CN87104316A

CN87104316A - Activated aluminum-hydrogen-oxygen coordination compound and preparation method thereof and purposes

Info

Publication number: CN87104316A
Application number: CN198787104316A
Authority: CN
Inventors: 弗莱德·B·伯那特
Original assignee: Research Corp Of America (us) 310 Franklin Center 29100 Northwestern Highway So
Current assignee: Research Corp Of America (us) 310 Franklin Center 29100 Northwestern Highway So
Priority date: 1986-05-13
Filing date: 1987-05-13
Publication date: 1988-03-09
Also published as: JPS6325218A; DE3715963A1; FI872098A0; PH24020A; NL8701149A; SE8701946D0; IT1204594B; FI872098A; SE8701946L; ES2005573A6; AU7279887A; FR2598700A1; KR870011043A; IT8720486A0; GB8711267D0; GB2191184A

Abstract

Disclosure of the Invention prepares the method for aluminum-hydrogen-oxygen coordination compound, this coordination compound is added to contain in oxygen and the hydrogen liquid to discharge hydrogen and oxygen when halide-containing exists.This method comprises: (1) makes the metal that contains trace silicon at least and concentration can remove the acid that oxide on surface can suppress to form oxide again and contacts, (2) acid-treated metal is contacted with the hydrargyrum source, (3) aluminum with contacted hydrargyrum is immersed in the halogen acids, makes its surface form coordination compound.Invention is also open, and coordination compound is placed halogen acids, forms suspension, after the cooling pH is transferred to 5.0～5.8, with the method for aluminum in the supending-hydrogen-oxygen coordination compound.

Description

The application is the applicant in the part continuation application that December in 1984 was submitted on the 26th, co-applications number is 686,147 application, is again the dividing an application of the 488th, No. 631 application (now being United States Patent (USP) 4,536,394) of application on April 26 nineteen eighty-three.The disclosure of above-mentioned patent application provides a reference.

The present invention relates to novel aluminum-hydrogen-oxygen coordination compound and preparation method thereof.Particularly this class coordination compound contains aluminum, oxygen and hydrogen with certain proportion and form, make this class coordination compound can be used for various compositionss, with the decomposition of control organic substance, as Del-Trac, the processing of brightening Emulsion, deodorizer, depilatory compositions and being used for biological substance.

The commercially available over-the-counter products that can be used for skin, for example cosmetics, enamel, antibacterial, medicine, deodorizer etc., their are according to the dilating effect or the contraction of skin pore are had an effect.Any acne of all curing unsatisfactorily.

Utilize those chemical compounds of dilating effect can eliminate foul on the skin, but consequence is that skin pore keeps expansion in the quite a long time, thereby is subjected to the immersion of air pollutants such as sulfur dioxide and tar especially easily.This product with dilating effect of life-time service consequently, can produce skin condition afterwards usually in short-term " effectively " and worsen.

Those utilize the compositions of contraction to use after cleaning skin with hydrogen peroxide or other strong oxidizer usually.Though the oxygen that hydrogen peroxide discharges effectively and immediately works, contraction has subsequently stoped cleans skin " going deep into ".

In addition, the compositions that is used for skin is decided according to the purpose of its use, must help to eliminate undesirable stink, reduces the stimulation of skin and make aerobic foreign body on the skin, and for example (Commidones) (as blackhead) or acne are dry.Because these compositionss are used on the skin, they also must suppress antibacterial, nontoxic, non-stimulated and be perfectly safe.

The research work of this respect is carrying out all the time, that make new advances with development or improved, compositions such as depilatory, Del-Trac, roll-on deodorizer that can be on being applied in skin and brighten the chemical compound that uses in the Emulsion.The present invention promptly is the achievement in research of this respect.

Therefore, catalogue of the present invention is to avoid the problems referred to above of the prior art or relax these problems substantially.

The more special purpose of the present invention is, a kind of aluminum-hydrogen-oxygen coordination compound is provided, and it can be used in the compositions that is applied on the skin.

Another object of the present invention is that the process of preparation this aluminum-hydrogen-oxygen coordination compound is provided.

A further object of the invention is that the method that this aluminum-hydrogen-oxygen coordination compound is applied to skin with the form of solid or semi-solid compound is provided.

Another purpose of the present invention is that the application process with this aluminum-the hydrogen-oxygen coordination compound gets up with one or more liquid combination is provided.

A further object of the present invention is the decomposition of control biological substance.

Other purpose of the present invention and advantage will be become apparent by the description of following the present invention's summary and preferable embodiment.

One aspect of the present invention provides the process of preparation reactive powder.This method is made up of the following step basically:

A. make purity be at least the 99.94%(weight ratio) and the metallic aluminium that contains trace silicon at least contact with a kind of acid source, the kind and the concentration of acid should be the oxides that can remove on the metal surface, formation that again can the inhibited oxidation thing;

Metallic aluminium through acid treatment is contacted in oxygen-containing atmosphere with a kind of hydrargyrum source; And

C. will be dipped in partly in a kind of hydrogen halide solution with the contacted aluminum of hydrargyrum, dip time should be enough to make on the aluminum surface of contacted hydrargyrum growth or form crystalline material, and this material is reactive powder

On the other hand, the invention provides the product of producing with this process.

Moreover, the invention provides a kind of process for preparing aluminum-hydrogen-oxygen coordination compound suspension, this aluminum-hydrogen-oxygen coordination compound can discharge oxygen and hydrogen in the presence of halide-containing.This method is made up of the following step substantially:

A. make purity be at least about the 99.94%(weight ratio) and the metallic aluminium that contains trace silicon at least contact with a kind of acid source, the kind and the concentration of acid should be the oxides that can remove on the metal surface, formation that again can the inhibited oxidation thing;

Metallic aluminium through acid treatment is contacted in oxygen-containing atmosphere with a kind of hydrargyrum source;

C. will be dipped in partly in a kind of halogen acid solution with the contacted aluminum of hydrargyrum, dip time should be enough to make coordination compound to begin growth on the aluminum surface of contacted hydrargyrum;

D. make coordination compound be dissolved in again at least in part in a kind of halogen acid solution with form suspension,

E. cool off this suspension; And

F. the pH value of suspension is brought up to about 5.0-5.8.

The present invention also provides the suspension of producing with the method.

In order to understand the present invention better, can be with reference to the accompanying drawings, wherein:

Fig. 1 is the sectional elevation sketch map of institute's operative installations and ingredient embodiment in two steps of process of the present invention.

Fig. 2 is the sketch map of similar Fig. 1, and the process of the present invention another embodiment in two step is shown.

Fig. 3 is the sketch map of similar Fig. 1, and the formation situation of aluminum on the metal surface of not immersing the hydrochloric acid tank liquor in the third step of the present invention-hydrogen-oxygen coordination compound is shown.

Fig. 4 is the sketch map of Soxhlet apparatus, and it is heavy molten in this device formed aluminum-hydrogen-oxygen coordination compound on the impregnating metal surface not to be carried out part.

Aluminium of the present invention-hydrogen-oxygen complex is a kind of lightweight, the snperoxiaized material of amorphous state, contains aluminium, oxygen, hydrogen and the unconjugated halogen of trace at least. Be used for generating this aluminium-metallic aluminium of hydrogen-oxygen complex and contain the silicon of trace hexagonal system structure form, this is critical condition restriction. This aluminium-hydrogen-oxygen complex does not burn, and does not have an explosivity.

This aluminium-hydrogen-oxygen complex also will further be narrated hereinafter, and it is considered to Al₁₂（H ₂O ₂） ₁₈H ₆, be a kind of blue-green amorphous substance, and in process process of the present invention, generate in untreated metal surface. Originally this aluminium-hydrogen-oxygen complex is called BB-1.

The term " activated aluminum " that is used for narrating the used aluminium of preparation BB-1 refers to process with the mercury source and followed and is being roughly room temperature and be not higher than the metallic aluminium that partly is dipped under the temperature between 40 ℃ in the halogen acids. Under this kind " activity " state, this metallic aluminium does not flood the surface at it and keeps its element morphology, but is " clathrate " form, wherein carries or be wrapped in " dissociating " chlorine (or other halogen) of trace secretly. And this free chlorine of carrying secretly in the clathrate mode can make aluminium of the present invention-hydrogen-oxygen complex discharge oxygen and hydrogen.

The trace silicon that must contain in the used metallic aluminium of the present invention, its structure have two kinds of forms. Its general form is spherical or cylindrical, but has fraction silicon to be in the second form, and its profile is hexagon. In most cases, in the whole invention book said silicon be a general name and no matter the structure of silicon how. But the existence of hexagon silicon is considered to obtain the key of aluminium of the present invention-hydrogen-oxygen complex desirable characteristics. Fix the ratio of these two kinds of form silicon, also be difficult to do so far obtain. As if, in containing the commercially available aluminium of silicon, the silicon of hexagonal crystal system is less than about 1% of total silicon amount.

Aluminium of the present invention-hydrogen-oxygen complex can prepare with multistep processes technology. Narrate this process below in conjunction with accompanying drawing.

Utilize device shown in Figure 1, aluminum strip or aluminium bar (1) are placed container (2), container is to be made as good with glass or other acid resisting material. The shallow-layer halogen acids of packing in the container take hydrochloric acid (3) as good, is covered aluminium slightly by acid. Although aluminium is generally take strip or bar-shaped as good, shape is not crucial.

Acid-treated purpose is to remove the lip-deep all oxides of aluminium, and suppresses to produce oxide on the surface again. Aluminium should be fine aluminium, and general purity is at least about 99.94%, and purity commonly used is at least about 99.98%, and the preferably is at least about 99.99%. The purity of aluminium because can raising suddenly by acid liquor temperature, the existence of oxide shows, so can easily be measured with the method for experiment.

But metallic aluminium must not be 100% fine aluminium. Must have some silicon to exist in the aluminium, general total silicon amount is about 30-100ppm, and total silicon amount commonly used is about 45-95ppm, and take total silicon amount of being about 60-90ppm as good. The total silicon amount of use about less than 30ppm can make the quantity not sufficient of the hydrogeneous and oxygen of the complex of generation to reach predetermined purpose. But, if the metallic aluminium that contains bigger composition hexagonal crystal system silicon than the aluminium of the low total silicon amount that can buy at present can be arranged, be favourable to the present invention then. Use the total silicon amount that surpasses about 100ppm, owing to silicon can make the solution heating and drive away required hydrogen and oxygen, thereby cause technologic trouble.

Other impurity is present in the aluminium in the scope that for example iron can be discussed in the above. The content of existing iron generally should be less than about 50% of silicon weight in the aluminium, take less than about 40% as the dust head, with less than about 30% for better. Preferably iron content is maintained minimum of a value because iron have with system in the trend of oxygen reaction, and the oxygen in the system is reduced.

Just contacted or coating with the mercury source after aluminium soaks in acid solution, and preferably aluminium was put in the device of liquid bath or similar type and contacted. This step is that oxygenous atmosphere is being arranged, and for example air carries out under existing. Mercury plays a part catalyst, and it causes the change of aluminium tissue.

Temperature when carrying out the first two step is not crucial, but must not be the temperature of impelling oxide and/or chlorine to generate. The temperature range that can adopt generally is about 10-45 ℃, take 15-35 ℃ as commonly used, again with 20-30 ℃ for better.

When needing, acid contact contacts and can carry out simultaneously with mercury, and as shown in Figure 2, wherein aluminium bar (1) is dipped in acid solution (3) and the heavier mercury solution (4).

No matter what use is Fig. 1 or device shown in Figure 2, the device that other is suitable, the time that contacts with mercury can be quite short, although the contact of long period there is no harm. The used time is generally at least about 15 seconds, and is about 15-60 commonly used second, better second with 15-30.

Mercury plays catalyst, and it can cause the change of aluminium tissue.

Aluminium so that form, contacted mercury just partly is dipped in the halogen acid solution then. The special good halogen acids that is used for this purpose is hydrochloric acid. This step causes not flooding the surface generation or forming blue-green amorphous substance aluminium-hydrogen-oxygen complex at the aluminium of contacted mercury, and it is considered to Al₁₂（H ₂O ₂） ₁₈H ₆。

This aluminium-hydrogen-oxygen complex produces along with the growth of BB-1 or formation, and it is collected and can directly uses with the form of powdered substance. As selection, this material can further be processed through the following step: (a) this complex is dissolved in the halogen acid solution at least in part again, to form a kind of suspension; (b) with this suspension cooling; And (c) the pH value of this suspension is brought up to about 5.0-5.8(BB-1 suspension).

The BB-1 complex can produce with number of ways, and used method itself is not crucial. For instance, with after mercury contacts, aluminum strip or the aluminium bar of processing so partly can be dipped in another container that hydrochloric acid tank liquor is housed, the concentration of hydrochloric acid can be determined with experiment, but generally be about 1-2N. Form a kind of blue-green amorphous substance in untreated metal surface then. This growing state is shown in Fig. 3, and wherein the not dipping surface that is represented as on acid solution of complex (5) forms, and becomes the powder of BB-1 complex when it is dry.

Temperature when complex forms generally should be about 5-40 ℃, and about 20-30 ℃ commonly used, and better with about 22-25 ℃. At this moment, if aluminum feedstock is not enough pure, then can cause the unexpected rising of disadvantageous reaction environment temperature. Because necessary hydrogen and oxygen can discharge under higher temperature in the BB-1 complex, so temperature must not be higher than 40 ℃. The temperature that is lower than 5 ℃ is nonconforming, because reaction is not suitable for industrial requirement under this temperature.

In another embodiment, complex produces with following method, namely process oxide-free aluminium with mercury, with the tissue that changes aluminium and make it activation, the aluminium that to process then is dipped in the hydrochloric acid partly, allow it contact with each other (or Continuous Contact), so that form aluminium-hydrogen-oxygen complex in the metal surface of contact. Contact procedure is take about 75-100 minute as good. Blue-green BB-1 complex is the product of this step.

At room temperature or better be in simple and easy drying box, to carry out drying with the BB-1 complex then. Used heat must not be high to chlorine is discharged. Temperature generally should be about 5-50 ℃, and temperature commonly used should be less than about 40 ℃, and take about 20-40 ℃ as good. Relative humidity preferably should be about 30%.

The dry used time can be determined with experiment, because it depends on the thickness of complex layer, and depend on the size of drying box. Common drying steps required time generally is about 30-150 minute, and about 50-125 minute commonly used, and take about 75-100 minute as good. The product of this drying steps is blue-green powder, i.e. BB-1.

For forming the BB-1 suspension, the BB-1 powder is introduced in the blind pipe (11) of Soxhlet apparatus shown in Figure 4 (12).In the flask (13) of Soxhlet apparatus (12) halogen acid solution being housed, is good with hydrochloric acid (14), and concentration is good about with 3N.Then, with conventional method flask (13) is heated to boiling point.Hydrogen chloride vapour transmission Soxhlet apparatus (12) is partly dissolved the powder in the blind pipe (11) after water cooled condenser (15) condensation, and at flask (13) internal reflux.The blind pipe (11) that this step can repeat Soxhlet apparatus (12) becomes till the sky.

The required time of the heavy molten step of this part can come definite with experiment, although generally available approximately 30-200 minute, about 50-150 minute commonly used, be preferably 70-120 minute.Then, the BB-1 powder at strong acid liquid, is for example reclaimed in the hydrochloric acid.A regenerant part is the form of solution, and a part is the cloudy suspensions form of carefully loosing, and is referred to as the BB-1 suspension.

Be cooled to certain temperature at suspension, be generally less than about 50 ℃, about 15-40 ℃ commonly used, preferable being about after 20-30 ℃, the pH value of coordination compound is brought up to generally be about 5.0-5.8, use always and be about 5.2-5.6, and be preferably 5.3-5.5.

PH value can improve with the method for strong basicity hydroxide such as sodium hydroxide or potassium hydroxide treatment.The concentration of hydroxide is not strict, generally can be 1-4N approximately, and about 1.5-3.5N commonly used is preferable with 3-4N.

The pH meter of the available routine of raising of pH value is monitored.

The BB-1 suspension that is made by this process can be applied in the various prescriptions in fields such as cosmetics, enamel, medicine, deodorizer by percentage, and this percentage ratio can easily be determined by experiment.

When this BB-1 suspension is used for containing the compositions of oxygen and hydrogen, for example cosmetics, medicine, enamel, deodorizer etc., promptly use amount is very little also has an ability (having in the presence of the halogen) unique, that discharge oxygen and hydrogen.These compositionss are usually used in skin.Must be understood that halogenide is generally all arranged on the skin, it is the product of normal physiological processes normally, thereby makes the activation of BB-1 suspension.

The BB-1 suspension can be according to final application and is used by the percent of following composition total weight: acne ointment or Del-Trac (about 3%), depilatory compositions (about 4.5-5.0%), face cream (about 5%), oxter deodorizer (about 3%).

The following example is further illustrated the present invention.Except as otherwise herein provided, all umber or percentage number average be by weight in embodiment and description and the claim.

Embodiment 1

Present embodiment is illustrated the equipment of BB-1.Prepare the aluminium bar of 500g, wherein impurity comprises that 30-100ppm silicon is not more than 0.02%, and aluminium bar is placed more shallow glass containers as shown in Figure 1,36 inches long.Aluminum is contacted with the hydrochloric acid of 3N down at 20 ℃, and the amount of hydrochloric acid should be enough to aluminium bar is covered.Afterwards, aluminium bar is taken out and under moist (relative humidity about 30%) air atmosphere condition, it is dipped in the mercury tank about 10 minutes from acid solution.

Then, will be dipped in partly again in the 2N hydrochloric acid tank liquor with the contacted aluminium bar of hydrargyrum.Can be observed on whole untreated aluminum surface has coordination compound to grow out, and aluminium bar begins to be dissolved in the hydrochloric acid tank liquor on the dipping surface.

The aeruginous amorphous substance that begins to form on non-impregnated surface is aluminum-hydrogen-oxygen coordination compound, is called BB-1.

This material is collected and be directly used in the processing of deodorizer, brightening agent, depilatory, biological substance, or be used to prepare various coordination compounds indirectly.

Embodiment 2

Present embodiment is illustrated the another kind of preparation method of BB-1.Used step is with embodiment 1, but raw material is the impure metal aluminium bar that is not more than 0.02% the about 0.3-1ppm of six side's sila matter.

Embodiment 3

This embodiment illustrates the preparation of BB-1 suspension.The BB-1 coordination compound of 100g embodiment 1 is introduced in the blind pipe (11) of Soxhlet apparatus (12).In flask (13), pack into 1000ml 3N hydrochloric acid (14) and be heated to boiling and make hydrochloric acid continue boiling and in about 90 minutes time, make acid solution circulation 4 times.At this moment, it is empty that the blind pipe (11) in the Soxhlet apparatus (12) becomes, and the liquid in the Soxhlet apparatus flask (13) is thin turbid solution or the suspension that looses.Be cooled to slowly add the 3N potassium hydroxide solution after about 20 ℃ at suspension, be increased to till about 5.4 up to pH.The rising of PH is monitored with Beckman (Beckman) pH meter.At this moment, in the extraordinary cosmetics of product-BB-1 suspension-can be used for, deodorizer, medicine and other prescription.

Embodiment 4

Following embodiment has illustrated and has used BB-1 suspension preparation of the present invention to help to treat the lotion of skin acne disease, and specifically, ingredients listed is used by listed percetage by weight in the table in the table 1

Table 1

The composition percetage by weight

Deionized water 65.419

BB-1 suspension 3.000

DDBS Special Richonate 6122

(dodecylbenzene sodium sulfonate) 1.800

Xylene monosulfonic acid potassium 3.550

Citric acid (anhydrous, American Pharmacopeia) 0.366

Antifoaming agent AF(DOW Corning produces) 0.005

Salicylic acid 0.500

Spice 0.050

Alcohol 95 % 23.000

Sodium carbonate (anhydrous)

Or potassium hydroxide 0.060

The Supercel(filter aid) (Rohm) ﹠amp; Haas produces) 0.250

Triethanolamine 2.000

100.000%

The container or the rustless steel container that deionized water are injected glass inner-lining prepare lotion.Then BB-1 suspension, dodecylbenzene sodium sulfonate, xylene monosulfonic acid potassium, citric acid and antifoaming agent AF are added in the entry.

Salicylic acid and spice is dissolved in is enough to dissolve in their a part of ethanol.The ethanol of remainder is added in the reaction vessel.Then, the solution that salicylic acid, spice and ethanol are formed is added in the container.

With sodium carbonate pH value is adjusted to 3.0.Add triethanolamine then.

Filtering mixt at room temperature.The preparation of filter aid is, the same operative liquid mixture of a part of Supercel is mixed and makes this concentrated solution transparent until filtrate by filter.In case of necessity, replaceable filter bed.Need not carry out ageing handles.

If reaction vessel is made of rustless steel,, then mixture should have been transferred in glass-lined hold-up tank or the bucket if long time stored.

Embodiment 5

Present embodiment is illustrated coordination compound of the present invention aspect health and beauty treatment, particularly the application aspect elimination acne formulation:

Following ingredients listed in the table 2 is mixed in agitator, obtain a kind of compositions of homogenizing.

Table 2

The composition percetage by weight ^*

Deionized water 65.419

BB-1 3.000

Dodecylbenzene sodium sulfonate 1.800

Xylene monosulfonic acid potassium 3.550

Citric acid (anhydrous, American Pharmacopeia) 0.366

Antifoaming agent AF 0.005

Salicylic acid 0.500

Alpine spice 6,321 0.050

Ethanol, 95% 23.000

Sodium carbonate (anhydrous) 0.060

The Supercel(filter aid) 0.250

Triethanolamine 2.000

100.000%

^*In composition total weight

Said composition can be directly used in the skin that is subjected to acne lesions.

BB-1 of the present invention believes that in the prior art mode of compositions works to be different from essence.Though coordination compound of the present invention has slight contraction, it neither makes chosure of pores, does not also make the pore expansion.Because it is rich in the oxygen that is easy to discharge, and because it is a halogen, for example sodium chloride (being present in from the antiperspirant that skin surface oozes out) activates, so this coordination compound discharges lasting and stable oxygen flow.

Blackhead directly is subjected to this oxygen invasion and attack that discharge.Because blackhead is isolated foreign body, Corium elephatis skin other parts do not have oxygen supply like that, so they are considered to become " air hunger ".The oxygen that discharges in the coordination compound can infiltrate blackhead easily and effectively and make their dryings, and the skin remainder is then unaffected.Using the oxygen carrier chemical compound, in the time of for example above-mentioned acne scavenger, affected skin has been subjected to control in acne in period of expansion.

This coordination compound can be used in other compositions of using on skin.A kind of in this based composition is oxter deodorizer.The problem that oxter of the prior art deodorizer is run into is the correct use amount of oxter part.Inoperative very little.Too much then may chafe.Yet coordination compound of the present invention is to the skin nonirritant.In addition, the salt in the antiperspirant promotes the release of hydrogen and oxygen.When stopping to perspire, the effect of aluminum-hydrogen-oxygen coordination compound stops immediately.When beginning to perspire heavily again, coordination compound begins heavily again to have an effect.

Embodiment 6

Present embodiment is illustrated and is used suspension of the present invention to prepare roll-on deodorizer.Used each becomes to be respectively in table 3 in the present embodiment, and shows corresponding percetage by weight:

Table 3

The composition percetage by weight

Container water 13.00

Almasilate (R.D.Vanderbilt) 0.43

Disodiumedetate NO.2 0.10

Water 37.23

Kisscowax-A-33（Mckesson & CO）

（PEG 400 MS） 2.89

Dupanol WA cream (Du Pont)

（Mapsofix WA） 0.56

Allantoin 0.05

Glycerol 4.50

Isopropyl alcohol 15.04

Polysorbas20 (polyoxyethylene (20) dehydration Pyrusussuriensis

Alcohol lauric acid monoesters) 0.69

Methyl Parabene(Atlas) 0.17

Spice (J﹠amp; J 6398) 0.15

BB-1 suspension 25.00

Color

Earlier water is added in the rustless steel vapor can.Mix with methyl Parabene then, till dissolving fully.May need heating so that dissolving is complete.

Make mixture cooling then and be sprinkling upon almasilate on the liquefied mixture surface and stirred the mixture about 15 minutes.After adding almasilate, the compositions restir was mixed 1 hour and make the mixture standing over night.Compositions is mixed, until fusing fully under 76 ℃ with disodiumedetate No.2, Kisscowax, dupanol, allantoin and glycerol.

Then, while stirring almasilate solution is heated to 71 ℃, up to forming isotropic phase.This isotropic phase should just mix with it after other mixture of ingredients mixes 1/2 hour.Mixture is cooled to 24 ℃ then.

Preparation is by isopropyl alcohol, polysorbas20 and spice (J﹠amp separately; J6398) solution of being formed.Mixture should be stirred to transparent, and transparent mixture should be added in the batching subsequently, and should add the BB-1 suspension in the mixture in about 3 hours time this moment.

Reach the final volume quality standard with deionized water, and make the painted standard that reaches of batching.

After discharging 2-3 gallon mixture, can get laboratory sample.Product can be preserved about 1 month after laboratory is checked and accepted in good condition as if in the Polythene Bag that is stored in sealing or in the rustless steel container.

Embodiment 7

Following embodiment illustrates the application of BB-1 of the present invention aspect the preparation skin whitener.Listed each composition all uses by listed percent in the table in the table 4:

Table 4

The composition percetage by weight

Hexamul AS(Hoechst produces) 12.0

Hexadecanol 5.0

Propyl group Parabene 0.1

Methyl Parabene 0.2

Citric acid 0.3

Water ^*79.7

BB-1 powder 2.0

Sodium sulfide 0.3

Pyrosulfurous acid hydrogen sodium 0.2

Stannous chloride 0.1

Dontill200(Dow Chemical produces)

Comprise rich amount, to allow its evaporation.

Be added to water in the blender and be heated to 82 ℃.Then, methyl Parabene is sneaked into wherein fully, sneak into stannous chloride afterwards again.

The mixture temperature that heated is dropped to 80 ℃ and sneak into Hexamul AS, hexadecanol, citric acid and propyl group Parabene and methyl Parabene.

The gained mixture is cooled to 50 ℃ and BB-1, sodium sulfide, pyrosulfurous acid hydrogen sodium and Dontill 200 fully mixed.

So just make final lotion, and can use on the skin at once.

In another kind is used, can make sewage deodorizing and reduce basicity, because oxygen enrichment can promote the decomposition of sewage.

This can be added to BB-1 in the sewage and finish.Because the variation of sewage character and required deodorization degree or response speed are different, BB-1 determines according to other obvious Consideration of pending predetermined substance, temperature and professional the special ratios fibrous root of sewage.As general range, every liter of about 1-20g BB-1 of sewage proves gratifying, and every liter of 2-12g is then better.

Though the present invention's rely is not understood fully as yet fully for the scientific phenomena on basis, and the applicant does not wish can believe that by any specific theoretical end of being made an appointment with the subgrain of aluminum is organized profound variation has been taken place seemingly under chemistry and electrochemical action yet.

Can think, because " free chlorine " of coordination compound, and, make the spherical shapes of silicon trace materials in the aluminum become six side's profiles because aluminum and hydrochloric acid solution that hydrargyrum was handled react to each other.People can observe, the hex hole in aluminum of the present invention-hydrogen-oxygen coordination compound and the profile similarity of six side's silicon crystal.It is relevant with a kind of phenomenon that can make coordination compound of the present invention discharge oxygen and hydrogen in the presence of catalyst that the character of BB-1 also can be thought.

In addition, when ordinary aluminum being placed the hydrochloric acid solution of 1N for example or 2N, produce aluminum chloride (and water).But when the aluminum of used contacted hydrargyrum was dipped in hydrochloric acid partly in process of the present invention, its behavior was quite inequality.Although still form aluminum chloride and other aluminium compound, after through about 8-72 hour, the coordination compound that occurs with the aeruginous amorphous substance during beginning is form on non-impregnated surface just.

Narrated in principle of the present invention, preferable embodiment and the mode of operation description in front.But, be intended to shall not be construed as and be limited to the particular forms disclosed in this invention of being protected, because they must regard elaboration as, and non-limiting.Only otherwise depart from spirit of the present invention, one of skill in the art can carry out various changes and change.

Claims

1, the process of preparation aluminum-hydrogen-oxygen coordination compound, this method comprises:

A. the metallic aluminium that makes purity be at least about 99.94% (weight) and contain trace silicon at least contacts with acid, and sour kind and concentration should be removed the oxide on the described metal, formation that again can the inhibited oxidation thing;

Metallic aluminium through acid treatment is contacted with the hydrargyrum source in oxygen-containing atmosphere; And

C. will make aluminum-hydrogen-oxygen coordination compound begin growth on the aluminum surface of contacted hydrargyrum through in halogen acid solution, flooding partly the sufficiently long time with the contacted aluminum of hydrargyrum.

2, the described process of claim 1, wherein said aluminum is at least about the aluminum of 99.99% purity, and contains the silicon of the 30-100ppm that has an appointment and be less than the ferrum of silicon weight about 40%.

3, the described process of claim 1, wherein step (c) is carried out under about 5-40 ℃ temperature.

4, the product of the described process of claim 1.

5, the product of the described process of claim 2.

6, the product of the described process of claim 3.

7, the described process of claim 1, wherein said aluminum is at least about the aluminum of 99.99% purity, and contains six side's silicon of the 0.3-1ppm that has an appointment.

8, the product of the described process of claim 7.

9, preparation can discharge the aluminum-hydrogen-oxygen coordination compound suspension of oxygen and hydrogen in the presence of halide-containing, and this method is made up of the following step basically:

A. purity is at least about 99.94%(weight) and contain at least that the metallic aluminium of trace silicon contacts with acid source, the kind of acid and concentration should be removed the oxide on the metal, can suppress the formation of oxide on the metal again;

Metallic aluminium through acid treatment is contacted with the hydrargyrum source in oxygen-containing atmosphere;

C. will make coordination compound on the aluminum surface of contacted hydrargyrum, begin growth through in halogen acid solution, flooding partly the sufficiently long time with the contacted aluminum of hydrargyrum;

Coordination compound heavily is dissolved in the halogen acid solution at least in part, to form suspension;

E. suspension is cooled off; And

F. the pH value with suspension is adjusted to about 5.0-5.8.

10, the described process of claim 9, wherein said aluminum are at least the aluminum of 99.94% purity and contain the ferrum that the 30-100ppm silicon peace treaty of having an appointment is less than silicon weight 40%.

11, the described process of claim 9, wherein step (c) is carried out under about 5-40 ℃ temperature.

12, the product of the described process of claim 9.

13, the product of the described process of claim 10.

14, the product of the described process of claim 11.

15, the process of preparation aluminum-hydrogen-oxygen powder, this method comprises:

A. make purity be at least 99.99%(weight) and the metallic aluminium that contains have an appointment 60-90ppm silicon and the ferrum that is less than silicon weight 30% contact with hydrochloric acid, the concentration of hydrochloric acid should be removed the oxide on the described metal surface, formation that again can the inhibited oxidation thing;

B. make metallic aluminium through acid treatment in oxygen-containing atmosphere with the hydrargyrum Metal Contact; And

C. will under about 20-30 ℃ temperature, in hydrochloric acid solution, flood partly the sufficiently long time through the contacted aluminum of hydrargyrum, and make on the aluminum of described contacted hydrargyrum to begin to form aluminum-hydrogen-oxygen powder.

16, the product of the described process of claim 15.

17, preparation can discharge the process of the aluminum-hydrogen-oxygen coordination compound suspension of oxygen and hydrogen in the presence of halide-containing, and this method comprises:

A. make purity be at least 99.99%(weight) and contain the 60-90ppm silicon of having an appointment and contact with hydrochloric acid with the metallic aluminium that is less than about 30% ferrum of silicon weight, the concentration of hydrochloric acid should be removed the oxide on the described metal, formation that again can inhibited oxidation;

Metallic aluminium through acid treatment is contacted with mercury metal in oxygen-containing atmosphere;

C. the aluminum with contacted hydrargyrum floods the sufficiently long time in the hydrochloric acid solution of about 20-30 ℃ temperature partly, makes on the aluminum surface of contacted hydrargyrum to begin the coordination compound of growing;

D. heavily be dissolved in the hydrochloric acid solution to major general's part coordination compound;

E. formed product is cooled to approximately temperature less than 50 ℃; And

The pH value that f. will cool off afterproduct is adjusted to about 5.3-5.5.

18, the product of the described process of claim 17.