CN103979497A - Method for preparing ultra-clean high-purity hydrochloric acid - Google Patents
Method for preparing ultra-clean high-purity hydrochloric acid Download PDFInfo
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- CN103979497A CN103979497A CN201410207482.8A CN201410207482A CN103979497A CN 103979497 A CN103979497 A CN 103979497A CN 201410207482 A CN201410207482 A CN 201410207482A CN 103979497 A CN103979497 A CN 103979497A
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- hydrochloric acid
- purity
- tetrafluoroethylene
- gas phase
- ultra
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- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 title claims abstract description 176
- 238000000034 method Methods 0.000 title claims abstract description 24
- 239000012498 ultrapure water Substances 0.000 claims abstract description 30
- 238000005406 washing Methods 0.000 claims abstract description 25
- 239000000126 substance Substances 0.000 claims abstract description 19
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000010439 graphite Substances 0.000 claims abstract description 16
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 16
- 238000010438 heat treatment Methods 0.000 claims abstract description 11
- 238000012856 packing Methods 0.000 claims abstract description 10
- 238000001914 filtration Methods 0.000 claims abstract description 7
- 238000005342 ion exchange Methods 0.000 claims abstract description 6
- 238000001704 evaporation Methods 0.000 claims abstract description 5
- 239000003957 anion exchange resin Substances 0.000 claims abstract description 4
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 claims description 42
- 239000012071 phase Substances 0.000 claims description 27
- 238000009835 boiling Methods 0.000 claims description 20
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical class C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 17
- 239000007788 liquid Substances 0.000 claims description 16
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 14
- 229910000375 tin(II) sulfate Inorganic materials 0.000 claims description 14
- RCIVOBGSMSSVTR-UHFFFAOYSA-L stannous sulfate Chemical compound [SnH2+2].[O-]S([O-])(=O)=O RCIVOBGSMSSVTR-UHFFFAOYSA-L 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 12
- 238000010521 absorption reaction Methods 0.000 claims description 10
- 238000010992 reflux Methods 0.000 claims description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 239000001913 cellulose Substances 0.000 claims description 9
- 229920002678 cellulose Polymers 0.000 claims description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 238000007598 dipping method Methods 0.000 claims description 6
- 239000000945 filler Substances 0.000 claims description 6
- 239000010453 quartz Substances 0.000 claims description 6
- 238000002203 pretreatment Methods 0.000 claims description 5
- 238000006298 dechlorination reaction Methods 0.000 claims description 4
- 230000008020 evaporation Effects 0.000 claims description 4
- 239000007791 liquid phase Substances 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- 238000000926 separation method Methods 0.000 claims description 4
- 238000002791 soaking Methods 0.000 claims description 4
- 239000000443 aerosol Substances 0.000 claims description 3
- 238000005470 impregnation Methods 0.000 claims description 3
- 238000002844 melting Methods 0.000 claims description 3
- 230000008018 melting Effects 0.000 claims description 3
- 230000007935 neutral effect Effects 0.000 claims description 3
- 238000009833 condensation Methods 0.000 claims description 2
- 230000005494 condensation Effects 0.000 claims description 2
- 238000000465 moulding Methods 0.000 claims description 2
- 238000007654 immersion Methods 0.000 claims 1
- 239000003153 chemical reaction reagent Substances 0.000 abstract description 31
- 238000004821 distillation Methods 0.000 abstract description 12
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- 238000000746 purification Methods 0.000 abstract description 3
- 229920000049 Carbon (fiber) Polymers 0.000 abstract description 2
- 238000010923 batch production Methods 0.000 abstract 1
- 230000000382 dechlorinating effect Effects 0.000 abstract 1
- 239000000047 product Substances 0.000 description 20
- 229910021645 metal ion Inorganic materials 0.000 description 17
- 239000011347 resin Substances 0.000 description 15
- 229920005989 resin Polymers 0.000 description 15
- 239000000243 solution Substances 0.000 description 10
- 239000002585 base Substances 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 7
- 238000002360 preparation method Methods 0.000 description 7
- 238000001816 cooling Methods 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 238000001179 sorption measurement Methods 0.000 description 5
- 238000003860 storage Methods 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 4
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 4
- 125000000129 anionic group Chemical group 0.000 description 3
- 150000001450 anions Chemical class 0.000 description 3
- 238000013459 approach Methods 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 239000003610 charcoal Substances 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 238000007689 inspection Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- 238000003556 assay Methods 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 239000002826 coolant Substances 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000000088 plastic resin Substances 0.000 description 2
- 230000000306 recurrent effect Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 230000003245 working effect Effects 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910001413 alkali metal ion Inorganic materials 0.000 description 1
- 229910001420 alkaline earth metal ion Inorganic materials 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 238000007084 catalytic combustion reaction Methods 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 230000003749 cleanliness Effects 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229910001510 metal chloride Inorganic materials 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000011236 particulate material Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 235000011150 stannous chloride Nutrition 0.000 description 1
- -1 styrene series anion Chemical class 0.000 description 1
- AXZWODMDQAVCJE-UHFFFAOYSA-L tin(II) chloride (anhydrous) Chemical compound [Cl-].[Cl-].[Sn+2] AXZWODMDQAVCJE-UHFFFAOYSA-L 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses an industrial method for preparing ultra-clean high-purity reagent-grade hydrochloric acid from industrial hydrochloric acid through purification. The method comprises the following steps: filtering the industrial hydrochloric acid, dechlorinating activated carbon fibers, performing ion exchange through an anion exchange resin column, heating and evaporating; removing high-boiling-point substances out of gas-phase fractions through a super-pure polytetrafluoroethylene-dipped graphite packing tower, washing the gas-phase fractions in a stannous mono-sulfate solution, washing with high-purity water, then absorbing the high-purity water , thus obtaining the ultra-clean high-purity hydrochloric acid product. The method also can comprise a step of second distillation. The aim of realizing high-quality high-efficiency industrial batch production of ultra-clean high-purity reagent hydrochloric acid is reached.
Description
Technical field
The present invention relates to the manufacture method of reagent grade hydrochloric acid, specifically from the purified industrial method of preparing ultra-clean and high pure chemical reagent grade hydrochloric acid of technical-grade hydrochloric acid.
Background technology
Ultra-clean and high pure chemical reagent (Ultra-clean and High-purity Reagents) is called process chemical (Process Chemicals) in the world, it is one of key basic chemical industry material in unicircuit (IC) and super large-scale integration (VLSI) making processes, be mainly used in cleaning, the etching of chip, ultra-clean and high pure chemical reagent is also for the cleaning on chip doping and depositing technology and silicon wafer surface in addition.The purity of ultra-clean and high pure chemical reagent and cleanliness factor yield rate, electrical property and the reliability on unicircuit all has very important impact.The main application fields of ultra-clean and high pure chemical reagent comprises semicon industry and sun power industry and precision components making, and semicon industry requires relatively high with ultra-clean and high pure chemical reagent, and China's high-end product mainly relies on import, domestic main production mid and low-end products at present.
Semiconductor equipment and material structure (SEMI) have been set up SEMI chemical reagent standard committee in 1975, formulate specially the international standard of ultra-clean and high pure chemical reagent.Current international SEMI standardization body is divided into 4 grades by ultra-clean and high pure chemical reagent by range of application: (1) SEMI-C1 standard (being applicable to the making of >1.2 μ m IC Technology); (2) SEMI-C7 standard (being suitable for the making of 0.8-1.2 μ m IC Technologies); (3) SEMI-C8 standard (being applicable to the making of 0.2-0.6 μ m IC Technology); (4) SEMI-C12 standard (being applicable to the making of 0.09-0.2 μ m IC Technology).
The production method of purification of ultra-clean and high pure chemical reagent hydrochloric acid is a lot of at present, there are isothermal diffusion process, distillation method, Asia boil method, rectification method, ion exchange adsorption, gas assimilating method etc., Asia in clean environment (or boiling in two Asia) the method for purification effect of boiling is best, and product purity is also the highest.Sub-boiling distillation is a kind of very effective means of removing metal ion and solia particle in liquid, the key of this technology be exactly by the liquid heat being purified to lower than boiling point with 5～20 DEG C.Because liquid does not reach boiling point, and the gas phase of liquid equilibrium is also just no longer made up of a large amount of steam thing grains, but with molecularity and liquid equilibrium, therefore in steam, seldom carries or do not carry secretly metal ion and solia particle secretly.But sub-boiling distillation exists the high deficiency of industrial production cost that yields poorly, the sub-boiling distillation to volatile products especially, because its tower reactor liquid phase temperature rate of change is larger, causes temperature control to regulate frequent, causes the stability decreases of technological operation.To produce in addition the high-purity hydrochloric acid that single metal ion is less than 0.1ppb, use technical-grade hydrochloric acid is raw material, single sub-boiling distillation cannot meet the specification of quality that single metal ion is less than the high-purity hydrochloric acid of 0.1ppb, industrialized sub-boiling distillation can not save the treatment step in early stage to raw material hydrochloric acid, still needs to take the multistage purifying process of distillation → physical or chemical treatment → gas absorption → sub-boiling distillation.
CN102923660A discloses a kind of preparation method of reagent hydrochloric acid, by the technical hydrochloric acid dilution of HCl >=36.5%, successively through plastic resin treatment, charcoal absorption processing, add tin protochloride to mix after distillation, collect cut and obtain reagent hydrochloric acid.Plastic resin treatment is to utilize most metal chlorides in concentrated hydrochloric acid easily to form the characteristic of network cl anion, as Zn
2+, Fe
3+, Cu
2+, Co
2+, Mn
2+in hydrochloric acid, generate anion complex: Me
n++ xCl
-=MeCl
x -(X – is n), use anionite-exchange resin by MeCl
x -(X – is n)adsorption
,but Ca
2+, Mg
2+, Na
+, Sr
2+, Ba
2+can not form MeCl in alkali and alkaline earth metal ions ion
x -(X – is n)and can not remove; Utilize the free Cl of charcoal absorption and organic substance; Utilize SnCl
2reductibility further process free Cl, reduction Fe
3+, As
3+.There are three deficiencies in the method: the one, and the free Cl in technical hydrochloric acid can be oxidized anionite-exchange resin, can there is part group and come off and chain rupture in the rear resin of oxidation, produce rudimentary amine and enter into hydrochloric acid soln, cause the pollution to hydrochloric acid, and negative resin exchange capacity is declined, shorten its work-ing life; The 2nd, the SnCl adding
2finally stay in dilute hydrochloric acid, the large concentration of volume is low, reclaims more difficult; The 3rd, SnCl
2can not remove the not adsorbable Ca of anionite-exchange resin
2+, Ba
2+, Sr
2+plasma.
Summary of the invention
Object of the present invention, for above technical problem, proposes a kind of method of efficiently preparing high-purity hydrochloric acid.
Concrete technical scheme of the present invention is as follows: technical hydrochloric acid is filtered by the micro-strainer in 0.45 μ m aperture, flow through after activated carbon fiber dechlorination, enter anion-exchange resin column and carry out ion-exchange, heater heats evaporation, control vapor pressure is 0.1～0.15MPa, gas phase fraction is removed after high boiling substance by the graphite packing tower of the ultrapure tetrafluoroethylene of dipping, enter gas-fog separator and isolate liquid phase, particulate and gas phase fraction, gas phase fraction enters 20～50 DEG C, the stannous sulfate solution of weight concentration 10～20% washs, after the high purity water washing of 10～20 DEG C, enter gas-fog separator again and carry out aerosol separation, gas phase fraction absorbs with the high purity water of 10～15 DEG C, when absorption liquid density d
15when=1.185～1.194g/ml, obtain SEMI-C8 level high-purity hydrochloric acid product.
For further improving the purity of hydrochloric acid, can also comprise second distillation, the SEMI-C8 level high-purity hydrochloric acid product obtaining is joined in rectifying tower, in the tower joint of rectifying tower, add thread high purity quartz as filler, heating kettle heating makes hydrochloric acid boiling rectifying, and controlling reflux ratio is 3～6 ︰ 1, and the gas phase fraction of tower top is after condensation, with the micro-strainer filtration in 0.1 μ m aperture, become SEMI-C12 level high-purity hydrochloric acid product.
In the present invention, micro-strainer preferably uses the micro-filter of ultrapure tetrafluoroethylene material, guarantees that pollutent does not appear in preparation process.
Activated carbon fiber is preferably used cellulose base activated carbon fiber, before use, carry out following pre-treatment: cellulose base activated carbon fiber is boiled and washed after 1～10 hour in pure water, soak 8～20 hours with the mixed organic solvents of the volume ratio of ethanol, methyl alcohol or Yi Bing Chun ︰ acetone=4～6 ︰ 1, wash 3～10 hours with the hydrochloric acid of 1～5wt% boiling again, then boil and wash 3～10 hours with the sodium hydroxide of 1～5wt%, finally with pure water soaking, boil and be washed till washing water and be neutral, be dried to constant weight at 100～120 DEG C.Free Cl can be adsorbed and reduce to activated carbon fiber after treatment, free Cl concentration can drop to 0.05～0.1ppm, its rate of adsorption is 10～100 times of gac, loading capacity is gac 5～10 times, except go back adsorb organic compound matter, part heavy metal ion.
Anionite-exchange resin adopts strong-basicity styrene series anion resin, as 201 × 7 strongly basic anionic resins, can exchange Zn
2+, Fe
3+, Cu
2+, Co
2+, Mn
2+in hydrochloric acid, generate anion complex Me
n++ xCl
-=MeCl
x -(X – is n), remove Zn
2+, Fe
3+, Cu
2+, Co
2+, Mn
2+deng metal ion.
Well heater preferably makes the heat exchanger obtaining with the following method: by the ultrapure tetrafluoroethylene of graphite impregnation melting or flood after ultrapure polytetrafluoroethylsolution solution, linking moulding by tetrafluoroethylene becomes interchanger.
The graphite packing of flooding ultrapure tetrafluoroethylene be by graphite impregnation at the ultrapure tetrafluoroethylene of melting or be immersed in the particulate material forming after ultrapure polytetrafluoroethylsolution solution, graphite is embedded in tetrafluoroethylene.
In above-mentioned stannous sulfate solution, can also contain appropriate sulfuric acid, as the sulfuric acid of 1～10wt%, become the sub-solution of tin of acid sulfuric acid, more be conducive to Ca
2+, Ba
2+, Sr
2+isoionic precipitation, and can prevent stannous sulfate hydrolytic precipitation.
The present invention overcome sub-boiling distillation and the current shortcoming and defect of prior art, reached the object of high-quality, efficient, industrialized mass production ultra-clean and high pure chemical reagent hydrochloric acid.Compared with prior art, tool has the following advantages in the present invention:
1, adopt the free Cl of pretreated cellulose base carbon fiber adsorption and catalytic combustion reduction, free Cl can drop to 0.05～0.1ppm, remove more than 99.8% free Cl in raw material hydrochloric acid (liquid phase), and the oxidation of the free Cl of minimizing to anionite-exchange resin, reduce the pollution of anionite-exchange resin oxidation products to hydrochloric acid, extend the work-ing life of anionite-exchange resin.
2, gas phase fraction is after 10～20% stannous sulfate solution washs, and reduciblely removes free Cl, Fe remaining in gas phase hydrochloric acid
3+, As
3+, can also remove the not adsorbable Ca of anionite-exchange resin with the form precipitation of vitriol
2+, Ba
2+, Sr
2+plasma.Collaborative, complementary, the synergy effect of negative resin Adsorption metal ion are played.Stannous sulfate strength of solution is high, volume is little, therefore make the recovery of pink salt become easy.
3, use the graphite packing tower of the ultrapure tetrafluoroethylene of dipping, the efficient gas-fog separator of two-stage carries out gas-liquid separation, remove or reduce metal ion, the solia particle that gas phase hydrochloric acid is carried secretly, both having ensured that rectifying had higher gas speed, having played again the effect of the sub-rectifying of boiling.High-purity hydrochloric acid product single metal ion after a rectifying drops to respectively 0.5～1ppb, and free Cl does not detect, and exceeds the specification of quality of SEMI-C8 grade standard, approaches or meets SEMI-C12 standard-required.
4, in the tower joint of rectifying tower, add thread high purity quartz as filler, make it possess good aerosol centrifugation, reduce metal ion and taken out of by steam simultaneously, improved the high and product purity of separation efficiency, after secondary rectifying, product quality indicator exceedes SEMI-C12 standard.
Brief description of the drawings
Fig. 1 is preparation process in one embodiment of the present invention and the equipment schematic diagram of use.
The device name that number in the figure is corresponding: the ultrapure tetrafluoroethylene micro-strainer of 1-aperture, 0.45 μ m; 2-pure quartz glass heat exchanger package; 3-activated carbon fiber post; 4-anion-exchange resin column; 5-flood the graphite heater of ultrapure tetrafluoroethylene; 6-flood the graphite heater of ultrapure tetrafluoroethylene; 7-flood the graphite packing stripping tower of ultrapure tetrafluoroethylene; 8-be incubated efficient gas-fog separator (liner is ultrapure tetrafluoroethylene); 9-stannous sulfate washing tank (liner is ultrapure tetrafluoroethylene, and built-in heat exchanger tube side is ultrapure tetrafluoroethylene tube bank); 10-high purity water washing tank (liner is ultrapure tetrafluoroethylene, and built-in heat exchanger tube side is ultrapure tetrafluoroethylene tube bank); 11-high purity water tourie (liner is ultrapure tetrafluoroethylene, and built-in heat exchanger tube side is ultrapure tetrafluoroethylene tube bank); 12-be incubated efficient gas-fog separator (liner is ultrapure tetrafluoroethylene); 13-Venturi spray tube (liner is ultrapure tetrafluoroethylene); 14-pure quartz glass spinner-type flowmeter (ultrapure tetrafluoroethylene rotor); 15-liner is the pump of ultrapure tetrafluoroethylene; The ultrapure tetrafluoroethylene micro-strainer of 16-aperture, 0.22 μ m; 17-middle product storage tank (liner is ultrapure tetrafluoroethylene); 18-high-purity thread quartz filler rectifying tower group; 19-ultra-clean and high pure chemical reagent hydrochloric acid tank (liner is ultrapure tetrafluoroethylene); The ultrapure tetrafluoroethylene micro-strainer of 20-aperture, 0.1 μ m.
Embodiment
Pre-treatment before cellulose base activated carbon fiber is used: first boil and wash 6 hours with pure water, with the water-soluble impurity of the remaining trace of stripping; By the ethanol of volume ratio 5 ︰ 1 and the mixed organic solvents soaking at room temperature of acetone 12 hours, with the absorption property of Activation Activity charcoal fiber and remove residual organic substance, organic solvent taked low temperature, vacuum analysis method to reclaim; Boil and wash 6 hours with the hydrochloric acid of 3wt% again, with the caustic solubility impurity of the remaining trace of stripping; Then boil and wash 6 hours with the aqueous sodium hydroxide solution of 3wt%, with the acid-soluble impurity of the remaining trace of stripping; Finally with pure water soaking, boil be washed till washing water be neutral only, and be dried to constant weight at 110 DEG C.
Embodiment 1:
A, pre-treatment and a rectifying:
By 36.5% technical hydrochloric acid, (single metal ion content is about respectively 1～80ppm, free Cl concentration is 60ppm) filter by the ultrapure tetrafluoroethylene micro-strainer 1 of aperture 0.45 μ m continuously with the speed of 500L/h, pure quartz glass heat exchanger package 2 tentatively heats, 3 dechlorinations of pretreated cellulose base activated carbon fiber post, after 201 × 7 strongly basic anionic resin post 4 ion-exchanges, adopt the graphite heater 5 of the high-purity tetrafluoroethylene of dipping, 6 heating evaporations, controlling vapor pressure is 0.12Mpa left and right, gas phase fraction is removed after high boiling substance (stripping rectifying) by flooding the graphite packing tower 7 of ultrapure tetrafluoroethylene, enter the efficient gas-fog separator 8 of insulation and remove droplet and particulate.Gas phase fraction enters the chemical treatment of B step.
Liquid fraction is 20.4～21.5% a dilute hydrochloric acid, mixes with technical hydrochloric acid without cooling, realizes after energy reuse, is directly used in the rectifying of general reagent hydrochloric acid.
To carrying out middle control inspection by the hydrochloric acid of cellulose base activated carbon fiber post 3, free Cl drops to 0.08ppm, and the gas phase hydrochloric acid after stripping rectifying is carried out to middle control inspection, and single metal ion drops to respectively 10～40ppb.
B, chemical treatment and pure water washing and absorption:
In washing tank 9, add the acid stannous sulfate aqueous solution that contains 5wt% sulfuric acid and 10wt% stannous sulfate, in high purity water washing tank 10, high purity water tourie 11, add respectively a certain amount of high purity water (resistivity 18.3 Ω cm), to open liner be ultrapure tetrafluoroethylene pump 15 makes in high purity water tourie 11 liquid is in recurrent state, and the size of its flow regulates by pure quartz glass spinner-type flowmeter 14.
Wash by washing tank 9 chemical subtractions, high purity water washing tank 10 respectively through the gas phase fraction of removing droplet and particulate in gas-fog separator 8, being incubated efficient gas-fog separator 12 removes after droplet and particulate, the negative pressure (0.01～-0.04MPa) being produced by Venturi spray tube 13 is extracted in high purity water tourie 11, and circulation absorbs becomes the middle product of ultra-clean and high pure chemical reagent hydrochloric acid.
In the middle of ultra-clean and high pure chemical reagent hydrochloric acid, in product preparation process, the temperature of the stannous sulfate chemical pretreatment solution in washing tank 9 is controlled between 25～50 DEG C, and should regularly replace, and relief liquor is for remanufacture technical grade stannic oxide.High purity water washings temperature in high purity water washing tank 10 is controlled at 15～20 DEG C, when its density d
20(content of hydrochloric acid: 31.14～32.00%), put it into common high purity reagent hydrochloric acid tank, and change high purity water when=1.155～1.158g/ml.
High purity water absorption liquid temperature in high purity water tourie 11 is controlled at 10～15 DEG C, when its density d
15when=1.185～1.194g/ml (content of hydrochloric acid 36.31～38.00wt%), after filtering by the ultrapure tetrafluoroethylene micro-strainer 16 of 0.22 μ m, product storage tank 17 in the middle of being pumped into by pump 15.
In hydrochloric acid warp in middle product storage tank 17, control detects, single metal ion drops to respectively 0.5～1ppb, and free Cl does not detect, and exceeds the specification of quality of SEMI-C8 grade standard, approach or meet SEMI-C12 standard-required, the salt acid product that can be used as SEMI-C8 standard-required uses.
C, secondary rectifying:
By product in the middle of ultra-clean and high pure chemical reagent hydrochloric acid with 300L/h, join continuously in rectifying tower group, in the tower joint of rectifying tower group 18, add thread high purity quartz as filler, when the volume of hydrochloric acid in heating kettle be heating kettle volume 30～50% time, start to carry out electrically heated rectifying, controlling gas phase fraction and condensing reflux weight ratio is 4 ︰ 1.The size of reflux ratio is taken over a business temperature and the flow of water coolant in tubular type reflux exchanger by control tower, regulate the opening degree of quantity of reflux variable valve, or the hold-time that electromagnetism pendulum opens and closes realizes.
After the gas phase fraction condensing cooling on after-fractionating tower top, enter ultra-clean and high pure chemical reagent hydrochloric acid tank 19, control its density d
15=1.190～1.194g/ml, through the ultra-clean filtration of the ultrapure tetrafluoroethylene micro-strainer 20 of 0.1 μ m, ultra-clean packing can obtain single metal ion and be less than 0.05～0.1ppb, the ultra-clean and high pure chemical reagent hydrochloric acid that content is 37.5%, its assay is in table 1, and quality index exceedes SEMI-C12 standard.
The liquid fraction of after-fractionating tower still is 20～21% secondary dilute hydrochloric acid, without the cooling pure quartz glass heat exchanger package 2 that directly enters, by with the thermal exchange of primary industry hydrochloric acid, realize energy reuse.20～21% secondary dilute hydrochloric acid is for 5N NH
4the preparation of the Cl aqueous solution.
Embodiment 2:
A, pre-treatment and a rectifying:
By 31% technical hydrochloric acid, (single metal ion content is about respectively 1～80ppm, free Cl concentration is 50ppm) filter by the ultrapure tetrafluoroethylene micro-strainer 1 of aperture 0.45 μ m continuously with the speed of 500L/h, pure quartz glass heat exchanger package 2 tentatively heats, 3 dechlorinations of pretreated cellulose base activated carbon fiber post, after 201 × 7 strongly basic anionic resin post 4 ion-exchanges, adopt the graphite heater 5 of the high-purity tetrafluoroethylene of dipping, 6 heating evaporations, controlling vapor pressure is 0.15Mpa left and right, gas phase fraction is removed after high boiling substance (stripping rectifying) by flooding the graphite packing tower 7 of ultrapure tetrafluoroethylene, enter the efficient gas-fog separator 8 of insulation and remove droplet and particulate.Gas phase fraction enters the chemical treatment of B step.
Liquid fraction is 20.4～21.5% a dilute hydrochloric acid, mixes with technical hydrochloric acid without cooling, realizes after energy reuse, is directly used in the rectifying of general reagent hydrochloric acid.
Through checking passing through control in the hydrochloric acid of cellulose base activated carbon fiber post 3, free Cl drops to 0.08ppm, and the gas phase hydrochloric acid after stripping rectifying is carried out to middle control inspection, and single metal ion drops to respectively 10～40ppb.
B, chemical treatment and pure water washing and absorption:
In washing tank 9, add the acid stannous sulfate aqueous solution that contains 5wt% sulfuric acid and 15wt% stannous sulfate, in high purity water washing tank 10, high purity water tourie 11, add respectively a certain amount of high purity water (resistivity 18.3 Ω cm), to open liner be ultrapure tetrafluoroethylene pump 15 makes in high purity water tourie 11 liquid is in recurrent state, and the size of its flow regulates by pure quartz glass spinner-type flowmeter 14.
Wash by washing tank 9 chemical subtractions, high purity water washing tank 10 respectively through the gas phase fraction of removing droplet and particulate in gas-fog separator 8, being incubated efficient gas-fog separator 12 removes after droplet and particulate, the negative pressure (0.01～-0.04MPa) being produced by Venturi spray tube 13 is extracted in high purity water tourie 11, and circulation absorbs becomes the middle product of ultra-clean and high pure chemical reagent hydrochloric acid.
In the middle of ultra-clean and high pure chemical reagent hydrochloric acid, in product preparation process, the temperature of the stannous sulfate chemical pretreatment solution in washing tank 9 is controlled between 25～50 DEG C, and should regularly replace, and relief liquor is for remanufacture technical grade stannic oxide.High purity water washings temperature in high purity water washing tank 10 is controlled at 15～20 DEG C, when its density d
20(content of hydrochloric acid: 31.14～32.00%), put it into common high purity reagent hydrochloric acid tank, and change high purity water when=1.155～1.158g/ml.
High purity water absorption liquid temperature in high purity water tourie 11 is controlled at 10～15 DEG C, when its density d
15when=1.185～1.194g/ml (content of hydrochloric acid 36.31～38.00wt%), after filtering by the ultrapure tetrafluoroethylene micro-strainer 16 of 0.22 μ m, product storage tank 17 in the middle of being pumped into by pump 15.
In hydrochloric acid warp in middle product storage tank 17, control detects, single metal ion drops to respectively 0.5～1ppb, and free Cl does not detect, and exceeds the specification of quality of SEMI-C8 grade standard, approach or meet SEMI-C12 standard-required, the salt acid product that can be used as SEMI-C8 standard-required uses.
C, secondary rectifying:
By product in the middle of ultra-clean and high pure chemical reagent hydrochloric acid with 300L/h, join continuously in rectifying tower group, in the tower joint of rectifying tower group 18, add thread high purity quartz as filler, when the volume of hydrochloric acid in heating kettle be heating kettle volume 30～50% time, start to carry out electrically heated rectifying, controlling gas phase fraction and condensing reflux weight ratio is 5 ︰ 1.The size of reflux ratio is taken over a business temperature and the flow of water coolant in tubular type reflux exchanger by control tower, regulate the opening degree of quantity of reflux variable valve, or the hold-time that electromagnetism pendulum opens and closes realizes.
After the gas phase fraction condensing cooling on after-fractionating tower top, enter ultra-clean and high pure chemical reagent hydrochloric acid tank 19, control its density d
15=1.190～1.194g/ml, through the ultra-clean filtration of the ultrapure tetrafluoroethylene micro-strainer 20 of 0.1 μ m, ultra-clean packing can obtain single metal ion and be less than 0.05～0.1ppb, the ultra-clean and high pure chemical reagent hydrochloric acid that content is 37.5%, its assay is in table 2, and quality index exceedes SEMI-C12 standard.
The liquid fraction of after-fractionating tower still is 20～21% secondary dilute hydrochloric acid, without the cooling pure quartz glass heat exchanger package 2 that directly enters, by with the thermal exchange of primary industry hydrochloric acid, realize energy reuse.20～21% secondary dilute hydrochloric acid is for 5N NH
4the preparation of the Cl aqueous solution.
Table 1:
Table 2:
Claims (6)
1. prepare the method for high-purity hydrochloric acid for one kind, it is characterized in that, technical hydrochloric acid is filtered by the micro-strainer in 0.45 μ m aperture, flow through after activated carbon fiber dechlorination, enter anion-exchange resin column and carry out ion-exchange, heater heats evaporation, control vapor pressure is 0.1～0.15MPa, gas phase fraction is removed after high boiling substance by the graphite packing tower of the ultrapure tetrafluoroethylene of dipping, enter gas-fog separator and isolate liquid phase, particulate and gas phase fraction, gas phase fraction enters 20～50 DEG C, the stannous sulfate solution of weight concentration 10～20% washs, after the high purity water washing of 10～20 DEG C, enter gas-fog separator again and carry out aerosol separation, gas phase fraction absorbs with the high purity water of 10～15 DEG C, when absorption liquid density d
15when=1.185～1.194g/ml, obtain SEMI-C8 level high-purity hydrochloric acid product.
2. prepare according to claim 1 the method for high-purity hydrochloric acid, it is characterized in that, also comprise secondary rectifying, the SEMI-C8 level high-purity hydrochloric acid product obtaining is joined in rectifying tower, in the tower joint of rectifying tower, add thread high purity quartz as filler, heating kettle heating makes hydrochloric acid boiling rectifying, controlling gas phase fraction and condensing reflux weight ratio is 3～6 ︰ 1, the gas phase fraction of tower top is after condensation, with the micro-strainer filtration in 0.1 μ m aperture, become SEMI-C12 level high-purity hydrochloric acid product.
3. according to the method for preparing high-purity hydrochloric acid described in claim 1 or 2, it is characterized in that, described activated carbon fiber is carried out following pre-treatment before using: activated carbon fiber is boiled in pure water and wash after 1～10 hour, the mixed organic solvents immersion forming by the volume ratio of ethanol, methyl alcohol or Yi Bing Chun ︰ acetone=4～6 ︰ 1 8～20 hours, wash 3～10 hours with the hydrochloric acid of 1～5wt% boiling again, then boil and wash 3～10 hours with the sodium hydroxide of 1～5wt%, finally with pure water soaking, boil and be washed till washing water and be neutral, be dried to constant weight at 100～120 DEG C.
4. the method for preparing according to claim 3 high-purity hydrochloric acid, is characterized in that, described activated carbon fiber is cellulose base activated carbon fiber.
5. according to the method for preparing high-purity hydrochloric acid described in claim 1 or 2, it is characterized in that, described well heater is by after the tetrafluoroethylene of graphite impregnation melting or dipping polytetrafluoroethylsolution solution, links the heat exchanger of moulding by tetrafluoroethylene.
6. according to the method for preparing high-purity hydrochloric acid described in claim 1 or 2, it is characterized in that, in described stannous sulfate solution, also contain the sulfuric acid of 1-10wt%.
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| CN105692554A (en) * | 2016-01-18 | 2016-06-22 | 广西柳化氯碱有限公司 | Method and equipment for producing high-concentration anhydrous hydrogen chloride methanol solution |
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| CN105233897A (en) * | 2015-11-10 | 2016-01-13 | 郝东辉 | Acid purification device with built-in temperature sensor |
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| CN112062089A (en) * | 2020-08-27 | 2020-12-11 | 福建天甫电子材料有限公司 | Preparation process of electronic grade hydrochloric acid |
| WO2022241690A1 (en) * | 2021-05-19 | 2022-11-24 | Dow Global Technologies Llc | Processes for purifying organic amines |
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