CN107140613A - A kind of method and its device for preparing thermal phosphoric acid and reclaiming heat energy - Google Patents
A kind of method and its device for preparing thermal phosphoric acid and reclaiming heat energy Download PDFInfo
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- CN107140613A CN107140613A CN201710498011.0A CN201710498011A CN107140613A CN 107140613 A CN107140613 A CN 107140613A CN 201710498011 A CN201710498011 A CN 201710498011A CN 107140613 A CN107140613 A CN 107140613A
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- Prior art keywords
- phosphoric acid
- gas
- heat
- yellow phosphorus
- reaction
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- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 title claims abstract description 163
- 229910000147 aluminium phosphate Inorganic materials 0.000 title claims abstract description 82
- 238000000034 method Methods 0.000 title claims abstract description 47
- 239000007789 gas Substances 0.000 claims abstract description 97
- OBSZRRSYVTXPNB-UHFFFAOYSA-N tetraphosphorus Chemical compound P12P3P1P32 OBSZRRSYVTXPNB-UHFFFAOYSA-N 0.000 claims abstract description 67
- 238000006243 chemical reaction Methods 0.000 claims abstract description 52
- DLYUQMMRRRQYAE-UHFFFAOYSA-N phosphorus pentoxide Inorganic materials O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 claims abstract description 51
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 45
- 239000006096 absorbing agent Substances 0.000 claims abstract description 37
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 34
- 239000008234 soft water Substances 0.000 claims abstract description 32
- 239000007788 liquid Substances 0.000 claims abstract description 27
- 238000011084 recovery Methods 0.000 claims abstract description 20
- 238000006703 hydration reaction Methods 0.000 claims abstract description 18
- 239000007791 liquid phase Substances 0.000 claims abstract description 18
- 239000000203 mixture Substances 0.000 claims abstract description 18
- 239000012071 phase Substances 0.000 claims abstract description 15
- 238000002485 combustion reaction Methods 0.000 claims abstract description 13
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 12
- 239000001301 oxygen Substances 0.000 claims abstract description 12
- 239000007800 oxidant agent Substances 0.000 claims abstract description 8
- 230000001590 oxidative effect Effects 0.000 claims abstract description 8
- 230000002745 absorbent Effects 0.000 claims description 35
- 239000002250 absorbent Substances 0.000 claims description 35
- 239000006185 dispersion Substances 0.000 claims description 35
- 239000000463 material Substances 0.000 claims description 15
- 238000005406 washing Methods 0.000 claims description 12
- 239000002253 acid Substances 0.000 claims description 10
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 8
- 230000008676 import Effects 0.000 claims description 7
- 229910052698 phosphorus Inorganic materials 0.000 claims description 7
- 239000011574 phosphorus Substances 0.000 claims description 7
- 238000002360 preparation method Methods 0.000 claims description 7
- 238000010521 absorption reaction Methods 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 239000007792 gaseous phase Substances 0.000 claims description 5
- 238000000926 separation method Methods 0.000 claims description 5
- 230000008859 change Effects 0.000 claims description 3
- 230000005540 biological transmission Effects 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- YWEUIGNSBFLMFL-UHFFFAOYSA-N diphosphonate Chemical compound O=P(=O)OP(=O)=O YWEUIGNSBFLMFL-UHFFFAOYSA-N 0.000 claims 3
- 238000004519 manufacturing process Methods 0.000 abstract description 13
- 230000008569 process Effects 0.000 description 18
- 239000000243 solution Substances 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- 230000036571 hydration Effects 0.000 description 5
- 238000012546 transfer Methods 0.000 description 5
- 229910019142 PO4 Inorganic materials 0.000 description 4
- 235000021317 phosphate Nutrition 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000010452 phosphate Substances 0.000 description 3
- -1 phosphate ester Chemical class 0.000 description 3
- 229920000137 polyphosphoric acid Polymers 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000003889 chemical engineering Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical group O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- JXBAVRIYDKLCOE-UHFFFAOYSA-N [C].[P] Chemical compound [C].[P] JXBAVRIYDKLCOE-UHFFFAOYSA-N 0.000 description 1
- KXEOSTAFIDYVEF-UHFFFAOYSA-N [Si](O)(O)(O)O.[F] Chemical compound [Si](O)(O)(O)O.[F] KXEOSTAFIDYVEF-UHFFFAOYSA-N 0.000 description 1
- 238000000889 atomisation Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 238000005649 metathesis reaction Methods 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000004886 process control Methods 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 238000013456 study Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010977 unit operation Methods 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
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/18—Phosphoric acid
- C01B25/20—Preparation from elemental phosphorus or phosphoric anhydride
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F22—STEAM GENERATION
- F22B—METHODS OF STEAM GENERATION; STEAM BOILERS
- F22B1/00—Methods of steam generation characterised by form of heating method
- F22B1/02—Methods of steam generation characterised by form of heating method by exploitation of the heat content of hot heat carriers
- F22B1/18—Methods of steam generation characterised by form of heating method by exploitation of the heat content of hot heat carriers the heat carrier being a hot gas, e.g. waste gas such as exhaust gas of internal-combustion engines
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Sustainable Development (AREA)
- Combustion & Propulsion (AREA)
- Life Sciences & Earth Sciences (AREA)
- Inorganic Chemistry (AREA)
- Sustainable Energy (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Mechanical Engineering (AREA)
- General Engineering & Computer Science (AREA)
- Gas Separation By Absorption (AREA)
- Treating Waste Gases (AREA)
Abstract
The present invention discloses a kind of method and its device for preparing thermal phosphoric acid and reclaiming heat energy, this method is absorbed heat with micro- absorber to the reaction heat of hydration reaction, knockout drum is brought into by gas-liquid mixture by reaction heat after micro- absorber, first pass through tail gas heat quantity reclaimer and concentrated phosphoric acid cooler absorbs the heat of gas phase and liquid phase respectively, the heat of gas phase and liquid phase is neutralized again, the last vaporising device for being delivered to yellow phosphorus boiler in saturation soft water form carries out steam, and heat energy can be reclaimed while prepared by phosphoric acid by realizing；The quality of oxygen is 1.2 2.6 times of yellow phosphorus quality used in described oxidant, and described hydrated agent is water or difference P2O5The solution of mass fraction, the quality of hydrated agent reclaimed water is 0.29 6 times of yellow phosphorus quality, and the water quality used for preparing saturation soft water is 1 20 times of yellow phosphorus quality, and the present invention can improve the combustion heat, the rate of recovery of the reaction heat of phosphorus pentoxide of yellow phosphorus, be conducive to saving the energy, effectively reduce into production cost.
Description
Technical field
The present invention relates to a kind of method and its device for preparing thermal phosphoric acid and reclaiming heat energy, belong to phosphoric acid and prepare and low level
The utilization technology field of heat energy.
Background technology
Phosphoric acid is product in the middle of a kind of important chemical industry, is the synthesis phosphorus-containing compound such as most phosphates and partial phosphate ester
Conventional raw material, be widely used in the industries such as food, medicine, electronics, oil, metallurgy, chemical industry.According to production technology, phosphoric acid
Source have phosphoric acid by wet process and thermal phosphoric acid.Phosphoric acid by wet process is to utilize strong acid --- it is typically sulfuric acid, also there is nitric acid, hydrochloric acid, fluorine
Silicic acid occurs metathesis reaction with phosphorus ore and obtains impure more raw phosphoric acid, is generally used for fertilizer., can after the phosphoric acid is purified
Obtain the phosphoric acid of food-grade；Thermal phosphoric acid is that sharp reduction with carbon phosphorus ore obtains yellow phosphorus at high temperature, and the yellow phosphorus that then burns obtains five oxygen
Change two phosphorus, then obtained by being reacted with water.Thermal phosphoric acid impurity is few, before wet phosphoric acid purifying Technique Popularizing, almost fine
The unique raw material of phosphate product.From the point of view of technological process, compared with thermal phosphoric acid, the technological process length of phosphoric acid by wet process and multiple
Miscellaneous, unit operation and auxiliary facility are more.But economically, phosphoric acid by wet process has a clear superiority compared with thermal phosphoric acid, thermal phosphoric acid cost
A high major reason is that energy consumption is big.Traditional phosphorous acid production by BEP technique is very extensive.Yellow phosphorus burning and aquation
Reaction heat is directly removed by low-temperature circulating water, becomes low level used heat, it is difficult to utilize, in recent years, in order to reduce thermal phosphoric acid into
This, the recovery of yellow phosphorus phosphoric acid release heat gradually receives much concern, and has also only carried out many correlative studys and practice, for example：
Patent of invention CN1355133A Phosphorus combustion heat recovery and utilization device and its thermal phosphoric acid production systems propose one
Plant the combustion heat energy retracting device and a phosphorous acid production by BEP system of similar boiler.The focusing on of the patent introduces the combustion heat
The device of energy retracting device, the consideration for the energy recovery technique of the high-temperature tail gas after separating device fails to jump out tradition completely
The pattern of hydrated tower.It is totally different due to air-liquid two-phase physical property and flow, thus in the way of hydrated tower jacketed simultaneously with
The thermal efficiency of air-liquid two-phase heat exchange is very limited.In addition, the species of absorbent in hydrated tower is not known in claim, only in reality
Apply to mention in example and directly use water, and do not refer to vent gas treatment.
Patent of invention CN201531862U yellow phosphorus burning heat energy recycling devices propose a kind of yellow phosphorus burning more insured
Heat-energy recovering apparatus, it does intermediate heat transfer medium using certain gas, can be prevented effectively from because the rupture of boiler heat exchange comb causes five
Aoxidize two phosphorus and soft water reaction generation phosphoric acid and etching apparatus, the patent does not refer to that the recovery of the heat of hydration and heat are integrated.
A kind of phosphorous acid production by BEP devices reclaimed with Lowlevel thermal energy of patent of invention CN105731405A propose one kind
It can not carry tail gas heat quantity with the device of recovery section aquation heat energy, gained vapour pressure highest 0.8MPa and reclaim integrated with heat.
It is a kind of similar that the device of patent of invention CN102910602A dual zone type high efficiente callback heat energy generated during combustion of yellow, which is proposed,
The heat-energy recovering apparatus of phosphoric acid-fired boiler, the recovery of device high-temperature tail gas heat energy and hydrated reaction heat is not considered.
The device of patent of invention CN102556990A absorbing heat energy from combustion of yellow phosphorus with heat transfer oil proposes one kind by conduction oil
Exchange heat, then discharge the device of heat, the invention need to use conduction oil and do intermediate heat transfer medium, and not mention device high-temperature tail gas
The recovery of heat energy and hydrated reaction heat.
At present, Patents, the report of document are mostly focused on the technique and equipment of heat energy generated during combustion of yellow recovery, and rarely have
The recovery of aquation heat energy and final tail gas band heat is noticed, the phosphoric acid that various concentrations are prepared into by raw material of yellow phosphorus is not referred to yet
Or the overall process system thermal of polyphosphoric acid is integrated, therefore energy recovery rate is not high.
Wherein, the utilization of the heat of hydration is very difficult in the sour technique of traditional hot method.The sour technique of the hot method of tradition is to avoid equipment
Corrosion, is made absorbent using substantial amounts of SAPMAC method acid and phosphorus pentoxide is absorbed in spray column, be no more than with control material temperature
80℃.80 DEG C of heat is difficult by.Therefore, it is necessary to improve the temperature of material in absorption process, and then need to select more
Expensive equipment and materials；For big equipment, upgrade of material means the increasing of equipment investment, and this can weaken heat recovery band
The benefit come.For this reason, it may be necessary to reduce equipment volume as far as possible.
Micro-reacting tcchnology is in recent years gradually by the new skill of the strengthening process transmission of extensive concern, accurate process control
Art.With the research of micro- Chemical Engineering Technology such as microring array and multiphase microfluidic, micro- heat exchange and mass transfer, minute yardstick reaction constantly obtain into
Exhibition, micro- Chemical Engineering Technology has been widely used in many research fields such as chemistry, chemical industry, material, the energy and environment, and
The fields such as the extensive controllable preparation of nano particle, extraction separation process reinforcing and fine chemicals production realize commercial Application；
One of implication of bright spot micro-of the technology refers under identical production intensity, bulk or microreactor that process occurs
Characteristic size is especially small relative to large scale equipments such as traditional tower, grooves, so that the miniaturization of factory, becoming more meticulous, being flexibly melted into
For possibility.For various process, the property of system is different, and the degree of above-mentioned micro-is also different, therefore, in micro-reacting tcchnology
In detailed process application, the characteristic size of proportioning is important parameter.
Hydration process in phosphorous acid production by BEP technique is a reactive absorption process.Reaction be embodied in phosphorus pentoxide with
The reaction of water, absorbs the phosphorus pentoxide being embodied in gas phase and is deviate from, and the import of gaseous phase materials is nitrogen, oxygen and gaseous state five
The mixed gas of two phosphorus is aoxidized, and it is mainly nitrogen and oxygen to export, absorbent is mainly the aqueous solution of phosphoric acid or polyphosphoric acid,
Its exit concentration at present, there is no the microreactor for this system higher than import, be that this present invention introduces microreactor
The process, and propose suitable microreactor characteristic size.
The content of the invention
The technical problem to be solved in the present invention is to provide a kind of method and its device for preparing thermal phosphoric acid and reclaiming heat energy,
The combustion heat, the rate of recovery of the reaction heat of phosphorus pentoxide of yellow phosphorus can be improved, is conducive to saving the energy, effectively reduces into and produce into
This, can overcome the deficiencies in the prior art.
The technical scheme is that：A kind of method for preparing thermal phosphoric acid and reclaiming heat energy, hair is contacted with oxidant by yellow phosphorus
Raw combustion reaction, generates the gas containing phosphorus pentoxide, and the gas containing phosphorus pentoxide is contacted with hydrated agent, occurs aquation anti-
Should, it is characterised in that：This method is absorbed heat with micro- absorber to the reaction heat of hydration reaction, passes through reaction heat after micro- absorber
Knockout drum is brought into by gas-liquid mixture, tail gas heat quantity reclaimer is first passed through and concentrated phosphoric acid cooler absorbs gas phase and liquid phase respectively
Heat, then the heat of gas phase and liquid phase is neutralized, the evaporation for being finally delivered to yellow phosphorus boiler in saturation soft water form is filled
Carry out steam is put, heat energy can be reclaimed while prepared by phosphoric acid by realizing；The quality of oxygen is yellow phosphorus matter used in described oxidant
1.2-2.6 times of amount, described hydrated agent is water or the solution of difference P2O5 mass fractions, and the quality of hydrated agent reclaimed water is yellow phosphorus
0.29-6 times of quality, the water quality of preparation saturation soft water used is 1-20 times of yellow phosphorus quality.
The above-mentioned gas containing phosphorus pentoxide is contacted with hydrated agent, and when occurring hydration reaction, required hydrated agent is one
Secondary property is added or after first time adds, added again at the downstream of the liquid phase of gas-liquid separation.
Above-mentioned tail gas heat quantity reclaimer includes exhaust gas cooler and 85 phosphoric acid coolers, and gas passes through exhaust gas cooler
The tail gas of cooling is delivered into exhaust scrubber after absorption heat to be washed, the consumption of washings is the 0.29-6 of yellow phosphorus quality
Times, the water after washing is used for hydration reaction.
A kind of device for preparing thermal phosphoric acid and reclaiming heat energy, it includes yellow phosphorus boiler, and the outlet of yellow phosphorus boiler is inhaled with micro-
The gas inlet end connection of device is received, is exported on micro- absorber provided with absorbent entrance and gas-liquid mixture, gas-liquid mixture goes out
Mouth is connected with knockout drum, and knockout drum gaseous phase outlet is connected with exhaust gas cooler, and exhaust gas cooler is connected with gas treatment equipment,
Knockout drum liquid-phase outlet is connected with concentrated phosphoric acid cooler, and the exhaust gas cooler is exported provided with soft water import and soft water preheating, in advance
Hot soft water outlet is connected with 85 phosphoric acid coolers, concentrated phosphoric acid cooler successively by pipeline, the saturation soft water of concentrated phosphoric acid cooler
Outlet is connected with the steam unit of yellow phosphorus boiler.
Above-mentioned micro- absorber includes bottom plate and cover plate, provided with the reaction plate on one in bottom plate and cover plate, in cover plate
Turning be provided with absorbent entrance, reaction plate correspondence position be provided with absorbent passage, in bottom plate and the upper face of reaction plate
Parallel channels are laid with, provided with vertical dispersion plate is moved towards with parallel channels at absorbent passage, are provided with dispersion plate
Dispersion hole, the groove for being bumped into dispersion plate is provided with the bottom of reaction plate, with being provided with gas on the bottom plate of absorbent passage the same side
Body import, provided with gas-liquid mixture outlet on the reaction plate away from absorbent passage side.
Above-mentioned parallel channels hydraulic radius is 0.05mm-10mm, and the radius of dispersion hole is 0.01mm-2mm, dispersion hole
The angle of axis and parallel channels axis is 20 ° -90 °, and the residence time of material is 1s-60s.
Prior art compares, and the present invention prepares thermal phosphoric acid and the method for reclaiming heat energy, and this method is with micro- absorber to water
The reaction heat for changing reaction is absorbed heat, and is brought knockout drum into by gas-liquid mixture by reaction heat after micro- absorber, is first passed through tail gas
Thermal recovery unit and concentrated phosphoric acid cooler absorb the heat of gas phase and liquid phase respectively, then by the heat progress of gas phase and liquid phase
With, finally with saturation soft water form be delivered to yellow phosphorus boiler vaporising device carry out steam, realize phosphoric acid prepare while can return
Receive heat energy；This method can improve the combustion heat of yellow phosphorus, the rate of recovery of the reaction heat of phosphorus pentoxide, drawn, used by experiment
This method is recycled using yellow phosphorus is produced the reaction heat that phosphoric acid discharges by raw material 95%, and the steam pressure of generation can be higher than
1.0MPa, meanwhile, the use of microreactor effectively improves heat recovery rate；
The quality of oxygen is 1.2-2.6 times of yellow phosphorus quality used in oxidant, and described hydrated agent is water or difference P2O5 matter
The solution of fraction is measured, the quality of hydrated agent reclaimed water is 0.29-6 times of yellow phosphorus quality, the water quality of preparation saturation soft water used is
1-20 times of yellow phosphorus quality, this data are the both economical energy-conservations that applicant draws by multiple experiment, and do not influence production
The critical data group of quality；
Gas containing phosphorus pentoxide is contacted with hydrated agent, when occurring hydration reaction, required hydrated agent be it is disposable add or
After first time adds, added again at the downstream of the liquid phase of gas-liquid separation, the hydrated agent so added is conducive to reaction
Carry out；
Tail gas heat quantity reclaimer includes exhaust gas cooler and 85 phosphoric acid coolers, and gas is absorbed after heat by exhaust gas cooler
The tail gas of cooling is delivered into exhaust scrubber to be washed, the consumption of washings is 0.29-6 times of yellow phosphorus quality, after washing
Water be used for hydration reaction, the consumption of such washings can guarantee that the clean result of tail gas, it is ensured that the discharge standard of tail gas,
The use water of circulation is conducive to saving financial cost simultaneously；
The outlet of the structure yellow phosphorus boiler is connected with the gas inlet end of micro- absorber, and absorbent entrance is provided with micro- absorber
With gas-liquid mixture outlet, gas-liquid mixture outlet is connected with knockout drum, and knockout drum gaseous phase outlet is connected with exhaust gas cooler, tail
Gas Cooler is connected with gas treatment equipment, and knockout drum liquid-phase outlet is connected with concentrated phosphoric acid cooler, the exhaust gas cooler
Exported provided with soft water import and soft water preheating, soft water preheating outlet is cooled down with 85 phosphoric acid coolers, concentrated phosphoric acid successively by pipeline
Device is connected, and the saturation soft water outlet of concentrated phosphoric acid cooler is connected with the steam unit of yellow phosphorus boiler, and such device will burn, water
Change the unified recovery of most of reaction heat of reaction, heat recovery, the high table of grade of regenerated heat energy have also particularly been carried out to tail gas
The pressure for producing steam now is more than 1.0MPa, both can be used as factory power, it is also possible to do thermal source；
Micro- absorber includes bottom plate and cover plate, provided with the reaction plate on one in bottom plate and cover plate, is provided with the turning of cover plate
Absorbent entrance, is provided with absorbent passage in the correspondence position of reaction plate, is laid with the upper face of bottom plate and reaction plate flat
Row of channels, provided with vertical dispersion plate is moved towards with parallel channels at absorbent passage, is provided with dispersion hole, anti-on dispersion plate
Answer the bottom of plate to be provided with and be bumped into the groove of dispersion plate, with being provided with gas feed on the bottom plate of absorbent passage the same side, remote
Reaction plate from absorbent passage side is exported provided with gas-liquid mixture, and such micro- absorber makes phosphorus pentoxide and aquation
Most reaction heat that agent occurs is taken away by phosphate mixture, and small part is stored in gas phase, is conducive to next step process to heat
Recovery；Dispersion plate is used to distribute absorbent in each bar shaped microchannel, to increase the surface area that gas is contacted；
Dispersion hole is used to allow absorbent by dispersion plate, to distribute absorbent in each bar shaped microchannel；
Contact and flowing of the parallel channels for gas with absorbent provide place；
Parallel channels hydraulic radius is 0.05mm-10mm, and the radius of dispersion hole is 0.01mm-2mm, the axis of dispersion hole with it is parallel
The angle of passage axis is 20 ° -90 °, and the residence time of material is 1s-60s, and micro- absorber of such size can preferably absorb
Heat, is conducive to improving the organic efficiency of heat, meanwhile, more traditional spray absorber, the mass transfer rate of micro- absorber is fast, anti-
High conversion rate is answered, therefore production intensity is greatly improved, equipment volume is substantially reduced, and the reduction of equipment volume means material capability
Can room for promotion it is big, and excellent material is to ensure that the key that aquation absorbs temperature height, the heat of hydration can be utilized, furthermore equipment
Other advantages of small volume have：Reduced investment, liquid holdup are low, operation is flexible, process regulation is rapid and accurate.
Brief description of the drawings
Fig. 1 is the structural representation of the present invention.
Fig. 2 is micro- absorber schematic diagram.
Fig. 3 is the structural representation of dispersion plate.
Fig. 4 is the structural representation of reaction plate.
Wherein, yellow phosphorus boiler 1；Micro- absorber 2；Knockout drum 3；Exhaust gas cooler 4；Exhaust scrubber 5；Concentrated phosphoric acid cooler
6；85 phosphoric acid coolers 7；Acid circulating pump 8；Wash water circulating pump 9；Exhaust fan 10.
Embodiment
A kind of method for preparing thermal phosphoric acid and reclaiming heat energy of the present invention, contacts generation burning with oxidant anti-by yellow phosphorus
Should, the gas containing phosphorus pentoxide is generated, the gas containing phosphorus pentoxide is contacted with hydrated agent, occur hydration reaction, this method
The reaction heat of hydration reaction is absorbed heat with micro- absorber 2, brought into point by gas-liquid mixture by reaction heat after micro- absorber 2
From tank 3, the heat that tail gas heat quantity reclaimer and concentrated phosphoric acid cooler 6 absorb gas phase and liquid phase respectively is first passed through, then by gas phase
Neutralized with the heat of liquid phase, the vaporising device for being finally delivered to yellow phosphorus boiler 1 in saturation soft water form carries out steam, realizes
Phosphoric acid can reclaim heat energy while preparation；The quality of oxygen is 1.2-2.6 times of yellow phosphorus quality used in described oxidant, institute
The hydrated agent stated is the solution of water or difference P2O5 mass fractions, and the quality of hydrated agent reclaimed water is 0.29-6 times of yellow phosphorus quality,
The water quality of preparation saturation soft water used is 1-20 times of yellow phosphorus quality, wherein, the gas containing phosphorus pentoxide connects with hydrated agent
Touch, when occurring hydration reaction, required hydrated agent be it is disposable add or after first time adds, from the liquid phase of gas-liquid separation
Added again at downstream；Tail gas heat quantity reclaimer includes the phosphoric acid cooler 7 of exhaust gas cooler 4 and 85, and gas is cold by tail gas
But the tail gas of cooling is delivered into exhaust scrubber 5 after the absorption of device 4 heat to be washed, the consumption of washings is yellow phosphorus quality
0.29-6 times, the water after washing is used for hydration reaction.
A kind of device for preparing thermal phosphoric acid and reclaiming heat energy, its structure are as shown in figure 1, it includes yellow phosphorus boiler 1, yellow phosphorus
The outlet of boiler 1 is connected with the gas inlet end of micro- absorber 2, and absorbent entrance and gas-liquid mixed are provided with micro- absorber 2
Thing is exported, and gas-liquid mixture outlet is connected with knockout drum 3, and the gaseous phase outlet of knockout drum 3 is connected with exhaust gas cooler 4, tail gas cooling
Device 4 is connected with gas treatment equipment, and the liquid-phase outlet of knockout drum 3 is connected with concentrated phosphoric acid cooler 6, and the exhaust gas cooler 4 is set
Have soft water import and soft water preheating outlet, soft water preheating outlet by pipeline successively with 85 phosphoric acid coolers 7, concentrated phosphoric acid cooler
6 are connected, and the saturation soft water outlet of concentrated phosphoric acid cooler 6 is connected with the steam unit of yellow phosphorus boiler 1.
Micro- absorber 2 includes bottom plate and cover plate, provided with the reaction plate on one in bottom plate and cover plate, at the turning of cover plate
Provided with absorbent entrance, absorbent passage is provided with the correspondence position of reaction plate, is laid in the upper face of bottom plate and reaction plate
There are parallel channels, provided with vertical dispersion plate is moved towards with parallel channels at absorbent passage, dispersion hole be provided with dispersion plate,
It is provided with the bottom of reaction plate and is bumped into the groove of dispersion plate, with being provided with gas feed on the bottom plate of absorbent passage the same side,
Provided with gas-liquid mixture outlet on the reaction plate away from absorbent passage side, the hydraulic radius of parallel channels is 0.05mm-
10mm, the radius of dispersion hole is 0.01mm-2mm, and the axis of dispersion hole and the angle of parallel channels axis are 20 ° -90 °, material
Residence time be 1s-60s.
The present invention discloses a kind of method and its device for preparing thermal phosphoric acid and reclaiming heat energy, its Principle of Process, such as Fig. 1 institutes
Show, 5.5t/h liquid phosphor is after atomization with 11.7Nm3/s air contacts and burning in yellow phosphorus boiler 1.Burning is released
The heat put produces saturated vapor or superheated steam by soft water or vapor absorption in boiler, while the gas containing phosphorus pentoxide
Body --- boiler tail furnace gas is cooled.The phosphorus pentoxide in boiler exhaust gas after cooling is anti-with hydrated agent in micro- absorber 2
Should, generation phosphoric acid or polyphosphoric acid solution --- concentrated phosphoric acid, while with unreacted oxygen and nitrogen --- aquation tail gas.The water
Agent is the aqueous solution that P2O5 mass fractions are more than 61.58%, and the gas-liquid mixture discharged from micro- absorber 2 is real in knockout drum 3
Now separate.Gas phase --- aquation tail gas is discharged after demisting from top, after reclaiming heat through exhaust gas cooler 4, then is washed through tail gas
Wash device 5 to purify and demisting, finally extracted out by tail gas, by the row of exhaust fan 10 to air, the wash water of the bottom of exhaust scrubber 5 exists
Under the conveying of wash water circulating pump 9, a part, which is recycled to after the top of exhaust scrubber 5 is mixed with desalted water, does exhaust scrubber 5
Water inlet, and another part is used to prepare the hydrated agent needed for micro- absorber 2.The concentrated phosphoric acid of the bottom of knockout drum 3 is cooled down through concentrated phosphoric acid
Device 6 is reclaimed after heat, and a part is sent to by acid circulating pump 8 to be mixed with entering the wash water of absorber 2 in a subtle way, is formed into absorber in a subtle way
2 hydrated agent, another part is sent to by acid circulating pump 8 and mixed with doing the desalted water of secondary water agent, realizes secondary hydration, generation
The acid of heat 85.The acid of heat 85 is deformed into cold 85 acid --- commercial phosphoric acid after reclaiming heat through 85 phosphoric acid coolers 7.Soft water needed for boiler
Aquation tail air and heat 85 is separately recovered in flow through exhaust gas cooler 4,85 phosphoric acid coolers 7, the concentrated phosphoric acid cooler 6 being sequentially connected in series
After acid and the heat of concentrated phosphoric acid, absorb the combustion heat into boiler and be changed into steam as previously described.
The use of micro- absorber 2：Absorbent is added from absorbent entrance, by below cover plate and below each layer of reaction plate
Gap after, enter through the aperture on dispersion plate contacted in the parallel channels of each layer of reaction plate or substrate with gas,
Mixing.Containing being entered by the gas of absorbent components from gas inlet end after absorber 2 in a subtle way, each layer of reaction plate or bottom plate are assigned to
In parallel channels above, after mixing is contacted with absorbent, micro- absorber 2 is left from the gas-liquid mixture port of export in the lump.
Embodiment 1：
Often using 1 ton of yellow phosphorus, the quality of oxygen is 1.2 tons of yellow phosphorus quality used, and described hydrated agent is water or difference P2O5
The solution of mass fraction, the quality of hydrated agent reclaimed water is 0.29 ton of yellow phosphorus quality, and the water quality of preparation saturation soft water used is
1 ton of yellow phosphorus quality, the consumption of washings is 0.29 ton of yellow phosphorus quality.
Micro- absorber 2 used, parallel channels hydraulic radius is 0.05mm, and the radius of dispersion hole is 0.01mm, dispersion hole
The angle of axis and parallel channels axis be 20 °, the residence time of material is 1s.
Embodiment 2：
Often using 1 ton of yellow phosphorus, the quality of oxygen is 2.4 tons of yellow phosphorus quality used, and described hydrated agent is water or difference P2O5
The solution of mass fraction, the quality of hydrated agent reclaimed water is 3 tons of yellow phosphorus quality, and the water quality used for preparing saturation soft water is yellow phosphorus
10 tons of quality, the consumption of washings is 3 tons of yellow phosphorus quality.
Micro- absorber 2 used, parallel channels hydraulic radius is 5mm, and the radius of dispersion hole is 1mm, the axis of dispersion hole
Angle with parallel channels axis is 55 °, and the residence time of material is 30s
Embodiment 3：
Often using 1 ton of yellow phosphorus, the quality of oxygen is 2.6 tons of yellow phosphorus quality used, and described hydrated agent is water or difference P2O5
The solution of mass fraction, the quality of hydrated agent reclaimed water is 6 tons of yellow phosphorus quality, and the water quality used for preparing saturation soft water is yellow phosphorus
20 tons of quality, the consumption of washings is 6 tons of yellow phosphorus quality.
Micro- absorber 2 used, parallel channels hydraulic radius is 10mm, and the radius of dispersion hole is 2mm, the axis of dispersion hole
Angle with parallel channels axis is 90 °, and the residence time of material is 60s.
By the experiment of embodiment 1,2,3, above-mentioned test data can have a relatively good test structure, and it meets
While the production requirement of thermal phosphoric acid, be conducive into the recycling of reaction heat and combustion heat heat energy during production again.
Claims (6)
1. a kind of method for preparing thermal phosphoric acid and reclaiming heat energy, generation combustion reaction is contacted with oxidant by yellow phosphorus, generation contains
The gas of phosphorus pentoxide, the gas containing phosphorus pentoxide is contacted with hydrated agent, occurs hydration reaction, it is characterised in that：The party
Method is absorbed heat with micro- absorber to the reaction heat of hydration reaction, is brought into point by gas-liquid mixture by reaction heat after micro- absorber
From tank, first pass through tail gas heat quantity reclaimer and concentrated phosphoric acid cooler absorb the heat of gas phase and liquid phase respectively, then by gas phase and
The heat of liquid phase is neutralized, and the vaporising device for being finally delivered to yellow phosphorus boiler in saturation soft water form carries out steam, realizes phosphorus
Acid can reclaim heat energy while preparation；The quality of oxygen is 1.2-2.6 times of yellow phosphorus quality used in described oxidant, described
Hydrated agent be water or difference P2O5The solution of mass fraction, the quality of hydrated agent reclaimed water is 0.29-6 times of yellow phosphorus quality, used
The water quality for preparing saturation soft water is 1-20 times of yellow phosphorus quality.
2. the method according to claim 1 for preparing thermal phosphoric acid and reclaiming heat energy, it is characterised in that：Containing phosphorus pentoxide
Gas contacted with hydrated agent, when occurring hydration reaction, required hydrated agent be it is disposable add or after first time adds, from
Added again at the downstream of the liquid phase of gas-liquid separation.
3. the method according to claim 1 for preparing thermal phosphoric acid and reclaiming heat energy, it is characterised in that：Described exhaust gas heat
Energy recovery device includes exhaust gas cooler and 85 phosphoric acid coolers, and gas is absorbed the tail of cooling after heat by exhaust gas cooler
Pneumatic transmission to exhaust scrubber is washed, and the consumption of washings is 0.29-6 times of yellow phosphorus quality, and the water after washing is used for water
Change reaction.
4. a kind of device for preparing thermal phosphoric acid and reclaiming heat energy, it includes yellow phosphorus boiler（1）, it is characterised in that：Yellow phosphorus boiler
（1）Outlet and micro- absorber（2）Gas inlet end connection, in micro- absorber（2）It is mixed provided with absorbent entrance and gas-liquid
Compound is exported, gas-liquid mixture outlet and knockout drum（3）It is connected, knockout drum（3）Gaseous phase outlet and exhaust gas cooler（4）Connection,
Exhaust gas cooler（4）It is connected with gas treatment equipment, knockout drum（3）Liquid-phase outlet and concentrated phosphoric acid cooler（6）It is connected, it is described
Exhaust gas cooler（4）Exported provided with soft water import and soft water preheating, soft water preheating outlet is cooled down with 85 phosphoric acid successively by pipeline
Device（7）, concentrated phosphoric acid cooler（6）It is connected, concentrated phosphoric acid cooler（6）Saturation soft water outlet and yellow phosphorus boiler（1）Steam dress
Put connected.
5. the device according to claim 4 for preparing thermal phosphoric acid and reclaiming heat energy, it is characterised in that：Described micro- absorption
Device（2）Including bottom plate and cover plate, provided with the reaction plate on one in bottom plate and cover plate, enter at the turning of cover plate provided with absorbent
Mouthful, absorbent passage is provided with the correspondence position of reaction plate, parallel channels are laid with the upper face of bottom plate and reaction plate,
Provided with vertical dispersion plate is moved towards with parallel channels at absorbent passage, dispersion hole is provided with dispersion plate, at the bottom of reaction plate
Portion, which is provided with, is bumped into the groove of dispersion plate, with being provided with gas feed on the bottom plate of absorbent passage the same side, away from absorbent
The reaction plate of passage side is exported provided with gas-liquid mixture.
6. the device according to claim 5 for preparing thermal phosphoric acid and reclaiming heat energy, it is characterised in that：Described is parallel logical
The hydraulic radius in road is 0.05mm-10mm, and the radius of dispersion hole is 0.01mm-2mm, axis and the parallel channels axis of dispersion hole
Angle be 20 ° -90 °, residence time of material is 1s-60s.
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| JPS5484890A (en) * | 1977-12-19 | 1979-07-06 | Kawasaki Heavy Ind Ltd | Apparatus for preparing phosphoric acid |
| CN101157449A (en) * | 2007-09-26 | 2008-04-09 | 云南常青树化工有限公司 | Kiln-way phosphoric acid absorbing defluorination method |
| CN101612510A (en) * | 2008-06-25 | 2009-12-30 | 中国科学院大连化学物理研究所 | A kind of absorption CO 2Micro-channel absorber |
| CN201942519U (en) * | 2010-03-02 | 2011-08-24 | 广西越洋化工有限责任公司 | Thermal energy recovery and utilization device in production of thermal phosphoric acid and production system of thermal energy recovery and utilization device |
| CN202430008U (en) * | 2011-12-23 | 2012-09-12 | 中国化学工程第七建设有限公司 | Device for phosphorus pentoxide production and thermal energy recovery |
| CN105080307A (en) * | 2014-05-12 | 2015-11-25 | 陈汇宏 | Desulfurization and denitrification method for tail gas, used equipment and product application thereof |
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2017
- 2017-06-27 CN CN201710498011.0A patent/CN107140613B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5484890A (en) * | 1977-12-19 | 1979-07-06 | Kawasaki Heavy Ind Ltd | Apparatus for preparing phosphoric acid |
| CN101157449A (en) * | 2007-09-26 | 2008-04-09 | 云南常青树化工有限公司 | Kiln-way phosphoric acid absorbing defluorination method |
| CN101612510A (en) * | 2008-06-25 | 2009-12-30 | 中国科学院大连化学物理研究所 | A kind of absorption CO 2Micro-channel absorber |
| CN201942519U (en) * | 2010-03-02 | 2011-08-24 | 广西越洋化工有限责任公司 | Thermal energy recovery and utilization device in production of thermal phosphoric acid and production system of thermal energy recovery and utilization device |
| CN202430008U (en) * | 2011-12-23 | 2012-09-12 | 中国化学工程第七建设有限公司 | Device for phosphorus pentoxide production and thermal energy recovery |
| CN105080307A (en) * | 2014-05-12 | 2015-11-25 | 陈汇宏 | Desulfurization and denitrification method for tail gas, used equipment and product application thereof |
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Effective date of registration: 20231206 Address after: Room 3025 and 3026, Third Floor, Phase I Building, Hubei Agricultural Science and Technology Research and Extension Center, No. 53 Nanhu Avenue, Hongshan District, Wuhan City, Hubei Province, 430070 Patentee after: WUHAN DONGSHENG JIENENG TECHNOLOGY Co.,Ltd. Address before: 550025 China Gui'an E-commerce Ecological City, Jing'an Avenue, Gui'an New District, Guiyang City, Guizhou Province Patentee before: GUIZHOU DONGSHENG JIENENG TECHNOLOGY CO.,LTD. |