CN110482764A - The regenerative system of raffinate in hydrogen dioxide solution production by anthraquinone process technique - Google Patents
The regenerative system of raffinate in hydrogen dioxide solution production by anthraquinone process technique Download PDFInfo
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- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 title claims abstract description 79
- 238000000034 method Methods 0.000 title claims abstract description 50
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 150000004056 anthraquinones Chemical class 0.000 title claims abstract description 34
- 230000008569 process Effects 0.000 title claims abstract description 32
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 23
- 230000001172 regenerating effect Effects 0.000 title claims abstract description 13
- 239000007788 liquid Substances 0.000 claims abstract description 84
- 238000003860 storage Methods 0.000 claims abstract description 17
- 239000012224 working solution Substances 0.000 claims description 39
- 239000000243 solution Substances 0.000 claims description 17
- 239000007789 gas Substances 0.000 claims description 14
- 238000009826 distribution Methods 0.000 claims description 10
- 230000008676 import Effects 0.000 claims description 9
- 230000000630 rising effect Effects 0.000 claims description 7
- -1 raffinate pipeline Chemical compound 0.000 abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 51
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 29
- 230000008929 regeneration Effects 0.000 description 20
- 238000011069 regeneration method Methods 0.000 description 20
- 238000000605 extraction Methods 0.000 description 16
- 239000007857 degradation product Substances 0.000 description 15
- 239000003513 alkali Substances 0.000 description 14
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 14
- 238000007254 oxidation reaction Methods 0.000 description 10
- 230000000694 effects Effects 0.000 description 9
- 239000001257 hydrogen Substances 0.000 description 9
- 229910052739 hydrogen Inorganic materials 0.000 description 9
- 230000003647 oxidation Effects 0.000 description 9
- WHRIKZCFRVTHJH-UHFFFAOYSA-N ethylhydrazine Chemical compound CCNN WHRIKZCFRVTHJH-UHFFFAOYSA-N 0.000 description 8
- 229910000027 potassium carbonate Inorganic materials 0.000 description 7
- 239000002585 base Substances 0.000 description 6
- 230000018044 dehydration Effects 0.000 description 6
- 238000006297 dehydration reaction Methods 0.000 description 6
- 238000005984 hydrogenation reaction Methods 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 238000007701 flash-distillation Methods 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- YEVQZPWSVWZAOB-UHFFFAOYSA-N 2-(bromomethyl)-1-iodo-4-(trifluoromethyl)benzene Chemical compound FC(F)(F)C1=CC=C(I)C(CBr)=C1 YEVQZPWSVWZAOB-UHFFFAOYSA-N 0.000 description 4
- JORLUGVBYJSSAW-UHFFFAOYSA-N 2-ethyl-1,2,3,4-tetrahydroanthracene-9,10-dione Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1CC(CC)CC2 JORLUGVBYJSSAW-UHFFFAOYSA-N 0.000 description 4
- 239000004593 Epoxy Substances 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 239000000284 extract Substances 0.000 description 4
- 239000002351 wastewater Substances 0.000 description 4
- SNDGLCYYBKJSOT-UHFFFAOYSA-N 1,1,3,3-tetrabutylurea Chemical compound CCCCN(CCCC)C(=O)N(CCCC)CCCC SNDGLCYYBKJSOT-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 3
- 125000001165 hydrophobic group Chemical group 0.000 description 3
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- RJGDLRCDCYRQOQ-UHFFFAOYSA-N anthrone Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3CC2=C1 RJGDLRCDCYRQOQ-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 229910001882 dioxygen Inorganic materials 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 238000012805 post-processing Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000010025 steaming Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- OTBHDFWQZHPNPU-UHFFFAOYSA-N 1,2,3,4-tetrahydroanthracene-9,10-dione Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1CCCC2 OTBHDFWQZHPNPU-UHFFFAOYSA-N 0.000 description 1
- NZTJFABTLXYHPJ-UHFFFAOYSA-N C(C)C1CC2=CC3=CC=CC=C3C=C2CC1 Chemical compound C(C)C1CC2=CC3=CC=CC=C3C=C2CC1 NZTJFABTLXYHPJ-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- QNEFNFIKZWUAEQ-UHFFFAOYSA-N carbonic acid;potassium Chemical compound [K].OC(O)=O QNEFNFIKZWUAEQ-UHFFFAOYSA-N 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 229910000078 germane Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 238000000053 physical method Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 238000010079 rubber tapping Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B15/00—Peroxides; Peroxyhydrates; Peroxyacids or salts thereof; Superoxides; Ozonides
- C01B15/01—Hydrogen peroxide
- C01B15/022—Preparation from organic compounds
- C01B15/023—Preparation from organic compounds by the alkyl-anthraquinone process
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F9/00—Multistage treatment of water, waste water or sewage
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/001—Processes for the treatment of water whereby the filtration technique is of importance
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/02—Treatment of water, waste water, or sewage by heating
- C02F1/04—Treatment of water, waste water, or sewage by heating by distillation or evaporation
- C02F1/06—Flash evaporation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/70—Treatment of water, waste water, or sewage by reduction
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/34—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2301/00—General aspects of water treatment
- C02F2301/08—Multistage treatments, e.g. repetition of the same process step under different conditions
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The regenerative system of raffinate in hydrogen dioxide solution production by anthraquinone process technique, it is related to the technical field of anthraquinone industrialized production hydrogen peroxide, including raffinate pipeline, carclazyte bed and regenerated liquid storage tank, according to feed liquor to the direction of liquid out, coalescer is sequentially connected in the liquid outlet of raffinate pipeline, primary flash device, two-stage flash device, carclazyte bed feed pump, the tube side inlet of the liquid outlet connection heat exchanger of carclazyte bed feed pump, the tube side liquid outlet of heat exchanger connects heater, the inlet of the liquid outlet connection carclazyte bed of heater, the liquid outlet of carclazyte bed is connected with the shell side inlet of heat exchanger, the shell side liquid outlet of heat exchanger is connected with regenerated liquid storage tank；Primary flash device is also connected with first-stage condenser, and first-stage condenser connects the first vacuum pump set；Two-stage flash device is also connected with secondary condenser, and secondary condenser connects the second vacuum pump set；The liquid outlet of primary flash device is connected with regenerated liquid storage tank.Production cost can be saved and ensure green production requirement.
Description
Technical field
The present invention relates to the technical field of anthraquinone industrialized production hydrogen peroxide, and in particular to generates in hydrogenation process
Hydrofenating anthraquinone degradation product (such as anthrone) be reduced into 2- ethyl hydrazine regeneration techniques, and remove most of moisture in raffinate
Keep the technology of catalyst activity.
Background technique
Industrial scale produces hydrogen peroxide (H2O2) conventional method be it is anthraquinone, mainly have hydrogenation process, oxidation
Reaction process, extraction and cleaning procedure, step for regeneration (also referred to as postprocessing working procedures).
Germane is: under palladium (Pd) catalytic action, 2- ethyl hydrazine and 2- ethyl tetrahydro-anthraquinone respectively with hydrogen
Solid/liquid/gas reactions generate 2- ethyl hydrogen anthraquinone and 2- ethyl tetrahydro hydrogen anthraquinone.The working solution generated during this we be known as hydrogenating
Liquid.
Redox reaction mechanism is: oxygen is occurred for oxygen in 2- ethyl hydrogen anthraquinone and 2- ethyl tetrahydro hydrogen anthraquinone and air
Change reaction, generates hydrogen peroxide, while 2- ethyl hydrogen anthraquinone and 2- ethyl tetrahydro hydrogen anthraquinone reduction are at 2- ethyl hydrazine and 2- second
Base tetrahydro-anthraquinone, this process generate working solution we be known as oxidation solution.
The mechanism of extraction is: using water as continuous phase, oxidation solution is dispersed phase, pure water from tower top flow to tower bottom during mistake
Oxidation hydrogen content gradually increases, and is finally also referred to as thick hydrogen peroxide from the extract liquor that the tower bottom of extraction tower flows out and (also becomes extraction
Liquid), then thick hydrogen peroxide again successively after purified, removal heavy aromatics, then is added into stabilizer, subsequently into hydrogen peroxide finished product packing
Process.Oxidation solution from extraction tower tower bottom upwards with pure water counter-current extraction during, hydrogen peroxide concentration gradually decreases, finally from extraction
Take column overhead to flow out, this liquid we be known as raffinate.
And passes through the above raffinate extracted and contain heavy aromatics, trioctyl phosphate, 2- ethyl hydrazine, 2- ethyl tetrahydro anthracene
Other than quinone, the also water containing free state and hydrogen peroxide, the water of solubilised state and hydrogen peroxide, hydrofenating anthraquinone degradation product and epoxy anthraquinone drops
Solve object.In order to keep working solution property (content of degradation product is too many, and working solution property changes) and catalyst activity (into
It is more to enter hydrogenation process band water, influences catalyst activity)；By physics or chemistry water removal and part hydrofenating anthraquinone degradation product is regenerated
It is reduced into the process of anthraquinone, the above treatment process is known as in the industry step for regeneration.
Traditional regeneration technology process is: first passing through potassium carbonate handle extraction in raffinate separator from the raffinate of extraction tower
The water of most of free state separates in extraction raffinate, then adsorbs most moisture using concentrated base, while decomposing most double
Oxygen water, then remove through alkali separator the lye of deentrainment, then by activated alumina in carclazyte bed by Anthraquinone reduction at 2- anthraquinone.
During traditional regeneration technology, most of moisture is absorbed although being removed through concentrated base absorption and alkali separator and has divided
Most of hydrogen peroxide has been solved, but has been entrained in anthrone there are also a large amount of lye and enters carclazyte bed, has caused the activity in carclazyte bed
Aluminium oxide is reacted with alkali, and generates powder phenomenon-tion, will have a direct impact on the service life of activated alumina.Secondly in carclazyte
Working solution temperature is always at 50 DEG C or so in bed, activated alumina at this temperature to the regeneration effect of anthraquinone degradation products not
It is good.
Therefore traditional regeneration technology has the following deficiencies:
1, it removes water (raffinate separator, washing tower (for removing CO2)) and except alkali (alkali separator) equipment needs biggish volume, initially filling is used
The liquid measure that works is more, and ancillary equipment is more (must cooperate and steam alkali system), and equipment investment cost is big, and land occupation is big.
2, working solution all passes through activated alumina processing, and the activated alumina of unit hydrogen peroxide consumes height, needs to dispose
The carclazyte bed volume of activated alumina is larger (100,000 tons/year of devices about 130m3 or so, three beds), the active oxidation of filling
Aluminum amount is more (filling 150t or so altogether).
3, activated alumina is since under alkaline environment, service life only about 1~2 month, main cause was white
The activated alumina powder phenomenon-tion of native bed bed bottom is serious, and easily generation activated alumina disappears loss.
4, water removal removes alkali equipment in traditional handicraft regeneration process and regeneration equipment volume is larger, initially loads the work used
Liquid measure is more.
5, it uses potassium carbonate as absorption deicer in raffinate separator, needs to consume a large amount of potassium carbonate, and carbonic acid
Potassium needs periodically displacement, generates largely useless potassium carbonate liquid.
6, dense potassium carbonate becomes dilute solution of potassium carbonate after adsorbing a large amount of water, needs to waste a large amount of steam dilute solution of potassium carbonate
Concentrate becomes concentrated base re-using.
7, since whole working solutions are through carclazyte bed in traditional handicraft regeneration process, and service life is shorter, unit hydrogen peroxide
Aluminium oxide consumption is high.
In short, conventional regeneration technique cannot not only reach the requirement of green production, also it is unfavorable for saving production.
Summary of the invention
The purpose of the invention is to overcome the deficiencies of the prior art and provide one kind to save production cost and guarantor
Hinder the regenerative system of raffinate in the hydrogen dioxide solution production by anthraquinone process technique that green production requires.
The object of the present invention is achieved like this: the regenerative system of raffinate in hydrogen dioxide solution production by anthraquinone process technique, including
Raffinate pipeline, carclazyte bed and regenerated liquid storage tank, according to feed liquor to the direction of liquid out, the raffinate pipeline liquid outlet according to
The liquid outlet connection heat of secondary connection coalescer, primary flash device, two-stage flash device, carclazyte bed feed pump, carclazyte bed feed pump is handed over
The tube side inlet of parallel operation, the tube side liquid outlet of heat exchanger connect heater, the liquid outlet connection carclazyte bed of heater into
Liquid mouth, the liquid outlet of carclazyte bed are connected with the shell side inlet of the heat exchanger, the shell side liquid outlet of heat exchanger and institute
Regenerated liquid storage tank is stated to be connected；The primary flash device is also connected with first-stage condenser, and first-stage condenser connects the first vacuum pump set；
The two-stage flash device is also connected with secondary condenser, and secondary condenser connects the second vacuum pump set；The primary flash device goes out
Liquid mouth is connected with regenerated liquid storage tank.
The working principle of the invention:
In raffinate other than containing heavy aromatics, trioctyl phosphate, tetrabutyl urea, 2- ethyl hydrazine, 2- ethyl tetrahydro-anthraquinone,
The also water containing free state and hydrogen peroxide, the water of solubilised state and hydrogen peroxide, hydrofenating anthraquinone degradation product and epoxy anthraquinone degradation products.
Coalescer is mainly made of hydrophobic group filter core, when the water of the free state in extract liquor touches hydrophobic group filter core,
The water of free state is easily detected by, and the water of such free state, which is gradually gathered into flood inside hydrophobic group filter core and drips, to sink to poly-
It ties device filter core bottom and coalescer bottom is discharged to by drainage blanket.
After the processing of the above raffinate coalescer, most of free state water and hydrogen peroxide are removed, in remaining working solution
Main component are as follows: heavy aromatics, trioctyl phosphate, tetrabutyl urea, 2- ethyl hydrazine and 2- ethyl tetrahydro-anthraquinone, there are also a small amount of free
State water and hydrogen peroxide, the water of solubilised state and hydrogen peroxide, hydrofenating anthraquinone degradation product and anthraquinone epoxy degradation product.
Pass through primary flash device, after flashing the water and hydrogen peroxide that vaporizing extract process removes most of solubilised state, remaining work again
Make main component in liquid are as follows: heavy aromatics, trioctyl phosphate, tetrabutyl urea, 2- ethyl hydrazine and 2- ethyl tetrahydro-anthraquinone, there are also few
Measure free state water and hydrogen peroxide, the water of a small amount of solubilised state and hydrogen peroxide, hydrofenating anthraquinone degradation product and epoxy degradation product.
Steam stripped most of working solution is flashed for the first time directly arrives regenerated liquid storage tank, and 20 through first time flash steam~
After 30% working solution carries out the water and hydrogen peroxide of second of flash distillation stripping removal solubilised state again, so that into the working solution of carclazyte bed
Water content is lower；Then regeneration hydrogenation anthraquinone degradation products are carried out by activated alumina after being just heated to 65~75 DEG C；Part hydrogen
Change anthraquinone degradation products and is reduced into 2- ethyl hydrazine.
The present invention is with the difference of traditional work technique again: the present invention absorbs non-free state water without concentrated base and separates to alkali
The step of, instead non-free state water is removed using the physical method of flash distillation.
This system can guarantee that water content is enough low in the working solution contacted with activated alumina, fully ensures that active oxidation
The service life of aluminium.It avoids using influence of the alkali to activated alumina, is in activated alumina under neutrallty condition and works, it can
Ensure that its property is more stable, small, service life extension is lost.In addition, due to there is no the consumption of alkali in this system and steaming alkali steam
Consumption, so not needing to save equipment, the investment of material, the feature of environmental protection is higher in production process using alkali separating step.Make
Water removal device and regeneration equipment volume can be made smaller with this regeneration process, the work liquid measure initially loaded is less, and initial outlay is few,
The waste water generated after dehydration more completely may return to extraction tower re-using.
This system can also flash the dissolved oxygen of oxidation operation in Hydrogen Peroxide Production and extraction process and be stripped off, and can ensure work
Enter hydrogenation process as liquid and no longer contain oxygen, thus the safety for guaranteeing hydrogenation process driving and parking and normally producing.To basic
On avoid system working solution and soda acid alternate run occur, prevented the lye string of traditional soda acid process unit post-processing to aoxidizing
Process, extracting and purifying process and cause decomposing hydrogen dioxide solution explode safety accident.
This system does not generate steaming alkali waste water, due to anthraquinone less degradation, works normally liquid washing and does not need alkali cleaning, need
It is less to wash water, so that 200,000 tons of daily wastewater flow rates of hydrogen peroxide (27.5%) device are only 20 tons or so；And traditional acid-base property
The sewage quantity that process unit generates daily is 60 tons or so.
This system designs primary flash device and two-stage flash device, by the water and hydrogen peroxide of coalescer removal not yet by the
It is divided into two parts after the water and hydrogen peroxide of the most of solubilised state of full flashing removal, is largely returned directly to regenerated liquid storage tank conduct
The raw material of hydrogen dioxide solution production by anthraquinone process, after in addition small part working solution removes part water and hydrogen peroxide into second of flash distillation again,
Then anthraquinone is reduced into the hydrofenating anthraquinone degradation product progress regeneration treatment in working solution by activated alumina and returns to regenerated liquid
Raw material of the storage tank as hydrogen dioxide solution production by anthraquinone process.
Primary flash device of the invention is as the structure of two-stage flash device, the shell including vacuum, at the top of shell
Working solution import and true air outlet slit are set, and in the bottom of shell, setting working solution is exported；Liquid point is fixed in the shell
Cloth device and column plate, liquid distribution trough are connected with working solution import, and the top of liquid distribution trough, column plate and shell is arranged in column plate
Between be tightly connected, air rising hole is set on column plate, gas gathering mask is connected at air rising hole, gas gathering mask is connected to the top of column plate,
A vertical tracheae is placed on gas gathering mask, in the top connecting cover plate of gas gathering mask, cover board is arranged in the top of tracheae and sets
There is gap.Raffinate reaches the working solution import at the top of flash vessel, then raffinate enters liquid distribution trough with certain pressure
On, raffinate is sprayed by liquid distribution trough by mist formation drop-wise；Then droplet shape working solution gradually reaches bottom of the invention.Water
And the method that the method that extracts from raffinate of hydrogen peroxide uses vacuum flash, by extraneous vacuum pump set shell
When intracorporal space degree of being evacuated is larger, most of water and hydrogen peroxide are in fast boiling in the raffinate droplet that sprays at this time
The water vapour (including dioxygen water vapour) of state, generation of boiling is reached up to very by the air rising hole of column plate above liquid distribution trough
Air outlet slit, cover board avoid the raffinate of droplet shape from being discharged upwards from tracheae, first water under being pulled by vacuum pump set vacuum
Vapour is extracted into recirculated water cooling condenser and is condensed, and the water vapour and dioxygen water vapour then not condensed are extracted into low temperature water condenser again
It is condensed again, then there are no a small amount of gases condensed out to be directly discharged to the external world by vacuum pump set extraction.
The first-stage condenser of invention has two, and two first-stage condensers mutually concatenate.
The shell side liquid outlet of the heat exchanger of invention connects filter, the liquid outlet of filter and the regenerated liquid storage tank phase
Connection.
The filter of invention has two, and two filters mutually concatenate.
Detailed description of the invention
Fig. 1 is the principle of the present invention schematic diagram.
Fig. 2 is the structural schematic diagram of primary flash device.
Fig. 3 is the portion A enlarged drawing in Fig. 2.
Specific embodiment
As shown in Figure 1, in hydrogen dioxide solution production by anthraquinone process technique raffinate regenerative system, including with extraction tower liquid outlet phase
Raffinate pipeline 1 even is sequentially connected coalescer 2, one in the liquid outlet of raffinate pipeline 1 according to feed liquor to the direction of liquid out
Grade flash vessel 3, two-stage flash device 7, carclazyte bed feed pump 14, the pipe of the liquid outlet connection heat exchanger 13 of carclazyte bed feed pump 14
Journey inlet, the tube side liquid outlet of heat exchanger 13 connect heater 11, the liquid outlet connection carclazyte bed 12 of heater 11 into
Liquid mouth, the liquid outlet of carclazyte bed 12 are connected with the shell side inlet of heat exchanger 13, and the shell side liquid outlet of heat exchanger 13 connects
Grade one filter 8 is connect, the liquid outlet of grade one filter 8 connects secondary filter 9, and the liquid outlet of secondary filter 9 connects regeneration
Liquid storage tank 10.Primary flash device 3 is also connected with first-stage condenser 4, and first-stage condenser 4 connects third condenser 5, third condenser 5
Connect the first vacuum pump set 15.Two-stage flash device 7 is also connected with secondary condenser 6, and secondary condenser 6 connects the second vacuum pump set
16.The liquid outlet of primary flash device 3 is connected with regenerated liquid storage tank 10.
Primary flash device 3 is identical with the structure of two-stage flash device 7, includes the shell 3-5 of vacuum, on the top of shell 3-5
Working solution import 3-1 and true air outlet slit 3-2 is arranged in portion, and in the bottom of shell 3-5, setting working solution exports 3-6.In shell 3-5
Interior fixed liquid distribution trough 3-4 and column plate 3-3, liquid distribution trough 3-4 are connected with working solution import 3-1, and column plate 3-3 setting exists
The top of liquid distribution trough 3-4 is tightly connected between column plate 3-3 and shell 3-5, and air rising hole 3-7, In are arranged on column plate 3-3
Gas gathering mask 3-8 is connected at air rising hole 3-7, gas gathering mask 3-8 is connected to the top of column plate 3-3, and one is placed on gas gathering mask 3-8 vertically
Tracheae 3-10, in the top connecting cover plate 3-9 of gas gathering mask 3-8, between cover board 3-9 is arranged in the top of tracheae 3-10 and is equipped with
Gap.
The liquid outlet of coalescer 2 is connected with the working solution import 3-1 of primary flash device 3, and the working solution of primary flash device 3 goes out
Mouth 3-6 is connected with the working solution import 3-1 of two-stage flash device 7, and the working solution outlet 3-6 and carclazyte bed of two-stage flash device 7 are fed
The inlet of pump 14 is connected.
Raffinate from extraction tower is after water-oil separating coalescer 2 removes the water of free state, then through primary flash device 3
Most of water and the hydrogen peroxide being dissolved in raffinate are removed, then separates 20-30% from 3 bottom tapping control valve of primary flash device
Working solution (after water removal be also referred to as working solution) enter two-stage flash device 7 by potential difference, carry out flash distillation water removal again in two-stage flash device 7
And hydrogen peroxide, the working solution after secondary flash water removal pressurize through carclazyte bed feed pump 14 through heat exchanger 13, heater 11, carclazyte
Bed 12, heat exchanger 13 return to regenerated liquid storage tank 10 and are recycled next time.In the regenerated process of this working solution, through coalescing
Dehydration, full flashing dehydration, secondary flash dehydration guarantee that the working solution water content for entering carclazyte bed is enough low, fully ensure that
The service life of activated alumina in carclazyte bed；It is heated to 65-75 DEG C before working solution enters carclazyte bed, is experimentally confirmed work
Property aluminium oxide at this temperature activity it is best to regenerating anthraquinone degradation products effect compared with by force；Work of the activated alumina in weakly acidic pH
Property is more stable under the conditions of liquid.
Advantages of the present invention:
1. the present invention is using coalescer, flash distillation water removal twice, the equipment volumes such as coalescer and flash vessel are smaller, and equipment investment is few,
Land occupation is few.
2. working solution of the present invention is that 20-30% flows through carclazyte bed, needing carclazyte bed volume compared with small, (100,000 tons/year of devices are big
About 60m3 or so, two beds), carclazyte bed investment cost is few, and the active oxidation aluminum amount (filling 50 tons or so altogether) initially filled is less.
3. activated alumina, catalyst relative to activated alumina under alkaline environment due to making under neutral environment in the present invention
Use longer life expectancy.
4. in the present invention, water removal device and regeneration equipment volume are smaller in regeneration technology process, the work used is initially loaded
It is less to make liquid measure, initial outlay is few.
5. in the present invention, regenerating using coalescer water removal, flash-evaporation dehydration in process, the waste water generated after dehydration more completely may be used
To return to extraction tower re-using.
6. in the present invention, being heated to due to being 20-30% treatment fluid flow through carclazyte bed, and into carclazyte bed working solution
At 65-75 DEG C, activity is most strong at this temperature for activated alumina, and regeneration effect is best, so that activated alumina service life
Longer, the consumption of unit hydrogen peroxide oxidation aluminium is low.
4, present invention regeneration process and traditional handicraft working solution regenerate process contrast table (to produce 100000 tons of devices per year, 27.5%
Hydrogen peroxide meter)
Claims (5)
1. the regenerative system of raffinate in hydrogen dioxide solution production by anthraquinone process technique, including raffinate pipeline, carclazyte bed and regenerated liquid storage
Slot, it is characterised in that: according to feed liquor to the direction of liquid out, be sequentially connected coalescer, one in the liquid outlet of the raffinate pipeline
Grade flash vessel, two-stage flash device, carclazyte bed feed pump, the tube side feed liquor of the liquid outlet connection heat exchanger of carclazyte bed feed pump
Mouthful, the tube side liquid outlet of heat exchanger connects heater, the inlet of the liquid outlet connection carclazyte bed of heater, and carclazyte bed goes out
Liquid mouth is connected with the shell side inlet of the heat exchanger, and the shell side liquid outlet of heat exchanger is connected with the regenerated liquid storage tank
It connects；The primary flash device is also connected with first-stage condenser, and first-stage condenser connects the first vacuum pump set；The two-stage flash device is also
Secondary condenser is connected, secondary condenser connects the second vacuum pump set；The liquid outlet and regenerated liquid storage tank of the primary flash device
It is connected.
2. according to claim 1 in hydrogen dioxide solution production by anthraquinone process technique raffinate regenerative system, it is characterised in that: it is described
Primary flash device is identical with the structure of two-stage flash device, includes the shell of vacuum, and working solution import is arranged at the top of shell
With true air outlet slit, in the bottom of shell, setting working solution is exported；Liquid distribution trough and column plate, liquid are fixed in the shell
Distributor is connected with working solution import, and the top of liquid distribution trough is arranged in column plate, is tightly connected between column plate and shell, In
Air rising hole is set on column plate, gas gathering mask is connected at air rising hole, gas gathering mask is connected to the top of column plate, one is placed on gas gathering mask
Vertical tracheae, in the top connecting cover plate of gas gathering mask, cover board is arranged in the top of tracheae and is equipped with gap.
3. according to claim 1 in hydrogen dioxide solution production by anthraquinone process technique raffinate regenerative system, it is characterised in that: it is described
First-stage condenser has two, and two first-stage condensers mutually concatenate.
4. according to claim 1 in hydrogen dioxide solution production by anthraquinone process technique raffinate regenerative system, it is characterised in that: it is described
The shell side liquid outlet of heat exchanger connects filter, and the liquid outlet of filter is connected with the regenerated liquid storage tank.
5. according to claim 4 in hydrogen dioxide solution production by anthraquinone process technique raffinate regenerative system, it is characterised in that: it is described
Filter has two, and two filters mutually concatenate.
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| CN115594153A (en) * | 2022-12-14 | 2023-01-13 | 扬州荣祥科技发展有限公司（Cn） | Regeneration process of working solution in process for producing hydrogen peroxide by anthraquinone method |
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