)-1.6Mpa (G), enters in ice chest and be cooled to-85 DEG C--95 DEG C are carried out cryogenic separation, HF, CH
3f and water are condensed, and nitrogen and boron trifluoride are still gas, remove residual HF, CH through cyclone separator
3f and water, boron triflouride gas and nitrogen remove the second exchange rectifying column; Methyl phenyl ethers anisole-boron trifluoride complex after purification removes cleavage column from the pumping of complex compound stripping tower tower reactor;
In cleavage column, there is cracking in methyl phenyl ethers anisole-boron trifluoride complex, boron triflouride gas from cleavage column tower top out, after compressor is compressed to 0.2Mpa (G)-1.6Mpa (G), enters in ice chest and be cooled to-85 DEG C--95 DEG C are carried out cryogenic separation, HF, CH
3f and water are condensed, and boron trifluoride is still gas, remove residual HF, CH in cyclone separator
3f and water, boron triflouride gas is all back to the second exchange rectifying column, keeps not discharging; Methyl phenyl ethers anisole from cleavage column tower reactor out, goes methyl phenyl ethers anisole purification and impurity removal tower and methyl phenyl ethers anisole drying tower to carry out purge drying processing, and the methyl phenyl ethers anisole liquid after purge drying removes methyl phenyl ethers anisole storage tank;
Eject next gas and contain boron trifluoride, nitrogen and hydrofluoric acid etc. from the first exchange rectifying tower, be cooled to-85 DEG C through ice chest--95 DEG C are carried out cryogenic separation, HF, CH
3f etc. are condensed into liquid, and boron trifluoride and nitrogen are still gas, enter out in cyclone separator, remove residual HF, CH from ice chest
3f etc., still for boron trifluoride and the nitrogen of gaseous state enter complexing tower tower reactor, in complexing tower packing there is complex reaction with the methyl phenyl ethers anisole liquid spraying downwards in the boron triflouride gas of rising, produces methyl phenyl ethers anisole-boron trifluoride complex;
Add continuously fresh boron triflouride gas to the first exchange rectifying column, along with boron trifluoride-10 are by transferring to gradually in liquid phase in gas phase, boron trifluoride-11 are item by transferring to gradually in gas phase in liquid phase, last boron trifluoride-10 at the bottom of the second exchange rectifying tower slowly enrichment get up, and boron trifluoride-11 the first exchange rectifying column tower top slowly enrichment get up;
The not discharging of boron-10 of cleavage column tower top, the also not discharging of complexing column overhead boron-11;
Through total system circulation in 72-148 hour, exchange rectifying column reached rectifying balance, and boron trifluoride-10 and boron trifluoride-11 abundance reach after designing requirement, can transfer smoothly normal production model to, simultaneously output boron trifluoride-10 and boron trifluoride-11 two kind of product.
2. according to a kind of start-up method of producing boron istope technique based on methyl phenyl ethers anisole-boron trifluoride claimed in claim 1, it is characterized in that can adopting sodium metal, calcium chloride, molecular sieve, active carbon, silica gel, ion to hand over the drier such as resin in nitrogen drying device; Methyl phenyl ethers anisole drying tower can be packed tower, plate column, valve tower or miscellaneous equipment form.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410414342.8A CN104190256B (en) | 2014-08-16 | 2014-08-16 | A kind of start-up method of producing boron istope technique based on methyl phenyl ethers anisole-boron trifluoride |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410414342.8A CN104190256B (en) | 2014-08-16 | 2014-08-16 | A kind of start-up method of producing boron istope technique based on methyl phenyl ethers anisole-boron trifluoride |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104190256A true CN104190256A (en) | 2014-12-10 |
| CN104190256B CN104190256B (en) | 2016-05-18 |
Family
ID=52075708
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410414342.8A Active CN104190256B (en) | 2014-08-16 | 2014-08-16 | A kind of start-up method of producing boron istope technique based on methyl phenyl ethers anisole-boron trifluoride |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104190256B (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106800299A (en) * | 2017-02-01 | 2017-06-06 | 洛阳和梦科技有限公司 | The quick preparation technology of high-purity boron trifluoride and recovery process for purification |
| CN111389224A (en) * | 2020-03-30 | 2020-07-10 | 辽宁鸿昊化学工业股份有限公司 | Method for enriching boron-10 isotope anti-blocking tower by distillation method |
| CN113583032A (en) * | 2021-07-23 | 2021-11-02 | 上海化工研究院有限公司 | Cracking device and method for boron trifluoride complex |
| CN113735132A (en) * | 2021-09-15 | 2021-12-03 | 黑龙江豪运药业有限公司 | Device and method for producing various abundant boron 10 isotopes in one tower |
| RU2777556C1 (en) * | 2021-07-29 | 2022-08-08 | Федеральное государственное бюджетное образовательное учреждение высшего образования "Российский химико-технологический университет имени Д.И. Менделеева" (РХТУ им. Д.И. Менделеева) | Boron isotope separation method |
| CN115608156A (en) * | 2022-12-19 | 2023-01-17 | 淄博颐康环保科技有限公司 | Sectional type cooling complexing device and complexing method for separating boron isotopes |
| CN116688756A (en) * | 2023-08-03 | 2023-09-05 | 天津天和盛新材料科技有限公司 | Continuous production process method for separating boron isotopes |
| CN116832615A (en) * | 2023-08-29 | 2023-10-03 | 天津天和盛新材料科技有限公司 | Continuous production process method for silicon isotopes |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS50119199A (en) * | 1974-03-07 | 1975-09-18 | ||
| US5419887A (en) * | 1994-01-25 | 1995-05-30 | Research & Development Institute, Inc. | Separation of the isotopes of boron by chemical exchange reactions |
| CN101993088A (en) * | 2010-10-15 | 2011-03-30 | 天津市泰源工业气体有限公司 | Technology of method for preparing high-purity boron trifluoride by rectification and adsorption combined purification mode |
| CN102774845A (en) * | 2012-07-06 | 2012-11-14 | 天津大学 | Device and method for producing boron trifluoride-11 electronic specific gas |
| CN102773016A (en) * | 2012-07-06 | 2012-11-14 | 天津大学 | Method and device for separately producing enriched boron-10 (10B) by using multiple serial towers |
-
2014
- 2014-08-16 CN CN201410414342.8A patent/CN104190256B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS50119199A (en) * | 1974-03-07 | 1975-09-18 | ||
| US5419887A (en) * | 1994-01-25 | 1995-05-30 | Research & Development Institute, Inc. | Separation of the isotopes of boron by chemical exchange reactions |
| CN101993088A (en) * | 2010-10-15 | 2011-03-30 | 天津市泰源工业气体有限公司 | Technology of method for preparing high-purity boron trifluoride by rectification and adsorption combined purification mode |
| CN102774845A (en) * | 2012-07-06 | 2012-11-14 | 天津大学 | Device and method for producing boron trifluoride-11 electronic specific gas |
| CN102773016A (en) * | 2012-07-06 | 2012-11-14 | 天津大学 | Method and device for separately producing enriched boron-10 (10B) by using multiple serial towers |
Non-Patent Citations (3)
| Title |
|---|
| SHUANG SONG ET AL: "Advances in boron-10 isotope separation by chemical exchange distillation", 《ANNALS OF NUCLEAR ENERGY》 * |
| 刘晶晶等: "硼同位素分离过程中络合剂的气提干燥模型", 《化学工程》 * |
| 王辉: "化学交换与精馏法分离硼同位素中试实验装置和分析装置的设计", 《中国优秀硕士学位论文全文数据库工程科技I辑》 * |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106800299A (en) * | 2017-02-01 | 2017-06-06 | 洛阳和梦科技有限公司 | The quick preparation technology of high-purity boron trifluoride and recovery process for purification |
| CN111389224A (en) * | 2020-03-30 | 2020-07-10 | 辽宁鸿昊化学工业股份有限公司 | Method for enriching boron-10 isotope anti-blocking tower by distillation method |
| CN113583032A (en) * | 2021-07-23 | 2021-11-02 | 上海化工研究院有限公司 | Cracking device and method for boron trifluoride complex |
| CN113583032B (en) * | 2021-07-23 | 2024-02-27 | 上海化工研究院有限公司 | Cracking device and method for boron trifluoride complex |
| RU2777556C1 (en) * | 2021-07-29 | 2022-08-08 | Федеральное государственное бюджетное образовательное учреждение высшего образования "Российский химико-технологический университет имени Д.И. Менделеева" (РХТУ им. Д.И. Менделеева) | Boron isotope separation method |
| CN113735132A (en) * | 2021-09-15 | 2021-12-03 | 黑龙江豪运药业有限公司 | Device and method for producing various abundant boron 10 isotopes in one tower |
| CN113735132B (en) * | 2021-09-15 | 2022-05-17 | 黑龙江豪运药业有限公司 | Device and method for producing various abundant boron 10 isotopes in one tower |
| CN115608156A (en) * | 2022-12-19 | 2023-01-17 | 淄博颐康环保科技有限公司 | Sectional type cooling complexing device and complexing method for separating boron isotopes |
| CN116688756A (en) * | 2023-08-03 | 2023-09-05 | 天津天和盛新材料科技有限公司 | Continuous production process method for separating boron isotopes |
| CN116688756B (en) * | 2023-08-03 | 2023-10-27 | 天津天和盛新材料科技有限公司 | Continuous production process method for separating boron isotopes |
| CN116832615A (en) * | 2023-08-29 | 2023-10-03 | 天津天和盛新材料科技有限公司 | Continuous production process method for silicon isotopes |
| CN116832615B (en) * | 2023-08-29 | 2023-11-21 | 天津天和盛新材料科技有限公司 | Continuous production process method for silicon isotopes |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104190256B (en) | 2016-05-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104190256B (en) | A kind of start-up method of producing boron istope technique based on methyl phenyl ethers anisole-boron trifluoride | |
| CN204746030U (en) | Carbon dioxide gas's device is absorbed to sled dress formula suitable for platform | |
| CN109999618B (en) | System and method for separating carbon dioxide from medium-high pressure gas source | |
| CN103435445A (en) | Method for separating mixture of ethanol alcohol and water | |
| CN102010294A (en) | Method and device for recovering polyethylene glycol raffinate byproduct from ethylene glycol process | |
| CN103435517A (en) | Yield-increasing and energy-saving technology of carbon dioxide stripping urea and equipment of carbon dioxide stripping urea | |
| CN204987654U (en) | Device is used multipurposely to synthetic ammonia tail gas | |
| CN106698785A (en) | Coal gasification wastewater phenol and ammonia recovery process | |
| CN103086822B (en) | A kind of separation method of m-pentadiene | |
| CN104045518A (en) | Preparation method of 2-methyl-3-butyne-2-ol | |
| CN101407444A (en) | Method for recovering methyl chloride in discharged tail gas of glyphosate / dimethyl phosphate production | |
| CN104209001B (en) | Method for industrial production of boron isotope products | |
| CN101012146A (en) | Method of separating and recovering methyl chloride from methyl chloride mixture gas | |
| CN101704709B (en) | Production method of high-purity vinylidene fluoride monomers | |
| CN104209003A (en) | Industrial production method for separating boron isotope product based on methyl-phenoxide-boron trifluoride complex | |
| CN102206196A (en) | Method for recovering morpholine from acidic waste water containing morpholine | |
| CN102173393B (en) | Sulfur tetrafluoride production technique | |
| CN102161925A (en) | Process for producing biological natural gas by using methane | |
| CN104926581A (en) | Process flow for dry separation of propylene and hydrogen chloride | |
| CN104844479A (en) | Tail gas recycling system and process used for stable co-production of melamine and urea | |
| CN102532060B (en) | Novel process for recovering N-methyl morpholine and N-ethyl morpholine | |
| CN108383082B (en) | Device and method for separating by-products generated in preparation of hydroxylamine hydrochloride by hydrolysis of nitromethane | |
| CN203128457U (en) | Device for removing saturated water in methane chloride | |
| CN105582811B (en) | A kind of purification of raw materials method for Separation of Boron Isotopes | |
| CN104230972B (en) | A kind of method to methyl phenyl ethers anisole-boron trifluoride complex purified treatment |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C41 | Transfer of patent application or patent right or utility model | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20160225 Address after: 100039, 2 floor, building 169, 4 Yongding Road, Beijing, Haidian District Applicant after: Beijing Genesis Technology Development Co., Ltd. Address before: 111000, Liaoning province Liaoyang Baita District East Three Street residential area North Gate No. 109 clean green dry cleaners Li Fengjie turn Applicant before: Liu Xiaoqin Applicant before: Wang Hong |
|
| C14 | Grant of patent or utility model | ||
| C41 | Transfer of patent application or patent right or utility model | ||
| GR01 | Patent grant | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20160425 Address after: 313299 Zhejiang city of Huzhou province Deqing County Wukang Changhong Street No. 198 Applicant after: ZHEJIANG CHUANGSHI LEIBO TECHNOLOGY CO., LTD. Address before: 100039, 2 floor, building 169, 4 Yongding Road, Beijing, Haidian District Applicant before: Beijing Genesis Technology Development Co., Ltd. |
|
| DD01 | Delivery of document by public notice |
Addressee: ZHEJIANG CHUANGSHI LEIBO TECHNOLOGY CO., LTD. Document name: Notification to Pay the Fees |
|
| DD01 | Delivery of document by public notice | ||
| DD01 | Delivery of document by public notice |
Addressee: ZHEJIANG CHUANGSHI LEIBO TECHNOLOGY Co.,Ltd. Document name: Notification of Termination of Patent Right |
|
| DD01 | Delivery of document by public notice | ||
| DD01 | Delivery of document by public notice |
Addressee: Patent director of Zhejiang Chuangshi Leibo Technology Co., Ltd Document name: Notice of approval of right to request |
|
| DD01 | Delivery of document by public notice | ||
| DD01 | Delivery of document by public notice |
Addressee: Patent director of Zhejiang Chuangshi Leibo Technology Co., Ltd Document name: payment instructions |
|
| DD01 | Delivery of document by public notice | ||
| DD01 | Delivery of document by public notice |
Addressee: Zhang Ling Document name: Notice of approval of request for restoration of rights |
|
| DD01 | Delivery of document by public notice |