CN110382459A - Liquid urea hydrohalide - Google Patents
Liquid urea hydrohalide Download PDFInfo
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- CN110382459A CN110382459A CN201880013394.0A CN201880013394A CN110382459A CN 110382459 A CN110382459 A CN 110382459A CN 201880013394 A CN201880013394 A CN 201880013394A CN 110382459 A CN110382459 A CN 110382459A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C273/00—Preparation of urea or its derivatives, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups
- C07C273/02—Preparation of urea or its derivatives, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups of urea, its salts, complexes or addition compounds
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/02—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing liquids as carriers, diluents or solvents
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B7/00—Halogens; Halogen acids
- C01B7/01—Chlorine; Hydrogen chloride
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B7/00—Halogens; Halogen acids
- C01B7/09—Bromine; Hydrogen bromide
- C01B7/093—Hydrogen bromide
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Abstract
Present invention offer contains 50% or more hydrohalide and the 8% hydrohalide aqueous solution composition to be lauched.The method containing the up to composition of 95% urea hydrohalide for being used to prepare and being in a liquid state at ambient temperature is provided.
Description
Technical field
The present invention relates to the liquid phase compositions of the hydrohalide comprising concentration and its preparation processes.Specifically, the present invention mentions
For solution middle and high concentration urea hydrohalide as manufacture halogen carbamide compounds precursor.
Background technique
Urea hydrohalide aqueous solution has been used for preparing biocide, for example, by the way that urea is dissolved in HBr or HCl
(referring to WO2013/132492 or WO2013/140402) in aqueous solution.From the perspective of the use, transport and storage of reagent,
It is advantageous using concentrated reagent.WO2013/132492 is mixed using 48%HBr with excess urea, is provided containing less than 30%
HBr and at least 30% water mixture.The concentration for further increasing HBr is needed using high vacuum and high temperature, this not only makes
Process complications, and also result in the formation enhancing of byproduct (such as biuret).In order to reduce required temperature, lead in the process
It crosses azeotropic distillation to promote that organic solvent can be used when water removal, then removes the organic solvent again.Above-mentioned technique was both time-consuming
It consumes energy again, and unwanted waste can be generated.Therefore, the purpose of the present invention is to utilize relatively easy and economic technique offer
High concentration urea hydrohalide solution.
It is a further object to provide a kind of methods for producing concentrated liquid urea hydrohalide, while excluding to steam
Evaporate step.
It is a further object to provide a kind of methods for producing concentrated liquid urea hydrohalide, while avoiding making
Use organic solvent.
It is a still further object of the present invention to provide a kind of stable, high concentration the Solution-Phase Combinatorial comprising urea hydrohalide
Object is used to prepare biocide formula.
It is a still further object of the present invention to provide the liquid urea hydrohalide of high concentration, it includes for manufacture bromo and
The bromide and/or chloride precursor of chloro biocide.
It is a still further object of the present invention to provide the stabilization liquid of high HBr content, are optionally mixed with HCl.
Other objects and advantages of the present invention will show with the progress of description.
Summary of the invention
Present invention offer is in a liquid state at room temperature and includes molecular formula
(NH2)2CO.HX
Shown in urea hydrohalide composition, wherein (NH2)2CO is urea, and HX is hydrogen halides, the composition packet
Containing at least 35% hydrogen halides HX and most 25% water.Term " % " refers to weight %.The composition preferably comprises at least
40% hydrogen halides and most 12% water.The hydrogen halides is selected from HBr and HCl.In a preferred embodiment, institute of the present invention
The HX in composition stated is HBr, and the molecular formula of the urea hydrohalide is
(NH2)2CO.HBr。
In a further advantageous embodiment, HX is the mixture of HCl and HBr, and composition of the present invention includes molecule
Formula (NH2)2Urea hydrobromide and molecular formula (NH shown in CO.HBr2)2The mixing of urea hydrochloride shown in CO.HCl
Object.In one embodiment, the mixing of HCl and HBr is equimolar.
In the first preferred aspect of the invention, the liquid phase compositions include at least 50% HBr and most 12% water,
The water of for example, at least 52% HBr and most 8%, the water of for example, at least 53% HBr and most 7%.Of the invention second
Preferred aspect, the liquid phase compositions include at least 30% HBr, the water of at least 13% HCl and most 12%, for example, at least
31% HBr, at least 14% HCl and most 8% water.
The present invention is provided comprising at least one molecular formula (NH2)2The liquid phase compositions of urea hydrohalide shown in CO.HX,
Wherein HX is selected from HBr and HCl, and the hydrohalide constitutes at least the 85% of the composition, such as the composition is at least
90%.Water preferably comprises the 4% to 12% of the composition.The composition may include at concentrations up to 5%, such as be up to
4%, such as up to 3%, such as up to 2%, such as up to 1% free urea.The composition also may include concentration height
Up to 5%, such as up to 4%, such as up to 3%, such as up to 2%, for example, up to 1% free HBr or HCl or they
Mixture.The composition is liquid at ambient temperature, the environment temperature usually between 15 DEG C to 35 DEG C, such as
Between 20 DEG C to 30 DEG C, such as 25 DEG C.If it is desired, the composition can be solidified using reducing temperature or reducing water content, this
It comes in handy in some applications.
It include at least one molecular formula (NH the present invention is provided to prepare2)2The group of urea hydrohalide shown in CO.HX
The technique for closing object, wherein (NH2)2CO is urea, and HX is the hydrogen halides selected from HBr and HCl, and the composition includes at least 35%
Hydrogen halides HX and most 25% water, including solid urea is added in step i) Xiang Shui or aqueous solution of hydrogen halide, to obtain
The aqueous slurry of urea；And ii) gaseous hydrogen halide or halide are added into slurry described in step i), to dissolve the slurry
Expect and obtain urea hydrohalide solution, while the cooling reaction mixture is to 90 DEG C of temperature below, such as 70 DEG C of highest
Temperature, preferably up to 60 DEG C；The composition is in a liquid state at ambient temperature or solid-state.In one aspect of the invention, pass through institute
Technique is stated to provide comprising the urea hydrohalide at concentrations up to 95% and the composition that is in a liquid state at ambient temperature.In the present invention
Another aspect, provide and be at least 80% comprising concentration, for example, at least for 90% urea hydrohalide composition, it is therein
Hydrohalide, preferably HBr, constitute at least the 45% of the composition, and more preferably at least 50%, for example, at least 52%, such as extremely
Few 54%, for example, at least 56%；At ambient temperature, the composition can be liquid or waxy solid.In yet a further aspect,
The urea of the molar excess of hydrohalide is comprised more than by the composition that the technique provides.
The present invention is provided to prepare the technique of above-mentioned hydrohalide composition, including step i) Xiang Shui or hydrogen halides it is water-soluble
Solid urea is added in liquid, to obtain the aqueous slurry of urea；And ii) gaseous state halogenation is added into slurry described in step i)
Hydrogen, to dissolve the slurry and obtain urea hydrohalide solution；The reaction mixture is cooled down simultaneously to preferred temperature 15
DEG C between 60 DEG C.Hydrogen halides described in step i) is selected from HBr and HCl；Independently, step ii) described in gaseous state halogenation
Hydrogen is selected from HBr and HCl.In one embodiment of technique of the present invention, the urea hydrogen halogen is added in second part urea
In compound solution, thus to obtain the second slurry, second part gaseous hydrogen halide is then added into second slurry, thus molten
It solves second slurry and obtains the second urea hydrohalide solution.Technique of the present invention preferably includes to measure the urea hydrogen
The step of content of at least one of halide solution component, wherein the component is selected from the group of water, HBr and HCl composition, if
The content value of measurement is different from predetermined value, further includes the steps that being sequentially added to lack a kind of reagent selected from urea, HBr and HCl.
Detailed description of the invention
It has now been discovered that the urea hydrobromide liquid of high concentration can be obtained with hydrogen bromide gas treatment urea slurry
Body.For example, obtaining high concentration urea hydrobromide (table by introducing HBr gas in the water of minimum volume or HBr aqueous solution
It is shown as " urea .HBr ")；The study found that the formation of soluble urea hydrobromide makes the slurry in exothermal reaction process
Dissolution rapidly.The reaction is conducive to provide more urea and more HBr in the solution, while reducing the dense of water in solution
Degree.The concentration of water can be adjusted required level, such as the value adjusted to most 10%.Thus, for example, obtaining high concentration
Urea hydrobromide solution, water content is down to 8% or lower, such as down to 7% or lower, such as 6% or lower.HBr
It is up at least 50%, for example, at least 51%, for example, at least 52%, or at least 53%, or at least 54% that content, which can be adjusted,.
It is surprising that even if can also be obtained at ambient temperature certainly under up to 93% or even 95% urea .HBr concentration
By the liquid flowed.These liquid can be used as precursor and reagent performs well in preparing biocide blend, such as with
When the oxidant reaction of NaOCl etc, while obtaining the activating agent of required various concentration.The high concentration of nonaqueous component allows for
The flexible use of precursor, and also reduce transportation cost；The high concentration of component further improves the steady of urea hydrobromide
It is qualitative.Even if can also obtain longer storage life in the case where being higher than 30 DEG C, such as 40 DEG C or higher temperature.This stability makes this
The reagent and precursor of invention can use under any actual ambient temperature.
Hydrogen halide can be used for preparing or mixtures thereof urea hydrohalide, is advantageously used in preparation and includes chlorourea, bromine
The biocide blend of or mixtures thereof urea.In one embodiment of the invention, HCL aqueous solution can be used (such as to wrap
Containing 32% to 37%)；It is preferred, however, that using gaseous HCl.It in some applications, can be the first of technique of the present invention
Stage uses HBr aqueous solution.In other applications, using liquid and/or gaseous HBr, gaseous HCl is then used.The party
Method can provide required high concentration HCl and/or HBr in biocide preparation.
By the new method of preparation high concentration liquid urea hydrohalide compared with various alternatives carry out experiment, inventor
These alternatives are partially used in its previous activity (referring to WO2013/132492).In alternative, also examine or check
Following procedure and step: a) high vacuum distillation (2mmHg under high temperature) of urea hydrobromide (urea .HBr) solution；B) it urinates
Organic solvent (hexane or heptane) azeotropic distillation of plain .HBr solution (urea: HBr=2:1.1), then removes the organic solvent；
C) it is bubbled into HBr gas in ethyl alcohol-urea slurry, ethyl alcohol is then removed in vacuum distillation (30mmHg).Of the invention
Preferred method includes that HBr gas sparging is made to pass through urea slurry, then adds other solid urea and other HBr gas.
Comparative test clearly shows the advantages of the method for the invention, including eliminating distillation or using the complicated step of organic solvent
Suddenly.The inventive process provides required mixtures, and are free of waste byproduct.
A free-revving engine of the invention is to provide a kind of liquid urea halogen acid salt of high concentration.The present invention, for example, mentioning
For the urea hydrobromide of liquid, include the HBr at concentrations up to 53%.It is of the present invention to prepare high concentration urea hydrohalide
Method include the steps that provide urea aqueous slurry, and into the slurry mix gaseous hydrogen halide the step of.The technique
By mildly cooling controlled, react lower than 75 DEG C at a temperature of carry out, usually carry out at relatively low temperature, example
Such as it is lower than 40 DEG C, such as less than 30 DEG C.It can be carried out at temperature identical with environment temperature.In the method for the invention,
Urea is gradually added into reaction mixture, so that it is constantly dissolved.In one embodiment, first part's urea in slurry
It is dissolved by the way that first part's hydrogen halides is added, then adds second part urea and hydrogen halides, etc..In one embodiment
In, solid urea and gaseous state HBr with many small increment additions or are added continuously in reaction mixture.The minimum of water can be achieved
Amount is above zero a few percent, and composition of the invention preferably comprises at least 4% water, the highest corresponding to HBr about 55%
Amount can be achieved.In a preferred embodiment, the present invention provides the urea that the concentration being in a liquid state at ambient temperature is about 95%
.HBr composition.The present invention provides, for example, be at least 88%, for example, at least 92% comprising concentration, for example, at least 94% urine
The liquid phase compositions of plain .HBr are respectively at least about 50%, about 53% it includes concentration, or about 54% HBr.
Technique of the invention provides, for example, the urea hydrobromide of concentration, comprising steps of with the urea and water of calculation amount
Urea slurry is prepared, gaseous state HBr is then added, to dissolve the slurry, several step addition reagents can be divided, until obtaining
Required water content and required HBr content.Inventive process avoids using evaporation, at the same it is real in final product salt
Highest HBr content is showed.The water of the minimum allowed in the final product advantageously makes product become liquid, although its concentration
It is unusually low, down to 6% or lower.Organic solvent can be used in technique including addition solid urea and gaseous state HBr, i.e.,
EtOH, but preferred solvent is water.Enriched product of the invention can be used as useful intermediate, such as prepare biocide group
When closing object, with the production of cost-effective program, it is easy to transport and storage-stable, even if at a high ambient temperature, such as be up to about
40℃。
It can modify to technique of the invention to provide the combination containing high concentration HBr and/or HCl and low concentration of water
Object, and the amide as active halogen solutions stabilizer.This composition especially has as the intermediate for preparing biocide
With.The stabilizer may include urea derivative, sulfamic acid, cyanoacetamide or alkyl hydantoin.High concentration it is steady
Determining agent-hydrogen halide liquid can be obtained by handling the slurry of stabilizer with hydrogen halide.For example, by by HBr gas
It is introduced into the slurry with least quantity or minimum HBr water-soluble liquid measure to obtain high stabilizer-hydrogen halide concentration；Stabilizer slurry
Material dissolution, usually dissolves in exothermal reaction process, the exothermic reaction increases the amount of stabilizer and HBr in solution, simultaneously
Reduce the relative amount of water.
The present invention provides the molecular formula (NH for being in a liquid state and include high concentration at room temperature2)2Urea hydrogen shown in CO.HX
The composition of halide, wherein (NH2)2CO is urea and X is halogen, wherein the composition includes at least 35% hydrogen halides
The water of HX and most 30%, wherein HX represents HBr or HCl or their mixture.In a preferred embodiment of the invention, HX is
HBr.In a further advantageous embodiment, HX represents the equimolar mixture of HBr and HCl.In a preferred embodiment of the invention,
The composition includes at least 40% hydrogen halides and most 20% water, for example, at least 45% hydrogen halides and most 10%
Water.In a preferred embodiment, the present invention provides the aqueous solution under the environment temperature being made of urea hydrohalide and water, wherein water
Content down to most 9%, such as most 8%, such as most 7%, such as most 6%, such as most 5%.Of the invention
In one preferred embodiment, the composition includes urea and HBr, Yi Jishui with equimolar ratio, and wherein water accounts for the combination
4% to the 12% of object.In one embodiment, the present invention provides a kind of urea hydrobromide composition, and it includes at least 50%
HBr, for example, at least 51%HBr, for example, at least 52%HBr, for example, at least 53%HBr, for example, at least 54%, for example, at least 55%
HBr.In another preferred embodiment of the invention, the composition includes the HBr and half mole of urea and half mole
HCl, and constitute the composition 4% to 12% water.In one embodiment, it includes urea .HBr and urine that the present invention, which provides,
The mixture of plain .HCl contains at least 43%HBr+HCl, for example, at least 44%HBr+HCl, for example, at least 45%HBr+HCl, example
Such as at least 46%HBr+HCl, for example, at least 47%HBr+HCl.In a preferred embodiment, composition of the present invention includes about
The water of 5% water to about 9%.Herein, term " water of about X% " refers to the water of X%+1%.Described in these preferred embodiments
Composition contains most about 9% water and at least 52% HBr, such as most about 7% water and at least 53% HBr, such as
About 6% water and about 54% HBr.The present invention is provided to prepare the molecular formula being in a liquid state at room temperature and comprising high concentration
(NH2)2The composition of urea hydrohalide shown in CO.HX, in the molecular formula, (the NH2)2CO is urea and the X is
Halogen, the composition include at least 40% hydrogen halides HX and most 20% water, the technique comprising steps of i) Xiang Shui or
Solid urea is added in aqueous solution of hydrogen halide, to obtain the aqueous slurry of urea；Ii) it is added into the slurry gaseous state halogenation
Hydrogen, to obtain urea hydrohalide solution；Iii the content of water or HX in the solution) is determined；And iv) if described aqueous
Amount is higher than predetermined value or the HX content is lower than predetermined value, repeats step i) to iii).In one embodiment, of the present invention
Technique comprising steps of first part's solid urea i) is added in Xiang Shui or aqueous solution of hydrogen halide, to obtain the first urea water
Property slurry；Ii gaseous hydrogen halide) is added in the first slurry of Xiang Suoshu, to obtain the first urea hydrohalide solution；Iii) to
Second part solid urea is added in the first urea hydrohalide solution, to obtain the second urea aqueous slurry；Iv) to
Hydrogen halides is added in second slurry, to obtain the second urea hydrohalide solution；V) water in second solution is determined
Or the content of HX；And vi) if the content of the water or HX are lower than predetermined value, repeat step iv) and v).The HX can be
HBr or HCl.For example, if required product is liquid (NH2)2CO.HBr, then the HX is HBr, and HBr is at least partly as gas
It uses, several parts is preferably divided to use.If required product is (NH2)2CO.HBr and (NH2)2The liquid phase of CO.HCl mixes
Object, then the HX is HBr and HCl, is preferably separable use, is used at least partly as gas, at least two independent steps
Middle to apply respectively, every kind of gas divides several parts to apply as far as possible.Technique of the present invention preferably includes to cool down the reaction
Mixture, the temperature being preferably cooled between 15 DEG C to 90 DEG C, preferably up between 80 DEG C, such as 15 DEG C to 60 DEG C.
In general, the stabilizer of reactive halogen is mixed with water or aqueous HBr to provide slurry in method of the present invention
Material, and the gaseous state HBr or HCl of predetermined amount are introduced into the slurry, as far as possible at a temperature of between environment temperature with 80 DEG C
Multiple steps and/or part are divided to introduce.In a preferred embodiment of the invention, the stabilizer is urea, provides environment temperature
Under the urea hydrobromide or urea hydrobromide/urea hydrochloride of the concentration that are in a liquid state.According to required application, liquid
Water content is predetermined, usually between 4% to 12%.Experienced operator calculates planned final products quantity
Required amount of reagent, for example, it is contemplated that actual conditions, when producing urea .HBr (hereinafter referred to as U.Br), using relative to urea
The HBr of equimolar amounts；When producing urea .HBr+ urea .HCl (hereinafter referred to as U.Br.Cl), using relative to half mole of urea
The HBr and HCl of amount.Following table provides the budget amount of reagent of every 100g product of six embodiments of concentrated liquid of the present invention
Example.For example, aqueous 8% urea hydrobromide product is expressed as U.Br.Cl (8) in table.
Amount of reagent needed for the every 100g liquid urea hydrohalide product of table 1 (unit: gram)
| Product | Water | Urea | HBr | HCl |
| U.Br(4) | 4 | 40.9 | 55.1 | 0 |
| U.Br(8) | 8 | 39.2 | 52.8 | 0 |
| U.Br(12) | 12 | 37.5 | 50.5 | 0 |
| U.Br.Cl(4) | 4 | 48.5 | 32.7 | 14.8 |
| U.Br.Cl(8) | 8 | 46.5 | 31.4 | 14.1 |
| U.Br.Cl(12) | 12 | 44.5 | 30.0 | 13.5 |
The present invention will be further described below and be illustrated by following embodiment.
Embodiment
Embodiment 1
Hydrodistillation prepares solid urea hydrobromide (urea: HBr=2:1.1 molar ratio)
By solid urea (98.6% purity；17.64g, Mw 60,289.9mmol) it is dissolved in 48%HBr (26.84g；
12.9g is 100%, Mw 80.92,159.21mmol) in aqueous solution, obtain 44.5g solution (urea 39.1%, HBr
28.96%).Water (calculated value 13.95g) is distilled using Rotary Evaporators, vacuum 3mbar is gradually heated up (extremely in 4 hours
75℃).Eliminate 14.26g water.Analytical calculation: urea 57.45%, HBr 42.55%；It was found that: urea 56.1%, HBr
41.8%.Obtain the soluble solid of urea hydrobromide (urea .HBr).Word " calculated " (calculating) is abbreviated as
“calcd”。
Embodiment 2
Solid urea .HBr (urea: HBr=3:1.1 molar ratio) is prepared by evaporation water
By solid urea (98.6% purity；26.6g, Mw 60,437.13mmol) being dissolved in 48%HBr, (12.96g is
100%, Mw 80.92,160.16mmol) in aqueous solution, obtain 53.6g solution (urea 48.9%；HBr 24.2%).It uses
Rotary Evaporators remove water (14.04g), and vacuum 2mbar was gradually heated up (to 75 DEG C) in 3.5 hours.Eliminate 14.65g water.
Analytical calculation: urea 66.92%, HBr 33.08%；It was found that: urea 61.1%, HBr 32.7%.Obtain soluble solid.
Embodiment 3
Solid urea .HBr (urea: HBr=1:1 molar ratio) is prepared by evaporation water
By solid urea (98.6% purity；8g, Mw 60,132.5mmol) it is dissolved in 48%HBr (22.42g；10.76g
In 100%, Mw 80.92,132.99mmol) aqueous solution, to obtain 30.5g solution (urea 26.09%, HBr 35.3).It uses
Rotary Evaporators remove water (12.8g), and vacuum 2mbar was gradually heated up (to 75 DEG C) in 1.3 hours.Eliminate 14.65g water.Point
Analysis: it calculates: urea 42.5%, HBr 57.5%.It was found that: urea 46.2%, HBr 52.7% obtain soluble solid.
Embodiment 4
Solid urea .HBr (urea: HBr=3:1.1 molar ratio) is prepared by normal heptane azeotropic distillation；Taz 79.2℃
By solid urea (98.6% purity；26.6g, Mw 60,437.1mmol) it is dissolved in 48%HBr (27g；13g is
100%, Mw 80.92,160.2mmol) in aqueous solution, obtain 53.6g solution (urea 48.92%, HBr 24.2%).Xiang Shui
95% normal heptane (60.4, g) is added in solution and starts azeotropic distillation (150 DEG C, 6hrs) under atmospheric pressure, then under vacuum
Remove normal heptane.14.3g water (being calculated as 14.04g) is eliminated, white solid (m.p.72.3-76 DEG C) is left.Analysis: urea
55.7%；HBr 38.7%；Biuret 3.14%；H2O 2.5% (calculating).
Embodiment 5
Urea .HBr (urea: HBr=1:1.06 molar ratio) is prepared by normal heptane vacuum distillation
By solid urea (98.6% purity；40.46g, Mw 60,655.7mmol) it is dissolved in 48%HBr (117.55g；
56.4g being 100%；Mw 80.92,697.3mmol) in aqueous solution, obtain 157.45g solution；D=1.419g/l.(urea
25%, HBr 35.84%).95% normal heptane (123.4, g) are added into aqueous solution.Pressure (80 DEG C, 32-43mbar,
It is distilled under 1hr), obtains 97.45g liquid, which is frozen into 1:0.97 urea: the waxy residue of HBr molar ratio.Urine
Element 41.55%；HBr 54.6%；Biuret 0.4%；H2O 2.5% (calculating).
Embodiment 6
Liquid urea .HBr (urea: HBr=1:1.07 molar ratio) is prepared by normal heptane vacuum distillation
By solid urea (98.6% purity；40.46g, Mw 60,655.7mmol) it is dissolved in 48%HBr (118.04g；
56.7g is pure, Mw 80.92,700.2mmol) in aqueous solution, obtain 157.9g solution；D=1.419g/l.(urea
24.9%, HBr 35.9%).95% normal heptane (123.4, g) are added into aqueous solution.Pressure (80 DEG C, 34-45mbar,
It is distilled under 1hr), obtains 97.45g clear solution (it is expected that 96g) residue being made of urea hydrobromate, urea: HBr's rubs
You are than being 1:0.94.D25℃1.763g/l.Urea 42.2%, HBr 53.6%；Biuret 0.4%, 3.8% water.
Embodiment 7
Pass through normal heptane: water vacuum distillation prepares liquid urea .HBr.HCl (urea: HBr:HCl=1.17:0.5:0.5
Molar ratio)
By solid urea (98.6% purity；66.93g, Mw 60,1100mmol) being dissolved in 48%HBr, (79.5g is
100%, Mw 80.92,38.15 is pure, 471.43mmol) and 32%HCl (53.6g, 17.15g are pure, Mw 36.45,
470.6) in aqueous solution, 200g solution is obtained；D=1.317g/l, urea 54%, HBr 19.07%；HCl 8.58%.Xiang Shui
95% normal heptane (192, g) are added in solution.It is distilled under pressure (80 DEG C, 26-38mbar, 5hr), obtaining molar ratio is
The urea of 1.18:0.5:0.36: the 119.2g clear solution residue of HBr:HCl composition.D25℃1.60g/l.Analysis:
It calculates: urea 54.41%, HBr 31.45%, HCl 14.14%.
It was found that: urea 56.3%, HBr 32.2%；HCl 10.38%.Biuret 0.56%, water 0.56%.
Embodiment 8
Use HBr gas and prepares solid urea .HBr (urea: HBr=2:1.1 molar ratio) using ethyl alcohol as solvent
Solid urea (66.93g, 98.6% purity, Mw 60,1314mmol) is added in ethyl alcohol (77.6g), is obtained
157.6g slurry, urea 50.04%, ethyl alcohol 49.2%.HBr gas (58.55g is added while cooling；Mw 80.92；
723.55mmol), 30 DEG C or less are maintained the temperature at.Obtain the urea for being 2:1.1 by molar ratio: HBr is formed colorless and transparent molten
Liquid.Solvent evaporates (50 DEG C, 2hrs, 27mBar) acquisition 76.8g white soluble solids.The material solidifies at room temperature, obtains
White solid.
Analysis is found: urea 55.0%, HBr 41.7%, biuret 0.61%, pH (1% solution) 1.4；GC-MS ethyl alcohol
(1.9%).Urea: the molar ratio of HBr is 1.95:1.1.
Embodiment 9
Solid urea .HBr (urea: HBr=1:1 molar ratio) is prepared using HBr gas and alcohol solvent
Solid urea (65.38g, 98.6% purity, Mw 60,1074.4mmol) is added in ethyl alcohol (63.9g), is obtained
129.26g slurry, urea 49.87%, ethyl alcohol 49.37%.HBr gas (87.12 is added while cooling；Mw 80.92,
1076.6mmol), 35 DEG C or less are maintained the temperature at.Obtain the urea for being 1:1 by molar ratio: HBr is formed colorless and transparent molten
Liquid.Solvent evaporates (50 DEG C, 8hrs, 23-27mBar) acquisition 65.4g white soluble solids.The material solidifies at room temperature, obtains
To white solid.
Analysis: discovery: urea 41.7%, HBr 52.9%, biuret 0.4%, pH (1% solution) 1.36；GC-MS ethyl alcohol
(3.9%).Urea: the molar ratio of HBr is 1.06:1.
Embodiment 10
Use the urea .HBr of the concentration of HBr gas preparation liquid, 11% water (urea: HBr=1:1 molar ratio)
Solid urea (66g, 98.6% purity, Mw 60,1099.3mmol) is added in water (19.4g, heat absorption), is obtained
Obtain 85.4g slurry, urea 76.1%, H2O 22.78%.(1hr, exothermic) HBr gas (88g is slowly added to while cooling；
Mw 80.92；1087.4mmol), 35 DEG C or less are maintained the temperature at.Obtain the urea for being 1:1 by molar ratio: the nothing that HBr is formed
Color clear solution.
Analysis (it was found that): urea 37.5%, HBr 50.9%, biuret 0.34%, H2O 11.3%, pH (1% solution)
1.37。
Embodiment 11
Liquid urea .HBr, 6% water (urea: HBr=1:1 molar ratio) are prepared using HBr gas
Solid urea (43.6g, 98.6% purity, Mw 60,716.2mmol) is added in water (12.84g, heat absorption),
Obtain 56.4g slurry (urea 76.1%, H2O 22.8%).(15min. is exothermic) HBr gas is slowly added to while cooling
25.75g (Mw 80.92,318.09mmol), maintains the temperature at 35 DEG C or less.Obtain colourless transparent solution.To the solution
The second urea dosage of middle addition (47.08, Mw 60,773.68mmol), formed again slurry (total 90.66, Mw 60,
1489.84mmol).HBr gas is added again, until total weight reaches 119.4g (Mw 80.92,1475.53mmol) (heat release
).It obtains and contains 6.2%H2The colourless transparent solution of O (calculating).
Analysis (it was found that): urea 39.9%, HBr 53.5%, biuret 0.39%, pH (1%) 1.42.
Solution 4 months stabilizations at 40 DEG C are not decomposed.
Embodiment 12
Using HBr gas and 32%HCl aqueous solution prepare liquid urea .HBr.HCl (urea: HBr:HCl=1:0.5:
0.5 molar ratio)
32%HCl aqueous solution (76.09g is added in solid urea (80.94g, 98.6% purity, Mw 60,1330mmol)；
24.35g is 100%, Mw 36.42,668.01mmol) in, generate 157.02g clear solution；Urea 50.8%, HCl
15.5%, H2O 32.95%.
It is slowly added to (48min. is exothermic) HBr gas 62.86g (Mw 80.92,776.8mmol) while cooling, is protected
Temperature is held at 35 DEG C or less.Obtain colourless transparent solution.Urea 37.9%, HBr 26.02%, HCl 11.21%；Biuret
0.39%；PH (1%) 1.28；24.5%H2O (calculating).
Solution 3 months stabilizations at 40 DEG C are not decomposed.
Embodiment 13
Using HBr gas and 37%HCl aqueous solution prepare liquid urea .HBr.HCl (urea: HBr:HCl=1:0.5:
0.5 molar ratio)
37%HCl aqueous solution is added in solid urea (81.5g, 98.6% purity, Mw 60,1336.8mmol)
(65.81g；24.35g is 100%, Mw 36.42,668.03mmol) in, generate 146.74g clear solution；Urea 54.38%,
HCl 16.6.5%, H2O 28.25%.
(40min. is exothermic) HBr gas (61.4g is slowly added to while cooling；Mw 80.92,758.77mmol), it protects
Temperature is held at 35 DEG C or less.Obtain colourless transparent solution.D=1.4550.
It analyzes (calculating): urea 39.85%, HBr 26.87%, HCl 12.1%, H2O 20.61%, D23.5℃
1.455g/l。
Analysis is found: urea 40.4%, HBr 27.14%, HCl 11.85%；Biuret 0.39%, pH (1%) 1.26.
Embodiment 14
Liquid urea .HBr, 7% water (urea: HBr=1:1 molar ratio) are prepared using HBr gas
48%HBr aqueous solution (38.53g is added in solid urea (114g, 98.6% purity, Mw 60,1873.9mmol)；
18.494g is 100%, Mw 80.92,228.55mmol) in, generate 152.5g clear solution；Urea 73.7%, HBr
12.12%, H2O 13.13%.
(62min. is exothermic) HBr gas (154.14g is slowly added to while cooling；Mw 80.92,1873mmol), it protects
Temperature is held at 50 DEG C or less.Obtain colourless transparent solution 288.21g (163.94ml)；D26.9℃1.758g/l。
It analyzes (calculating): urea 39.01%, HBr 53.48%, H2O 6.95%, D26.9℃ 1.758g/l。
Analysis is found: urea 40%, HBr 53.2%, biuret 0.41%, pH (1%) 1.23.
It is placed at 50 DEG C after 7 hours, analysis result is identical: urea 40%, HBr 53.2%, biuret 0.41%, pH
(1%) 1.23.
Embodiment 15
It prepares bromourea (urea: HBr:NaOCl=1:1:0.85 molar ratio)
In 244g H2It is (real that urea hydrobromide solution { 6.3g, urea 41.4mmol and HBr 41.4mmol } is diluted in O
Apply example 14).
223g H is used in individual flask2O dilutes NaOCl aqueous solution, and (25.9g, 9.65% is Cl2w/w；2.5g；
35.2mmol)。
Described two solution are mixed, obtaining 499.25g microbicide solution, (0.5% is Cl2).The solution with lower concentration
The solution of form preparation has same biocidal effect.
Embodiment 16
Liquid urea .HBr, 8% water (urea: HBr=1:1 molar ratio) are prepared using HBr gas
By solid urea (106.23g, 98.6% purity, Mw 60；1745.7mmol) 48%HBr aqueous solution is added
(38.53g；18.494g is 100%, Mw 80.92,228.55mmol) in, generate 146.26g clear solution；Urea 71.6%,
HBr 12.64%, H2O 14.72%.
(35min. is exothermic) HBr gas is slowly added to (to 141.25g in total while cooling；Mw 80.92,
1745.6mmol), 60 DEG C or less are maintained the temperature at.Obtain colourless transparent solution 269g (154.25ml)；D29.5℃
1.744g/l。
Analytical calculation: urea 38.93%, HBr 52.5%, H2O 8%.
Analysis is found: urea 39.1%, HBr 52.6%, biuret 0.37%, pH (1%) 1.27, D25℃ 1.746g/
l.It is placed at 50 DEG C after 7 hours: urea 39.2%, HBr 52.5%, biuret 0.37%, pH (1%) 1.26.
Embodiment 17
Liquid urea .HBr, 9% water (urea: HBr=1:1 molar ratio) are prepared using HBr gas
By solid urea (105.4g, 98.6% purity, Mw 60；1732.07mmol) 48%HBr aqueous solution is added
(40.41g；19.4g is 100%, Mw 80.92,239.74mmol) in, generate 145.81g clear solution；Urea 69.7%,
HBr 13%, H2O 16.3%.
(35min. is exothermic) HBr gas is slowly added to (to 141.25g in total while cooling；Mw 80.92,
1732.7mmol), 60 DEG C or less are maintained the temperature at.Obtain colourless transparent solution 269.9g (154.84ml)；D28.5℃
1.734g/l。
Analytical calculation: urea 38.8%, HBr 51.95%, H2O 9%.
Analysis is found: urea 38.8%, HBr 52%, biuret 0.37%, pH (1%) 1.25, D25℃ 1.743g/l。
It is placed at 50 DEG C after 7 hours: urea 39.4%, HBr 51.9%, biuret 0.35%, pH (1%) 1.26.
Embodiment 18
Liquid urea .HBr, 6% water (urea: HBr=1:1 molar ratio) are prepared using HBr gas
By solid urea (105.98g, 98.6% purity, Mw 60；1741.5mmol) 48%HBr aqueous solution is added
(24.7g；11.85g is 100%, Mw 80.92,146.44mmol) in, generate 130.7g clear solution；Urea 80%, HBr
9.07%, H2O 9.83%.
Then (53min. is exothermic) HBr gas is slowly added to (to 140.92g in total while cooling；Mw80.92,
1741.5mmol), 50 DEG C or less are maintained the temperature at.Obtain colourless transparent solution 262.9g (148.9ml)；D28℃ 1.76g/l。
Analytical calculation: urea 39.9%, HBr 53.85%, H2O 5.8%.
Analysis is found: urea 40.3%, HBr 52.8%, biuret 0.41%, pH (1%) 1.25, D33℃ 1.759g/l。
It is placed at 50 DEG C after 7 hours: urea 40%, HBr 53%, biuret 0.42%, pH (1%) 1.26.
Embodiment 19
Liquid urea .HBr.HCl is prepared using HBr gas and HCl gas, 7% water (urea: HBr:HCl=1:0.5:
0.5 molar ratio)
By solid urea (80.93g, 98.6% purity, Mw 60；48%HBr aqueous solution (20g 1329.95mmol) is added；
9.6g is 100%, Mw 80.92,118.64mmol) in, generate 100.93g slurry liquid；Urea 79.06%, HBr 9.51%,
H2O 10.3%.
Then (50min. is exothermic) HBr gas is slowly added to (to 54.06g in total while cooling；Mw80.92,
668.07mmol), 60 DEG C or less are maintained the temperature at.
HCl gas (24.35g is slowly added in 25min. while cooling；Mw 36.45；668.04mmol), it keeps
Temperature is at 60 DEG C or less.Obtain colourless transparent solution 169.74g.
It analyzes (calculating): urea 47%, HBr 31.85%, HCl 14.35%；H2O 6.13%.
Embodiment 20
The urea .HBr.HCl being concentrated using HBr gas and the preparation of HCl gas, 7% water (urea: HBr:HCl=1.2:
0.5:0.5 molar ratio)
By solid urea (97.2g；98.6% purity, Mw 60；48%HBr aqueous solution (22.5g 1597.3mmol) is added；
10.8g is 100%, Mw 80.92,133.47mmol) in, generate 119.7g slurry liquid；Urea 80.07%, HBr 9%, H2O
9.77%.
Then (50min. is exothermic) HBr gas is slowly added to (to 54.06g in total while cooling；Mw80.92,
668.07mmol), 60 DEG C or less are maintained the temperature at.
HCl gas (24.35g is slowly added in 25min. while cooling；Mw 36.45；668.04mmol), it keeps
Temperature is at 60 DEG C or less.Obtain colourless transparent solution 187.3g.
Analysis: urea 51.17%, HBr 28.9%, HCl 13%, H2O 6.25%.
Although having used some specific embodiments, invention has been described, many modifications and variations can be carried out.
It is to be understood, therefore, that the present invention is not restricted in any way, in addition to being limited by the scope of the appended claims.
Claims (16)
1. being in a liquid state at room temperature and including molecular formula (NH2)2The composition of urea hydrohalide shown in CO.HX, wherein (NH2)2CO is urea and HX is hydrogen halides, and the composition includes at least 35% hydrogen halides HX and most 25% water.
2. composition described in claim 1 includes at least 40% hydrogen halides and most 12% water.
3. any composition of claim 1~2, wherein HX is HBr or HCl.
4. any composition of claim 1~2, wherein the HX is HBr, and the urea hydrohalide has point
Minor (NH2)2CO.HBr。
5. any composition of claims 1 to 3, wherein the HX is the mixture of HCl and HBr.
6. composition as claimed in claim 4 includes at least 50% HBr and most 12% water.
7. composition as claimed in claim 6 includes at least 52% HBr and most 8% water.
8. composition as claimed in claim 7 includes at least 53% HBr and most 7% water.
9. composition described in claim 5 includes at least 30% HBr, the water of at least 13% HCl and most 12%.
10. composition as claimed in claim 9 includes at least 31% HBr, the water of at least 14% HCl and most 8%.
11. any composition of claim 1~10, includes at least 4% water.
12. it is used to prepare the technique of any hydrohalide composition of claim 1~11, comprising steps of
I) solid urea is added in water or aqueous solution of hydrogen halide, to obtain the aqueous slurry of urea；With
Ii gaseous hydrogen halide) is added into slurry described in step i), to dissolve the slurry and obtain urea hydrohalide
Solution；
Simultaneously cooling reaction mixture to 15 DEG C to 60 DEG C between temperature.
13. technique described in claim 12, wherein hydrogen halides described in step i) is selected from HBr and HCl.
14. technique described in claim 13, wherein step ii) described in gaseous hydrogen halide be selected from HBr and HCl.
15. technique described in claim 14, including second part urea is added into the urea hydrohalide solution, thus
The second slurry is obtained, and second part gaseous hydrogen halide is added into second slurry, to dissolve second slurry simultaneously
Obtain the second urea hydrohalide solution.
16. any technique of claim 12~15, further includes measuring at least one of described urea hydrohalide solution
The step of content of component, wherein the component is selected from the group of water, HBr and HCl composition, if the content value of measurement is different from advance
Definite value further includes the steps that being sequentially added to lack a kind of reagent selected from urea, HBr and HCl.
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| US201762462392P | 2017-02-23 | 2017-02-23 | |
| US62/462,392 | 2017-02-23 | ||
| PCT/IL2018/050144 WO2018154560A1 (en) | 2017-02-23 | 2018-02-08 | Liquid urea hydrohalides |
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|---|---|
| EP (1) | EP3585766A4 (en) |
| JP (1) | JP2020508321A (en) |
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| WO (1) | WO2018154560A1 (en) |
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|---|---|---|---|---|
| US5672279A (en) * | 1992-07-24 | 1997-09-30 | Peach State Labs, Inc. | Method for using urea hydrochloride |
| CN1337919A (en) * | 1999-04-21 | 2002-02-27 | 纳尔科化学公司 | Stable oxidizing bromine formulations, method of manufacture and uses thereof for biofouling control |
| CN103391917A (en) * | 2010-09-21 | 2013-11-13 | 溴品有限公司 | Method for preparing bromourea |
| KR20140091392A (en) * | 2013-01-11 | 2014-07-21 | 주식회사 부광산업 | The Highly Efficient Etchant Composition for Semiconductor Processing and Producing |
| US20150037234A1 (en) * | 2013-07-31 | 2015-02-05 | Schlumberger Technology Corporation | Aqueous solution and method for use thereof |
| US20150099014A1 (en) * | 2012-03-08 | 2015-04-09 | Bromine Compounds Ltd. | Method for preparing biocidal and antifouling aqueous compositions comprising hydrobromic acid, urea and sodium hypochlorite |
| US20150240147A1 (en) * | 2014-02-25 | 2015-08-27 | Schlumberger Technology Corporation | Aqueous solution and methods for manufacture and use |
| US9365810B2 (en) * | 2009-04-07 | 2016-06-14 | Green Products & Technologies, L.L.C. | Urea hydrochloride compositions |
| CN105693557A (en) * | 2016-01-04 | 2016-06-22 | 湖北卓熙氟化股份有限公司 | Hydrogen fluoride urea and preparation method thereof |
-
2018
- 2018-02-08 CN CN201880013394.0A patent/CN110382459A/en active Pending
- 2018-02-08 WO PCT/IL2018/050144 patent/WO2018154560A1/en unknown
- 2018-02-08 EP EP18756858.9A patent/EP3585766A4/en not_active Withdrawn
- 2018-02-08 JP JP2019545764A patent/JP2020508321A/en active Pending
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5672279A (en) * | 1992-07-24 | 1997-09-30 | Peach State Labs, Inc. | Method for using urea hydrochloride |
| CN1337919A (en) * | 1999-04-21 | 2002-02-27 | 纳尔科化学公司 | Stable oxidizing bromine formulations, method of manufacture and uses thereof for biofouling control |
| US9365810B2 (en) * | 2009-04-07 | 2016-06-14 | Green Products & Technologies, L.L.C. | Urea hydrochloride compositions |
| CN103391917A (en) * | 2010-09-21 | 2013-11-13 | 溴品有限公司 | Method for preparing bromourea |
| US20150099014A1 (en) * | 2012-03-08 | 2015-04-09 | Bromine Compounds Ltd. | Method for preparing biocidal and antifouling aqueous compositions comprising hydrobromic acid, urea and sodium hypochlorite |
| KR20140091392A (en) * | 2013-01-11 | 2014-07-21 | 주식회사 부광산업 | The Highly Efficient Etchant Composition for Semiconductor Processing and Producing |
| US20150037234A1 (en) * | 2013-07-31 | 2015-02-05 | Schlumberger Technology Corporation | Aqueous solution and method for use thereof |
| US20150240147A1 (en) * | 2014-02-25 | 2015-08-27 | Schlumberger Technology Corporation | Aqueous solution and methods for manufacture and use |
| CN105693557A (en) * | 2016-01-04 | 2016-06-22 | 湖北卓熙氟化股份有限公司 | Hydrogen fluoride urea and preparation method thereof |
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| JP2020508321A (en) | 2020-03-19 |
| WO2018154560A1 (en) | 2018-08-30 |
| EP3585766A4 (en) | 2020-11-25 |
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