WO2001053426A1 - Process for manufacturing environmentally safe anti-freeze liquid - Google Patents
Process for manufacturing environmentally safe anti-freeze liquid Download PDFInfo
- Publication number
- WO2001053426A1 WO2001053426A1 PCT/HU2001/000003 HU0100003W WO0153426A1 WO 2001053426 A1 WO2001053426 A1 WO 2001053426A1 HU 0100003 W HU0100003 W HU 0100003W WO 0153426 A1 WO0153426 A1 WO 0153426A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- nitrate
- liquid
- concentrates
- ammonium
- compounds
- Prior art date
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- 239000007788 liquid Substances 0.000 title claims abstract description 35
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 24
- 238000000034 method Methods 0.000 title claims abstract description 16
- 230000008569 process Effects 0.000 title claims abstract description 15
- 108010053481 Antifreeze Proteins Proteins 0.000 title description 2
- 230000002528 anti-freeze Effects 0.000 title description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000012141 concentrate Substances 0.000 claims abstract description 17
- 150000001875 compounds Chemical class 0.000 claims abstract description 13
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 claims abstract description 12
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000003112 inhibitor Substances 0.000 claims abstract description 9
- 238000002156 mixing Methods 0.000 claims abstract description 9
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 9
- 238000001704 evaporation Methods 0.000 claims abstract description 6
- 150000001408 amides Chemical class 0.000 claims abstract description 5
- 230000008020 evaporation Effects 0.000 claims abstract description 5
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000004202 carbamide Substances 0.000 claims abstract description 4
- 229910002651 NO3 Inorganic materials 0.000 claims abstract description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000012736 aqueous medium Substances 0.000 claims abstract description 3
- 230000001105 regulatory effect Effects 0.000 claims abstract description 3
- 150000002823 nitrates Chemical class 0.000 claims abstract 2
- 239000000654 additive Substances 0.000 claims description 6
- 238000009835 boiling Methods 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 239000007787 solid Substances 0.000 description 11
- 239000000203 mixture Substances 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- 238000004880 explosion Methods 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 235000002639 sodium chloride Nutrition 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 238000004090 dissolution Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 238000006386 neutralization reaction Methods 0.000 description 4
- 239000011780 sodium chloride Substances 0.000 description 4
- 238000005260 corrosion Methods 0.000 description 3
- 230000018044 dehydration Effects 0.000 description 3
- 238000006297 dehydration reaction Methods 0.000 description 3
- 239000003337 fertilizer Substances 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 230000008014 freezing Effects 0.000 description 3
- 238000007710 freezing Methods 0.000 description 3
- 239000008187 granular material Substances 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- 230000003993 interaction Effects 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- KXDHJXZQYSOELW-UHFFFAOYSA-M Carbamate Chemical group NC([O-])=O KXDHJXZQYSOELW-UHFFFAOYSA-M 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 235000019738 Limestone Nutrition 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000008030 elimination Effects 0.000 description 2
- 238000003379 elimination reaction Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 239000006028 limestone Substances 0.000 description 2
- 229910017464 nitrogen compound Inorganic materials 0.000 description 2
- 150000002830 nitrogen compounds Chemical class 0.000 description 2
- 239000000618 nitrogen fertilizer Substances 0.000 description 2
- 238000007788 roughening Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000004576 sand Substances 0.000 description 2
- 238000004062 sedimentation Methods 0.000 description 2
- 239000002689 soil Substances 0.000 description 2
- 230000007480 spreading Effects 0.000 description 2
- 238000003892 spreading Methods 0.000 description 2
- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- 229940126062 Compound A Drugs 0.000 description 1
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000010426 asphalt Substances 0.000 description 1
- 230000003190 augmentative effect Effects 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- -1 benzoate compounds Chemical class 0.000 description 1
- 238000006065 biodegradation reaction Methods 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000002939 deleterious effect Effects 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 239000010459 dolomite Substances 0.000 description 1
- 229910000514 dolomite Inorganic materials 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 1
- 229940093476 ethylene glycol Drugs 0.000 description 1
- 230000005496 eutectics Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000007717 exclusion Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 230000000873 masking effect Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 238000005649 metathesis reaction Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000009938 salting Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 238000010408 sweeping Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
- C09K3/18—Materials not provided for elsewhere for application to surfaces to minimize adherence of ice, mist or water thereto; Thawing or antifreeze materials for application to surfaces
- C09K3/185—Thawing materials
Definitions
- the invention concerns a process for manufacturing an environmentally safe, quickly acting snow and ice dissolving liquid chiefly composed of amide and nitrate 0 compounds in aqueous medium by reactions in liquid state.
- the sleet and the poorly visible ice film stemming from the hoar-frost on the road surface is particularly dangerous the prevention, removal and hindering in regeneration of which can be attained reasonably such as without the expensive and circumstantial heating of the road surface only by use of ice dissolving compounds according to the present state of the art.
- rock salt As snow and ice melting compound rock salt is predominantly used first of all by economic reasons. Because of its limited solubility in water (slightly above 300 g/liter), it is generally strewn out in solid state that, in turn, leads to deceleration in ice melting and to troubles in uniform spreading. At the same time the economy as such becomes contestable due to the fact that to the uniform spreading of the rock salt, all the more to enable the speed-controlled dosage by the salt-strewing vehicle complicated and expensive equipment are needed, whilst the uniform strewing out of the liquid can be attained (in given cases with some transformation) by the summer street-sprinklers that are idle in winter.
- ethylene-glycol containing compositions have also been used first of all for airdrome runways' deicing in order to decrease in corrosion activating effect of the salt.
- This method has increasingly been restricted recently on account of the heavily toxic effect of the glycol, especially if it can get as far as the subsoil water before being biologically decomposed to a satisfactory degree.
- An anti-skid liquid chiefly composed of nitrogen chemical fertilizer components (urea [K] and ammonium-nitrate [A]) can be learnt in the description of the Hungarian patent No. 216865 and European patent No. 0824575 offering detailed grounds for the prescribed mass ratio of the main components (i.e water, K- and A) in view of the manner of action and of other, e.g. environment protection aspects, without giving instructions for the way of manufacture.
- the only inference can be drawn even by the specialist that the said three main components are to be mixed with one another in the given ratio in order to produce the ice melting target-liquid in a direct or indirect way.
- the indirect way consists in providing the prescribed nitrogen compounds in part as liquid nitrogen chemical fertilizer, in part, however, as solid A to the manufacturing of the target-product.
- the recognition of the compound formation contributed to the realization of the process in compliance with the invention (direct liquid synthesis), because the K - A interaction and the availability of the extreme concentration ratios taking their origin therein enables the combination of the K and A manufacturing steps in an advantageous phase as well as the elimination of their preparation in solid state together with the use and thereafter the filtration of additives hindering from cxplo- sion-and sticking along with the additional expenses of the evaporation and the technical-economic advantages thereof.
- ammonium-carbamatc is produced in the first step by having liquid ammonia and carbon-dioxide gas reacted, then water will be split off therefrom by thermal decomposition that results in molten K formation containing about 20% water at 180 - 200 °C ( ⁇ 360 - 390 °F).
- the granular final product is usually attained by its (mostly two-step) evaporation.
- the present day processes start from a 45 - 65% nitric acid solution and ammonia gas, having them reacted at atmospheric pressure or at slight overpressure, then the aqueous A concentrate originated in metathesis is evaporated in part by the heat of reaction, in part by external heating in (mostly multi-step) vacuum-evaporators, combined with graining, sizing and powdering.
- the K. and A containing concentrates are mixed in the 4 and 7 A content ratio in the phase of the evaporative operations that has the water quantity corresponding to the prescribed 5 weight ratios got into the produced mixture.
- the treated combination of the K. and A manufacturing operations is more advantageous even in view of the productivity than the blending the A, the and the inhibitor compounds with water at ambient temperature, as it would be done basic to the patents treated.
- the specific quantity of the water is also to be set corresponding to the prescribed weight fraction 5, i.e. 3 1 ,25 % (regardless of the slight change due to the inhibitors).
- the weight fraction of the water can reliably be controlled in continuous way of operation both by choosing the rate (degree) of the multi-step evaporation and by prescription of the nitric acid concentration used to the A manufacture inside the generally applied 45 - 65 % range.
- ammonium-nitrate manufacturing variety the produced ammonium-nitrate solution is partially re-circulated into the upper part of the atmospheric neutralization tower and saturated with ammonia again, then this alkaline solution is reneu- tralizcd with nitric acid solution fed at the bottom of the bent-tube, while in the lower part of the column the neutral ammonium-nitrate solution is evaporated, i.e. concentrated by means of air blowing in.
- This technology enables all kinds of ammonium-nitrate concentrate side-draw that ensures its concentrating needed to the urea-melt (stemming from the carbamate-splitting unit generally in a concentration of about 80 %) in order to maintain continuously the main components' 5:4:7 weight-fractions in the target-make as prescribed in the foregoing.
- the carbamate decomposer whatever the degree of the carbamatc re- circulation, generally provides a urea-melt concentration of about 80 % and the occasional fluctuation thereof doesn't constitute any hardship in the regulation of the ammonium-nitrate concentrate feeding either and since nor the construction and way of operation of the target-make reactor depend on the raw-material main components' producing conditions, it is in this example only the side-draw carrying out of the ammonium-nitrate concentrate in the prescribed quality and concentration that departs from the solution according to the previous or other examples.
- nitric acid is neutralized at moderate overpressure that enables a continuous NH 4 N0 3 concentration setting prescribed and regulated between 60 - 70 % by the vapor-withdrawal rate in the liquid separator after the neutralizing reactor and before the multi-step evaporator.
- the NH 4 N0 3 concentration of 63,6 % according to the previous example can be maintained and in the following the feeding and operational prescriptions detailed therein are to be observed.
- the advantages of the process according to the invention lie in enabling the elimination and saving of the nitrogen-fertilizer main components' complete concentrating, evaporating, graining, powdering, then that of the target-make sedimentation and/or filtration as well as in the exclusion of the explosion hazard along with the drawbacks due to the grains' sticking, in making use of the operational advantages inherent in the homogeneous reactions ensured by the liquid reactants, in intensification of the manufacturing, in accomplishment of the perfectly interdependent chemical combine system by disconnecting the shipment of the nitrogen fertilizer intermediates.
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Combustion & Propulsion (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention concerns a process for manufacturing an environmentally safe, quickly acting snow and ice dissolving liquid chiefly composed of amide and nitrate compounds in aqueous medium by reactions in liquid state, connecting the said process with the manufacture of urea and ammonium-nitrate by blending the aqueous concentrates of these compounds in a ratio corresponding to the amide and nitrate concentration of the anti-skid liquid target-make, the water content of which is set by regulating the total water content of the aqueous concentrates, choosing in part the concentration of the nitric acid serving for the ammonium-nitrate manufacture and/or in part the degree of the concentrates' evaporation, whilst the anti-corrosive inhibitors are fed directly after the blending of the concentrates into the still warm liquid.
Description
PROCESS FOR MANUFACTURING ENVIRONMENTALLY SAFE ANTI-FREEZE LIQUID
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Technical Field
The invention concerns a process for manufacturing an environmentally safe, quickly acting snow and ice dissolving liquid chiefly composed of amide and nitrate 0 compounds in aqueous medium by reactions in liquid state.
The freeing from snow and ice of public roads, sidewalks, railway switches and other objects to be protected from slippcrincss hazard and operating troubles in winter is an important requirement in view of the transport and facilities safety and, first of all, on account of the life danger. On the other hand, it is a fact of experience, that the complete removal of the slippcrincss producing frozen moisture by mechanic means (shoveling, sweeping or „plowing") cannot in most cases be attained satisfactorily, since the slipperiness takes its origin first of all in the thin ice film adhering to the surface of e.g. asphalt and concrete. The sleet and the poorly visible ice film stemming from the hoar-frost on the road surface is particularly dangerous the prevention, removal and hindering in regeneration of which can be attained reasonably such as without the expensive and circumstantial heating of the road surface only by use of ice dissolving compounds according to the present state of the art.
Background Art
As snow and ice melting compound rock salt is predominantly used first of all by economic reasons. Because of its limited solubility in water (slightly above 300
g/liter), it is generally strewn out in solid state that, in turn, leads to deceleration in ice melting and to troubles in uniform spreading. At the same time the economy as such becomes contestable due to the fact that to the uniform spreading of the rock salt, all the more to enable the speed-controlled dosage by the salt-strewing vehicle complicated and expensive equipment are needed, whilst the uniform strewing out of the liquid can be attained (in given cases with some transformation) by the summer street-sprinklers that are idle in winter. The use of the solid rock salt becomes even more expensive by its wetting in order to prevent it from being whirled away by the wind that results, besides additional expenses, in further cumbersome opera- tions. If, however, the salt - for roughening the road surface - is mixed with sand as well, in addition to the expenses linked with the said mixing, the expenses will further be augmented by the spring clearing away o the sand.
Accordingly, it is obvious that to the technical-economic comparison of the solid and liquid compositions a complex evaluation is needed, the mere contrasting of the chemicals' prices isn't satisfactory. On this account the liquid anti-skid agents have also come to the fore recently, all the more so because the corrosive effect of the rock salt is particularly deleterious to the metallic elements of vehicles, bridges, overpasses and subsoil objects. Another objection is that the vegetation is also suffering damage by the salting of the soil.
As anti-skid liquid, ethylene-glycol containing compositions have also been used first of all for airdrome runways' deicing in order to decrease in corrosion activating effect of the salt. This method, however, has increasingly been restricted recently on account of the heavily toxic effect of the glycol, especially if it can get as far as the subsoil water before being biologically decomposed to a satisfactory degree.
An anti-skid liquid chiefly composed of nitrogen chemical fertilizer components (urea [K] and ammonium-nitrate [A]) can be learnt in the description of the Hungarian patent No. 216865 and European patent No. 0824575 offering detailed
grounds for the prescribed mass ratio of the main components (i.e water, K- and A) in view of the manner of action and of other, e.g. environment protection aspects, without giving instructions for the way of manufacture. On this account the only inference can be drawn even by the specialist that the said three main components are to be mixed with one another in the given ratio in order to produce the ice melting target-liquid in a direct or indirect way. The indirect way consists in providing the prescribed nitrogen compounds in part as liquid nitrogen chemical fertilizer, in part, however, as solid A to the manufacturing of the target-product.
Grounds for the Target
When producing liquid makes, it is always advantageous from operational point of view if also the main raw materials arc in liquid state available and i f the least possible solid components' quantity using up or transitional formation occurs. In addi- tion, the explosion hazard of the A must also be taken into account in the given case allowing for a number of accidents having taken place so far. The operations with solid A become troublesome also because of its hygroscopic nature that makes the calculated quantity of the raw material uncertain and the wet granules' sticking makes circumstantial the operations too. This latter hardship, albeit in a less degree, arises in case of the K. as well.
In the course of the A manufacture, to the still warm, from the bottom of the sprinkler conveyed granules, fine limestone, dolomite or bentonite dust suitable for coating their surface is fed in the air circulating rotary cooler, in order to decrease in explosion hazard and to prevent the granules from sticking. On this account, the original 35% nitrogen content of the pure A will be decreased to 34%, this is usually marked with inscription „34 N" on the sacked shipment. Since the mass of the additive makes in round figure 3% referred to the compound A, the ice combating liquid will be strongly turbid owing to the insoluble suspended impurities therein.
Although this is not disadvantageous for the ice combating (the roughening additive is even advantageous), in order to prevent the spraying nozzles from getting clogged, however, the sedimentation and/or filtration of the turbid liquid is indispensable. When starting from nitrogen chemical fertilizers widely used in agrieul- ture consisting of A and limestone mixture, that can in given cases constitute a ,,26 N" quality according to the previous treatment, the problems stemming from the solid A feeding become still more conspicuous.
The Inventive Steps
From the said data the inference can be drawn that the target-make described in the Hungarian patent No. 216865 and European patent No. 0824575 is, as far as possible, to be got avoiding the use of the solid main component prime materials. Since the A and are, as a matter of fact, manufactured (albeit in several variations as far as the details arc concerned) according to the present state of the art by dehydration of the concentrates having come into being after the neutralization of the nitric acid and the thermal decomposition of the carbamate respectively and the said dehydration is connected with graining and powdering in different constructional and operational ways in multi-step evaporators, the main components of the target-make are to be mixed in prescribed ratio in the phase of dehydration that the anti- explosion and anti-adhesion additives haven't yet been fed to the concentrate in. If the complete concentrating of the prime components is eliminated, both the explosion and sticking hazard can obviously be avoided.
A further inference leading to the invention was that the liquid described in the patents treated characteristic for the present state of the art cannot be theoretically regarded as simple mixture of the components (as e.g. the ethanol - water or ethanol - glycol mixture), since the properties of the liquid, upon getting to the prescribed mass ratio (5 parts water + 4 parts K + 7 parts A) undergo an abrupt change in
quality due to a compound-formation. The 4:7 K:A ratio at 8 parts of mass water represents the eutectic composition with -28 °C (= - 18,4 °F) freezing point ensuring at the same time the greatest possible decrease in freezing point, i.e. the lowest freezing point whatever the other than 8 water mass ratio. The presence of water mediates a special type of interaction between the acceptor nitrogen of the amide substitucnts of the K. and NH + cations of the A on the one hand and the donor nitrogen of the N03 ~ anions on the other leading among others to a drastic increase in solubility both for A and (in fact, the A and the react with one another too in the presence of water). This peculiar effect can be elucidated by the following data.
At ambient temperature nearly one weight fraction of K. and Λ respectively can be dissolved in one weight fraction of water (it is of primary concern in view of the concrete technology that the water-solubility of both compounds rapidly increases on increase in temperature). If, however, both K. and A are together in a mass ratio of 4:7 at ambient temperature, 2 weight fractions of and 3,5 weight fractions of A pass into the liquid state beside one weight fraction of water resulting in a 2:4:7 watcr-K-A mass ratio. Since in this liquid beside one weight fraction water there arc 5,5 weight fractions of A + K, albeit in case of pure A or K only one weight fraction of either of them could be in dissolved state, it is obvious that the A and K have re- acted with one another i.e. they have dissolved one another mutually by the mediation of water. This interaction, or, from another aspect, compound formation evidences itself in the change of several macroscopic properties, such as decrease in propensity to corrosion and explosion, biodegradation accelerated by the organic components in the soil as well as the significant change in the original properties of the A and K compounds (masking by A and K linkage in chemical bond).
The compound producing manifests itself also by one of its fundamental criteria: the 2:4:7 mass ratio corresponds to a 5:3:4 molar ratio (allowing for the nearly complete suppression of the A dissociation). Accordingly, the law of constant proportions is also fulfilled.
The recognition of the compound formation contributed to the realization of the process in compliance with the invention (direct liquid synthesis), because the K - A interaction and the availability of the extreme concentration ratios taking their origin therein enables the combination of the K and A manufacturing steps in an advantageous phase as well as the elimination of their preparation in solid state together with the use and thereafter the filtration of additives hindering from cxplo- sion-and sticking along with the additional expenses of the evaporation and the technical-economic advantages thereof.
Disclosure of the Invention
Although the equipment and operations of the K. and A manufacturing technology arc different as far as the details arc concerned, they functionally fit in with one an- other to such an extent that the operational phase needed to the carrying out of the process according to the invention is generally within reach.
When manufacturing the K, ammonium-carbamatc is produced in the first step by having liquid ammonia and carbon-dioxide gas reacted, then water will be split off therefrom by thermal decomposition that results in molten K formation containing about 20% water at 180 - 200 °C (~ 360 - 390 °F). The granular final product is usually attained by its (mostly two-step) evaporation. When manufacturing A, the present day processes start from a 45 - 65% nitric acid solution and ammonia gas, having them reacted at atmospheric pressure or at slight overpressure, then the aqueous A concentrate originated in metathesis is evaporated in part by the heat of reaction, in part by external heating in (mostly multi-step) vacuum-evaporators, combined with graining, sizing and powdering.
Applying the process according to the invention, the K. and A containing concentrates are mixed in the 4 and 7 A content ratio in the phase of the evaporative operations that has the water quantity corresponding to the prescribed 5 weight ratios got into the produced mixture. This ensures, at the same time, due to the compound formation treated, that the produced liquid keeps the nitrogen-compounds in liquid state at any temperature, containing even excess water in such an extent, that enables the quick dissolution of the anti-corrosion inhibitors at the temperature of the formation in spite of the endothermic process of the 4K - 7A compound buildup. The heat needed to it is, however, ensured by the heat capacity of the liquid itself. This leads to the decrease in the temperature of the hot concentrates' mixture by about 20 °C (36 °F) but it remains even then at about 100 °C (~ 210 °F) or in a region thercabove. This ensures the quick dissolution of the solid inhibitors fed into the hot liquid during agitation.. Since the dissolution rate of the solid additives is a productivity determining factor in the given case and, on the other hand, since this rate increases exponentially on increase in temperature, the treated combination of the K. and A manufacturing operations is more advantageous even in view of the productivity than the blending the A, the and the inhibitor compounds with water at ambient temperature, as it would be done basic to the patents treated. When combining the A and manufacturing steps, beside ensuring the 4:7 K:A ratio in the make as treated, the specific quantity of the water is also to be set corresponding to the prescribed weight fraction 5, i.e. 3 1 ,25 % (regardless of the slight change due to the inhibitors). The weight fraction of the water can reliably be controlled in continuous way of operation both by choosing the rate (degree) of the multi-step evaporation and by prescription of the nitric acid concentration used to the A manufacture inside the generally applied 45 - 65 % range.
Best Mode for Carrying out of the Invention
Although the implementation of the process according to the invention represents the knowledge of the trade, the following examples can serve as further elucidation to the technical solution, remarking that the data therein can be changed adjusting themselves to the A and K manufacturing technology according to the sense.
EXAMPLE 1 Manufacture connected with the Hobbler's nitric acid neutralization
In this ammonium-nitrate manufacturing variety the produced ammonium-nitrate solution is partially re-circulated into the upper part of the atmospheric neutralization tower and saturated with ammonia again, then this alkaline solution is reneu- tralizcd with nitric acid solution fed at the bottom of the bent-tube, while in the lower part of the column the neutral ammonium-nitrate solution is evaporated, i.e. concentrated by means of air blowing in. This technology enables all kinds of ammonium-nitrate concentrate side-draw that ensures its concentrating needed to the urea-melt (stemming from the carbamate-splitting unit generally in a concentration of about 80 %) in order to maintain continuously the main components' 5:4:7 weight-fractions in the target-make as prescribed in the foregoing. In case of the example, to manufacture (without inhibitors) a 3200 kg make batch, 2200 kg ammonium-nitrate concentrate of 63,6 % is introduced into the target-make producing blending reactor from the Hobbler neutralizer section before the vacuum evaporator and 1000 kg urea melt of 80% is fed thereto, then, during continuous agitation, the inhibitors (among others the benzoate compounds) are fed into the liquid still of 100 °C (~ 210 °F) in spite of its cooling by about 20 °C (36 °F) during the instantaneous reaction. Under such circumstances the complete dissolution of the inhibitors proceeds during short time (not more than five minutes).
EXAMPLE 2 Manufacture connected with ITN-type nitric acid neutralization
Since the carbamate decomposer, whatever the degree of the carbamatc re- circulation, generally provides a urea-melt concentration of about 80 % and the occasional fluctuation thereof doesn't constitute any hardship in the regulation of the ammonium-nitrate concentrate feeding either and since nor the construction and way of operation of the target-make reactor depend on the raw-material main components' producing conditions, it is in this example only the side-draw carrying out of the ammonium-nitrate concentrate in the prescribed quality and concentration that departs from the solution according to the previous or other examples.
In the ITN reactor relatively thin (~ 48 %) nitric acid is neutralized at moderate overpressure that enables a continuous NH4N03 concentration setting prescribed and regulated between 60 - 70 % by the vapor-withdrawal rate in the liquid separator after the neutralizing reactor and before the multi-step evaporator. In this way the NH4N03 concentration of 63,6 % according to the previous example can be maintained and in the following the feeding and operational prescriptions detailed therein are to be observed.
Accordingly, the advantages of the process according to the invention, contrary to the solutions representing the current state of the art, i.e. blending the main components of the target-make directly, lie in enabling the elimination and saving of the nitrogen-fertilizer main components' complete concentrating, evaporating, graining, powdering, then that of the target-make sedimentation and/or filtration as well as in the exclusion of the explosion hazard along with the drawbacks due to the grains' sticking, in making use of the operational advantages inherent in the homogeneous reactions ensured by the liquid reactants, in intensification of the manufacturing, in
accomplishment of the perfectly interdependent chemical combine system by disconnecting the shipment of the nitrogen fertilizer intermediates.
Claims
1. Process for manufacturing snow-and ice combating anti-skid liquid composed of an amide-and nitrate compounds' combination in aqueous medium characterized in that its operations are connected with the urea and ammonium-nitrate producing ones by blending the aqueous concentrate of these compounds in a ratio corresponding to the amide and nitrate concentration ofthe anti-skid liquid prior to their boiling dry, graining and mixing with anti-sticking additives.
2. Process according to claim 1, characteri zed i n that the water content of the anti-skid liquid is set by regulating the total water content of the aqueous concentrates, choosing in part the concentration ofthe nitric acid serving for the ammonium-nitrate manufacture and/or in part the degree ofthe concentrates' evaporation.
3. Process according to claim 1, charac teri zed i n th at the anti- corrosive inhibitors are fed directly after the blending ofthe concentrates into the still warm liquid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| AU26972/01A AU2697201A (en) | 2000-01-18 | 2001-01-17 | Process for manufacturing environmentally safe anti-freeze liquid |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| HUP0000154 | 2000-01-18 | ||
| HU0000154A HU0000154D0 (en) | 2000-01-18 | 2000-01-18 | Process for producing environment-frienoly supperyless liquid |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO2001053426A1 true WO2001053426A1 (en) | 2001-07-26 |
Family
ID=89978020
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/HU2001/000003 WO2001053426A1 (en) | 2000-01-18 | 2001-01-17 | Process for manufacturing environmentally safe anti-freeze liquid |
Country Status (3)
| Country | Link |
|---|---|
| AU (1) | AU2697201A (en) |
| HU (1) | HU0000154D0 (en) |
| WO (1) | WO2001053426A1 (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4174379A (en) * | 1978-04-13 | 1979-11-13 | Foster Wheeler Energy Corporation | Manufacture of ammonium nitrate |
| US4230479A (en) * | 1979-03-30 | 1980-10-28 | Phillips Petroleum Company | Process for improving the quality of urea-ammonium nitrate solution |
| US4439223A (en) * | 1982-12-10 | 1984-03-27 | Tennessee Valley Authority | Production of urea-ammonium nitrate suspension fertilizer |
| US4689165A (en) * | 1984-07-18 | 1987-08-25 | Komaromi Koolajipari Vallalat | Heat transfer liquid |
| WO1996034927A1 (en) * | 1995-05-03 | 1996-11-07 | Kerti Jozsef | Environmentally safe snow and ice dissolving liquid |
-
2000
- 2000-01-18 HU HU0000154A patent/HU0000154D0/en unknown
-
2001
- 2001-01-17 WO PCT/HU2001/000003 patent/WO2001053426A1/en active Application Filing
- 2001-01-17 AU AU26972/01A patent/AU2697201A/en not_active Abandoned
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4174379A (en) * | 1978-04-13 | 1979-11-13 | Foster Wheeler Energy Corporation | Manufacture of ammonium nitrate |
| US4230479A (en) * | 1979-03-30 | 1980-10-28 | Phillips Petroleum Company | Process for improving the quality of urea-ammonium nitrate solution |
| US4439223A (en) * | 1982-12-10 | 1984-03-27 | Tennessee Valley Authority | Production of urea-ammonium nitrate suspension fertilizer |
| US4689165A (en) * | 1984-07-18 | 1987-08-25 | Komaromi Koolajipari Vallalat | Heat transfer liquid |
| WO1996034927A1 (en) * | 1995-05-03 | 1996-11-07 | Kerti Jozsef | Environmentally safe snow and ice dissolving liquid |
Also Published As
| Publication number | Publication date |
|---|---|
| AU2697201A (en) | 2001-07-31 |
| HU0000154D0 (en) | 2000-03-28 |
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