CN102120613A - High-purity high-activity alkali type acyl zirconium carbonate and preparation method thereof - Google Patents
High-purity high-activity alkali type acyl zirconium carbonate and preparation method thereof Download PDFInfo
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Abstract
The invention discloses high-purity high-activity alkali type acyl zirconium carbonate and a preparation method thereof. In the preparation method, zirconyl chloride octahydrate, sulfuric acid or sodium sulfate or sodium carbonate or sodium (ammonium) bicarbonate is used as a raw material, and the alkali type acyl zirconium carbonate is produced through vulcanization, carbonization and activation. The process in the invention is simple and reasonable, the prepared alkali type acyl zirconium carbonate has advantages of high quality, good property, strong practicability and wide application range; the control of vulcanization process is rigorous in no need of adding an organic catalyst, so that the alkali type acyl zirconium carbonate with a large particle size is prepared, and a large three-dimensional space is provided for storing effective carbon in high-purity high-activity alkali type acyl zirconium carbonate production; an activated process is added, the hydroxyl ratio in a finished product is reduced, the microstructure of the alkali type acyl zirconium carbonate is changed, the metastability of the alkali type acyl zirconium carbonate is activated, and the use property of the alkali type acyl zirconium carbonate is enhanced.
Description
Technical field
The present invention relates to a kind of zirconium carbonate and preparation method thereof, particularly a kind of high-purity high-activity alkali formula acyl group zirconium carbonate and preparation method thereof.
Background technology
Alkali formula acyl group zirconium carbonate is different with performance according to its quality, is divided into common zirconium carbonate and high-purity high reactivity carbonic acid zirconium; According to its production technique difference, the strong acid salt that is divided into zirconium follows the carbonate of basic metal or ammonium to play replacement(metathesis)reaction, a kind of is reaction in solution, as a Chinese patent " production method of zirconyl carbonate " (application number 200910207729.5, be called for short prior art 1) in mention: with in a kind of acidic cpd with unnecessary yellow soda ash, the slurry acidity of regulating sodium zirconium carbonate is to pH3.5-4.5, vacuum filtration, centrifuge dehydration, obtain containing 35-40% zirconium white, 8-10% carbonate, be lower than the zirconyl carbonate of 0.1% sodium ion.According to the structural formula of its sodium zirconium carbonate, its general formula should be ZrO
2CO
2NH
2O, the concrete industrial use of this zirconium carbonate then offers some clarification on, and the production technique to this zirconyl carbonate just briefly touches upon in the literary composition, and those skilled in the art can't this processing step of detail knowledge.
Chinese patent " sodium zirconium carbonate and zirconyl carbonate and preparation method thereof " (application number 01821766.4, publication number CN 1484617A, hereinafter referred to as prior art 2), the contriver of this application and prior art 1 is the Lei Mengde J king of Indiana, USA, it is identical with prior art 1 described product that the zirconyl carbonate of this invention contains zirconium white, carbonate, impurity natrium ionic amount, only rises to below 0.01% by the 0wt% of prior art 1 in the content narration of sulfate radical, chlorion; The structural formula of zirconyl carbonate has also had clear and definite explanation, and promptly two zirconium atoms link to each other with four hydroxide radicals with three oxygen, and the carbon of carbonyl links to each other with one oxygen hydroxy, and general formula should be: (ZrO)
2(OH)
4COnH
2O, the industrial use of this zirconium carbonate is tended to medical field of dialysis, in the literary composition sodium zirconium carbonate there is comparatively detailed requirement introduction, mention more with the zirconium phosphate that invention does not reach mutually, zirconyl carbonate is to do raw material with the sodium zirconium carbonate of this invention, its process introduction is similar with prior art 1, aspect the zirconium carbonate slurry acidity adjustment simple variation is being arranged, slurry acidity pH control 3.5-4.5 by original sodium zirconium carbonate adjusts to pH3.5-4.0, the specification sheets (the 15th page) of the 2/5th page of its claims and back mentions that the technology content of zirconyl carbonate is basic identical, and the mode of production of zirconyl carbonate is not equally carried at all among simple in the back two embodiment.
A PCT patent " zirconium white of finely powdered; zirconyl carbonate and their preparation method " (domestic application number: 01814992.8, enter country's time: 2003.02.08 contriver J-V Martin, hereinafter to be referred as prior art 3), the manufacture craft of this invention zirconyl carbonate is the zirconic granularity service of its invention of preparation merely, and its invention product tends to cl content less than 300ppm, sulphur content is less than 30ppm, and the apparent size of the crystal of zirconium oxide of producing after calcining is at 0.1-0.6um; Embodiment 1 usefulness chlorine oxygen zirconium solution and ammonium bicarbonate soln are pressed CO
3 2-The mol ratio of/Zr is to mix at 1: 1, and the pH with ammoniacal liquor control solution reaches 4.8 during operation.
The strong acid salt of zirconium is a solid reaction with the another kind of form of the carbonate replacement(metathesis)reaction of basic metal or ammonium, as Chinese patent " a kind of solid-state production process " (application number: 01127301.1, hereinafter to be referred as prior art 4), it directly is to react between the solid reactant, the solid-state production process of this disclosure of the Invention is meant the production method with the carbonate direct production zirconyl carbonate of the strong acid salt of zirconium and alkali or alkaline-earth metal (comprising ammonium), the processing compound that this method embodies is zirconates and carbonate generation equivalent replacement(metathesis)reaction, the emphasis washing times is minimum, selected carbonate must be water-soluble, reclaims byproduct; Traditional zirconyl carbonate is narrated in this invention in background technology production technique is that eight hydration zirconium oxychloride solution and sulfuric acid or vitriol are hydrolyzed into zirconium basic sulphate, generate zirconyl carbonate with supercarbonate or carbonate carbonization again, obtain finished product through washing, centrifuge dehydration, do not have important follow-up activation procedure.The zirconyl carbonate of this invention can only be used for general vitrified bond, is very narrow a kind of of industrial use.This zirconyl carbonate that generates naturally generally in mineral acid dissolving better, in acetate, propionic acid, cyclohexane acid, isocaprylic acid, volatile salt dissolving very poor, promptly the normal lytic activity of saying is low in the field in; And the reaction pair chlorine oxygen zirconium between the solid and the specification of quality of carbonate or supercarbonate are very high, otherwise the quality of finished product can't guarantee, select for use its cost of high-quality industrial raw material to increase certainly.
The exercise question that Jiangxi Kingan Hi-Tech Co., Ltd. delivered on volume the 1st phase " rare metal " monthly magazine January the 27th in 2003 is the web page files (hereinafter to be referred as prior art 5) of " character of zirconium sulfate, zirconium carbonate, application and production technology summary ", wherein pointed out the simple production process of zirconium carbonate, this process is mentioned zirconium basic sulphate crystal formation and growth conditions, conversion, catalytic theory and catalytic mechanism, the selected technology of catalyzer, the gordian techniquies such as design of special-purpose reaction system; The present invention's tendency is selected suitable zirconium liquid concentration, low temperature rise rate, suitable zirconium sulphur proportioning and static soaking time for use, such technology controlling and process can widen the spacing of lattice of acyl group zirconium basic sulphate, production technique with prior art 5 " substep liquid-phase precipitation method " is far from each other, do not relate to that alkali formula acyl group zirconium sulfate forms and necessary catalytic theory of growth conditions and catalytic mechanism, let alone the gordian techniquies such as design of the selected technology of what catalyzer, special-purpose reaction system; Processing condition of the present invention have determined the product performance of alkali formula acyl group zirconium sulfate, and the similarities and differences are formed in the crystal of prior art 5 narrations, and the difference of structure is that the different institutes of the reaction mechanism of its production process cause; The alkali formula acyl group zirconium sulfate slurry of the big particle diameter that the present invention will make, bottom land pump water overflow washing, make alkali formula acyl group zirconium sulfate in washing process, be in suspended state, the alkali formula acyl group zirconium sulfate of not exerting pressure keeps original apparent condition, not sealing, synergetic alkali formula acyl group zirconium sulfate keep the primary surfactivity, and the zirconium basic sulphate of microcosmic macroscopic viewization provides big skeleton storage carbon space for producing zirconium carbonate; Big particle diameter zirconium basic sulphate, generate the zirconium carbonate slurry with solvable carbonate reaction, obtain the zirconium carbonate that the surface keeps original activity with same mode of washing, wash contact area on a large scale for the activation removal of impurities provides, and prior art 5 is quite different, one road suction filtration goes down, zirconium basic sulphate behind the suction filtration, zirconium carbonate particle diameter are close to overlapping, dwindled effective contact surface, covered surface impurity deeply, the disorderly arrangement of its matrix skeleton useful space; Zirconium carbonate slurry after the countercurrent washing is activated, washing, centrifuge dehydration just obtain being soluble in mineral acid, organic acid and solvable carbonate high-purity, high reactivity product.Zirconium carbon number ratio was that 2, two zirconium acyl groups link to each other with the oxygen of two carbonates and the hydroxide radical of two band water separately during this product was formed, and general formula is: (ZrO)
2(HO)
2CO
3NH
2O, the content of general zirconium white (hafnium) is at 40-42%, and the effective carbon dioxide content of the ratio of corresponding zirconium is at 7-7.5%.Expression formula from prior art 5 described zirconium carbonates, the composition of its zirconium carbonate is that zirconium, carbon number ratio are 1: 1, and zirconium carbon number ratio of the present invention is 2: 1, and this is different with technology of the present invention relevant with prior art 5, different reaction mechanisms, the composition structure difference of resultant; The substep liquid-phase precipitation termination operation of prior art 5 terminates in " zirconium basic sulphate after will washing and carbonate wash (suction filtration simultaneously) after reacting at normal temperatures and pressures, " and does not set up important activation procedure, does not have aftertreatment of the present invention.Every its quality of zirconium carbonate of not carrying out activation treatment is not the foreign matter content height, be exactly that comprehensive solvability is bad, or both haves both at the same time.Guaranteeing under the prerequisite of effective carbon, except that user's particular requirement, pH value is near the zirconium carbonate of theoretical composition, and ammonium salt that carbonization is used or sodium salt under equal conditions (refer to the water yield and temperature) separating effect is best; The good more activity of the zirconium carbonate that the hydroxide radical group is many more, the stability after its ageing is low more, and volatile salt and organic acid solvability are poor more.The active high major cause of zirconium carbonate that generates of U.S. Magnesium Elektron Inc. (being called for short MEI) and Britain Melchbmicals (being called for short MEL) why that Here it is.
Zirconium carbonate is crucial compound, it not only can be used for the zirconic production of fineness and be used to do the presoma of the air-breathing zirconium phosphate of dialysis, more be mainly used in makeup and make antiperspirant coagent aluminum zirconium glycine, in paper-making industry, be used as the zirconium carbonate ammonia of alkaline bleach liquor sizing, the adhesive aid and the paint drier of vehicle exhaust three-element catalytic aspect, annual 10% the speed increase of pressing of market demand.
The production of zirconium carbonate at present there is no report except that the paper publishing of above-mentioned four patent applications, the brilliant peace in Jiangxi company, the application requires the production method of invention high quality zirconium carbonate according to different user.The high quality zirconium carbonate refers to that not only its chemical purity is higher than industry standard, and solubility property is good in mineral acid, organic acid and sal volatile.
Summary of the invention
The objective of the invention is to overcome the deficiencies in the prior art, a kind of high-purity high-activity alkali formula acyl group zirconium carbonate and preparation method thereof is provided, the zirconium carbonate that this method is produced is soluble in mineral acid, organic acid and volatile salt.
High-purity high-activity alkali formula acyl group zirconium carbonate of the present invention, its structural formula is:
The preparation method of above-mentioned high-purity high-activity alkali formula acyl group zirconium carbonate has two kinds, and first method may further comprise the steps:
1) eight hydration zirconium oxychlorides and sodium sulfate are pressed zirconium sulphur mol ratio 1: 0.55-0.6 mixing, be dissolved in 45-50 ℃ the water solid-to-liquid ratio 1: 4.5-1 after the mixing: 5.5 filter, and heat temperature raising is to 95-98 ℃, be incubated 60-80 minute, get alkali formula acyl group zirconium sulfate mixed slurry;
2) the alkali formula acyl group zirconium sulfate slurry that step 1) is obtained is put in the settling bath, with 50-55 ℃ water overflow washing, Cl in alkali formula acyl group zirconium sulfate slurry
-Be lower than 100ppm, naturally filter do alkali formula acyl group zirconium sulfate throw out;
3) with step 2) the alkali formula acyl group zirconium sulfate throw out that obtains moves to and adds water to solid-to-liquid ratio 1: 2 in the retort, add saturated soda ash solution again and be heated to 45-50 ℃ of insulation 50-70 minute by sulphur carbon mol ratio 1: 1.05-1.1, promptly get alkali formula acyl group zirconium carbonate slurry, washed 15 minutes with 45-50 ℃ water overflow, filter is done naturally;
4) the alkali formula acyl group zirconium carbonate that step 3) is obtained [H
+]: the sulphuric acid soln activation of 0.8-1.0mol/L, 45 ℃ of constant temperature are regulated acidity and are made pH be stabilized in 3.5-7.0 maintenance 30-40 minute, filter drip washing SO in alkali formula acyl group zirconium carbonate
4 2-Less than 50ppm, centrifuge dehydration gets alkali formula acyl group zirconium carbonate finished product.
Above-mentioned steps 1) eight hydration zirconium oxychloride content are greater than 98% in, and sodium sulphate content is greater than 98%; The mixed solution control temperature rise rate of eight hydration zirconium oxychlorides and sodium sulfate is 0.5 ℃/min.
Second method may further comprise the steps:
1) eight hydration zirconium oxychlorides are soluble in water, solid-to-liquid ratio 1: 3.5-4.0 filters, and presses zirconium sulphur mol ratio 1: 0.55-0.6 and adds 1: 1 sulphuric acid soln, and 1: 1 sulphuric acid soln wherein is meant that sulfuric acid mixes with the water equal-volume; Heat temperature raising is incubated 60-80 minute to 95-98 ℃, gets alkali formula acyl group zirconium sulfate mixed slurry;
2) the alkali formula acyl group zirconium sulfate slurry that step 1) is obtained is put in the settling bath, with 50-55 ℃ water overflow washing, Cl in alkali formula acyl group zirconium sulfate slurry
-Be lower than 100ppm, naturally filter do alkali formula acyl group zirconium sulfate throw out;
3) with step 2) the alkali formula acyl group zirconium sulfate throw out that obtains moves to and adds water to solid-to-liquid ratio 1: 2 in the retort, add saturated soda ash solution again and be heated to 45-50 ℃ of insulation 50-70 minute by sulphur carbon mol ratio 1: 1.05-1.1, get alkali formula acyl group zirconium carbonate slurry, washed 15 minutes with 45-50 ℃ water overflow, filter is done naturally;
4) the alkali formula acyl group zirconium carbonate that step 3) is obtained [H
+]: the sulphuric acid soln activation of 0.8-1.0mol/L, 45 ℃ of constant temperature are regulated acidity and are made pH be stabilized in 3.5-7.0 maintenance 30-40 minute, filter drip washing SO in alkali formula acyl group zirconium carbonate slurry
4 2-Less than 50ppm, centrifuge dehydration gets alkali formula acyl group zirconium carbonate finished product.
Above-mentioned steps 1) eight hydration zirconium oxychloride content are greater than 98% in, and sulfuric acid content is 0.5 ℃/min greater than 98%, eight hydration zirconium oxychloride and sulfuric acid mixture liquid control temperature rise rate.
Below set forth beneficial effect of the present invention in conjunction with prior art in detail:
1, about the step 1 among two kinds of preparation methods
Step 1) among two kinds of preparation methods is all filtered the solution of chlorine oxygen zirconium, sodium sulfate mixture or single chlorine oxygen zirconium.
The chlorine oxygen zirconium of technical grade since in the circulation technology mother liquor of evaporation concentration or repeatedly the mother liquor blending in original clear liquid, the xln absorption former colloid of wetting ability silicon and other impurity level of chlorine oxygen zirconium increase, cause its dissolving back clarity not high, generally all will filter.The mixed dissolution of chlorine oxygen zirconium and sodium sulfate, suitable solvent temperature, filter effect is better than single filtration sodium sulfate or chlorine oxygen zirconium effect.
Prior art 4 direct solid reactions do not filter, and the insoluble impurity of all carbonate that chlorine oxygen zirconium carries all can be brought in the finished product zirconium carbonate and go.Other application does not all have this operation.Prior art 5 does not offer some clarification on the restriction of chlorine oxygen zirconium dissolution mechanism and concentration value and the temperature increasing schedule that reaction is carried out, and tends to selection of catalysts and catalyzed conversion when sulfuration.
The present invention draws by orthogonal test repeatedly: suitable zirconium, sulphur mixes or single zirconium solution concentration, low temperature rise rate, suitable zirconium sulphur proportioning and static soaking time can widen the spacing of lattice of alkali formula acyl group zirconium sulfate.The alkali formula acyl group zirconium sulfate of big particle diameter is taken assorted few quality height, is convenient to washing; The alkali formula acyl group zirconium sulfate that high acidity generates, high volence metal ion such as impurity iron, titanium is further separated in the raw material.The hydrogenchloride that this workshop section generates when using sulfuric acid to do raw material reaction becomes the industrial salt acid product after the soft water spray absorbs.
2, the step 2 among a kind of preparation method of high-purity high-activity alkali formula acyl group zirconium carbonate
The alkali formula acyl group zirconium sulfate that the present invention makes is the basis that produces the high quality zirconium carbonate, and its reaction conditions is gentle, does not relate to High Temperature High Pressure and catalyzed conversion; Adopt bottom land water inlet overflow washing, make alkali formula acyl group zirconium sulfate be in suspended state in washing process, the alkali formula acyl group zirconium sulfate of not exerting pressure keeps original apparent condition, does not have sealing, synergetic zirconium basic sulphate to keep big original surface.By multi-wash test, the content of the completeness of its zirconium basic sulphate carbonization and effective carbon is relevant with particle diameter, the mode of washing of zirconium sulfate.The particle diameter of identical zirconium sulfate, its mode of washing difference, the content of effective carbon is also different during carbonization, and the solvability of organic acid, volatile salt is also different.
Prior art 5 washing rooms then tend to the drip washing of band filter suction filtration, the mode of washing that suction filtration is exerted pressure can make the amorphous zirconium basic sulphate of intensity weakness overlap each other and fall into rank, both covered surface impurity deeply, the disorderly again arrangement of its matrix skeleton useful space, carbonization, activation effect are relatively poor.Other patent documentation does not have to focus on or have novelty to mention in this workshop section.The present invention does raw material as using sodium sulfate, obtains technical grade product after the sodium-chlor that cover is washed enrichment concentrates.
3, about the step 3 among two kinds of preparation methods
The acyl group zirconyl carbonate slurry that this workshop section makes is after bottom land water inlet overflow cover is washed, chemical quality with the low titanium of low iron, strong solution after cover is washed, evaporation concentration makes technical grade sodium sulfate, process is the too many water of needs as prior art 4 is said not, and washing water are more direct exhaust emission environment; This application mentions that the mode of production of zirconium carbonate is the strong acid salt of zirconium and soluble carbon hydrochlorate process solid mixed grinding, washing separates sodium-chlor or the ammonium chloride that generates then, in this reactive mode, not only all water-fast carbonate and other water-fast impurity all enter in the product in the raw material, comprise mechanical impurity, and lytic activity and poor, so this quality product can only be used for the manufacturing of the very low ceramic of requirement.
It is on February 28th, 2003 that prior art 3 enters country's time, has only the forming process of zirconium carbonate in the embodiment, it directly is not described in detail as product, lays particular emphasis on as the ideal zirconium oxide precursor.Its reaction ratio CO
3 2-/ Zr mol ratio is 1, reaches 4.8 with ammoniacal liquor balance acidity-basicity ph value.
It is on July 4th, 2003 that prior art 2 enters country's time, this application discloses a kind of mode of production of zirconium carbonate, be acid reagent titration sodium zirconium carbonate slurry to pH value 3.5-4.0, carry out vacuum filtration then, and this filter back thing is carried out simple quality describe: zirconium white is 35-40%.Carbonate is 8-10%, and sodium ion is lower than 1000PPM, discloses the sulfate radical of this zirconium carbonate and the content of chlorion is lower than 0.01% in the 15th page in specification sheets, and the structure of this zirconium carbonate is described.Wish that purposes is the Plessy's green as the hemodialysis aspect; But in the end show no sign of the production method of mentioning zirconium carbonate in two simple embodiment.
Prior art 1 is just simply mentioned in that the 6th page of described zirconium carbonate content of specification sheets and prior art 2 are the same, is illustrated that the sulfate radical of this zirconium carbonate and the content of chlorion are lower than 0.01%, and the structure of this zirconium carbonate has been carried out identical description.
Prior art 5 has been narrated the product structure of zirconium carbonate, find out obviously that from its expression formula the zirconium carbon ratio is 1: 1, and the present invention is 2: 1, its product structure difference, and performance is totally different certainly; The filtration washing prior art 5 of process all is to adopt band filter to carry out filtering and washing, exist water outlet, suction, filter cloth travelling speed inharmonious owing to be in the narrow and total system of the fixedly drip washing pipe water outlet coverage rate of circular flow filter cloth top, cause the material washing uneven, not in place or the zirconium carbonate that is in the dead angle of drip washing behind centrifuge dripping it sodium ion or sulfate radical up to thousands of ppm, impurity exceeds standard tens times, and high-quality zirconium carbonate all will advance groove and wash once more; High negative pressure parameter causes the fine particle slurry to penetrate from the filter cloth reverse side of tightening simultaneously, and loss is with bigger, and the operation yield is low; Band filter is good in be far from aspect filtration washing zirconium basic sulphate and the zirconium carbonate normal pressure or suction filtration trough washing effect, and final product quality is extremely unstable, does not have advantage more not have strong point on year-on-year basis.
4, about the step 4 among two kinds of preparation methods
This step is washed the overflow of zirconium carbonate slurry warm water earlier, keep macroscopical external form of zirconium carbonate not change, be exposed to the impurity separate easily on throw out surface, treat after the sodium sulfate that soluble carbon hydrochlorate that flush away is excessive or supercarbonate and reaction generate,, wish the lytic activity that zirconium carbonate is regulated in acid with low according to customer requirements, not sealing, synergetic zirconium carbonate keep the original surface state, the diluted acid contact surface is big, and activation effect is good, macroscopic view, microcosmic uniformity; Select for use sulfuric acid to do the activation medium, do not introduce new impurity, keep the consistence of zirconium carbonate system; Because sulfate radical has bigger ion particle diameter, in above-mentioned wash conditions the zirconium carbonate that this technology generates is carried out the sulfate radical separating treatment, than selecting for use hydrochloric acid and nitric acid to come the separate sulfur acid group under the condition same activation effect and washing quality being arranged on year-on-year basis.And prior art 4 is zirconium carbonates that reaction obtains between the solid, and its product structure, quality, purposes all do not offer some clarification on.Prior art 1 and 2 is that the source goes out same contriver, this invention is to make sodium zirconium carbonate earlier, regulating the sodium zirconium carbonate pH value of slurry with diluted acid then is 3.5-4.0, carry out vacuum filtration then, its quality zirconium white of the zirconium carbonate that obtains after the filter is 35-40%, and carbonate is 8-10%, sodium ion is lower than 1000PPM, the content of sulfate radical and chlorion is lower than 0.01%, and the structure of this zirconium carbonate is described, and its purposes is to do matrix as the zirconium phosphate of hemodialysis aspect.The forming process of having only zirconium carbonate among the embodiment of prior art 3, its product structure, quality index do not offer some clarification on, and its purposes is the zirconium white presoma that lays particular emphasis on as granularity requirements; Though the production process of prior art 5 adopts catalyzed conversion, the zirconium carbonate particle diameter is still little, does not have reactivation process.Every do not have an activatory zirconium carbonate, hydroxyl content height in its matrix, and organic acid, volatile salt solvability are very poor.The present invention compares with prior art 1,2,3,4,5 technologies, and its quality height, performance is good, purposes is wide, both can be used as the zirconium white presoma of simple high-ratio surface, and the zirconium phosphate matrix of can dialysing has again comprised all purposes of prior art 4 especially.In addition, this product is more suitable for making antiperspirant coagent aluminum zirconium glycine as makeup, is used as the zirconium carbonate ammonia of alkaline bleach liquor sizing in the paper-making industry, the adhesive aid and the paint drier of vehicle exhaust three-element catalytic aspect.
Zirconium carbonate of the present invention is compared and be the results are shown in national sector standard, the brilliant peace in Jiangxi company, illiteracy moral J king application
Table 1:
The present invention caters to the newly-increased isocaprylic acid of customer requirement, acetic acid, volatile salt dissolving project.
Zirconium carbonate of the present invention is compared and be the results are shown in table 2 with the brilliant peace in Jiangxi company, U.S. Mars Inc. quality:
The present invention compares with the technology of the brilliant peace in Jiangxi company with above-mentioned patent application, has following advantage:
1, chlorine oxygen zirconium, sodium sulfate mixed solution or the single chlorine oxygen zirconium clear solution of handling well early stage guaranteed sulfuration workshop section materials quality, lays a solid foundation for making high-quality alkali formula acyl group zirconium sulfate;
2, suitable zirconium sulphur mixes or single zirconium solution concentration, low temperature rise rate, preferred zirconium sulphur proportioning and static soaking time, need not to add organic catalyst and just can make big particle diameter alkali formula acyl group zirconium sulfate, and it is taken and mixes less, the quality height, is convenient to washing;
The overflow washing of 3, not exerting pressure guarantees that material is in suspended state in washing process, and not sealing, synergetic washes keep the primary condition of surface, does not have destroyed zirconium carbonate pedestal activation homogeneous, effectively the stability maintenance height of carbon;
4, high spacious zirconium basic sulphate micro-space, suitable carbonization temperature, zirconium carbon ratio have guaranteed the storage of the effective carbon of high reactivity carbonic acid zirconium;
5, newly-increased acid adjustment operation has reduced ratio hydroxy in the finished product, and the microstructure of zirconium carbonate is changed, and has intensified zirconium carbonate meta activity, strengthens the use properties of high quality zirconium carbonate.
6, product of the present invention is soluble in mineral acid, organic acid and volatile salt, and zirconium carbon number ratio was 2 during it was formed, and its structure is that two acyl group zirconiums link to each other with the oxygen of two carbonates and the hydroxide radical of two band water separately, and general formula is: (ZrO)
2(HO)
2CO
3NH
2O, the content of zirconium white (hafnium) are at 40-42%, and the content of the effective carbonic acid gas of ratio of corresponding zirconium is 7-7.5%.
Do not add specified otherwise; the described chlorine oxygen of the application zirconium all is eight hydration zirconium oxychlorides; zirconium sulfate of the present invention, zirconium carbonate or zirconium basic sulphate, zirconyl carbonate all are that the form with alkali formula acyl group salt exists; described solid-to-liquid ratio all is a weight ratio; institute's water is deionized water; effectively the explanation of carbon is the total amount of the carbonate that directly links to each other with the acyl group zirconium, and Jiangxi crystalline substance peace company refers to prior art 5.
Embodiment
Embodiment 1:
Purity was pressed zirconium sulphur mol ratio 1: 0.58 greater than 98% chlorine oxygen zirconium and purity greater than 98% sodium sulfate, be dissolved in 45 ℃ the water, the solid-liquid weight ratio is filtered at 1: 4.5, filtrate pumps in the retort 0.5 ℃/min of control temperature rise rate heat to 95 ℃, static insulation 60 minutes, the zirconium basic sulphate mixed slurry, Cl to the slurry is washed in overflow
-Be lower than 100ppm; naturally filter is done; throw out moves into the interior solid-to-liquid ratio of retort and adds water at 1: 2; add saturated soda ash filter back liquid and be heated to 45 ℃ of insulations 50 minutes at 1: 1.05 by sulphur carbon mol ratio; static state is incubated half an hour and promptly gets alkali formula acyl group zirconium carbonate slurry; this slurry is put into rinse bath, wash with 45 ℃ of water overflows and moved in the retort adding [H in 15 minutes
+]: 45 ℃ of the sulphuric acid soln constant temperature of 0.8mol/L kept 30 minutes to pH3.5, high reactivity carbonic acid zirconium slurry, this slurry is put into the drip washing of rinse bath suction filtration, until SO
4 2-Till 50ppm, the zirconium carbonate centrifuge dehydration of filter back got the zirconium carbonate finished product in ten minutes.Process concentrates cover and washes sodium-chlor, sodium sulfate strong solution, gets technical grade sodium-chlor and reuse sodium sulfate byproduct of the present invention.
Embodiment 2:
Purity was pressed zirconium sulphur mol ratio 1: 0.60 greater than 98% chlorine oxygen zirconium and purity greater than 98% sodium sulfate, be dissolved in 50 ℃ the water, the solid-liquid weight ratio is filtered at 1: 5.5, filtrate pumps in the retort 0.5 ℃/min of control temperature rise rate heat to 98 ℃, static insulation 80 minutes, get the zirconium basic sulphate mixed slurry, overflow is washed to slurry C l
-Be lower than 100ppm; naturally filter is done; throw out moves into the interior solid-to-liquid ratio of retort and adds water at 1: 2; add saturated soda ash filter back solution and be heated to 50 ℃ of insulations 70 minutes at 1: 1.1 by sulphur carbon mol ratio; static state is incubated half an hour and promptly gets alkali formula acyl group zirconium carbonate slurry; this slurry is put into rinse bath, and overflow is washed and was moved in the retort in 15 minutes, adds [H
+]: 45 ℃ of the sulphuric acid soln constant temperature of 1.0mol/L kept 40 minutes to pH7.0, high reactivity carbonic acid zirconium slurry, this slurry is put into the drip washing of rinse bath suction filtration, until SO
4 2-Till 50ppm, the zirconium carbonate centrifuge dehydration of filter back got the zirconium carbonate finished product in ten minutes.Process concentrates cover and washes sodium-chlor, sodium sulfate strong solution, gets technical grade sodium-chlor and reuse sodium sulfate byproduct of the present invention.
Embodiment 3:
Purity was pressed zirconium sulphur mol ratio 1: 0.59 greater than 98% chlorine oxygen zirconium and purity greater than 98% sodium sulfate, be dissolved in 48 ℃ the water, the solid-liquid weight ratio is filtered at 1: 5.0, filtrate pumps in the retort 0.5 ℃/min of control temperature rise rate heat to 97 ℃, static insulation 70 minutes, get the zirconium basic sulphate mixed slurry, overflow is washed to slurry C l
-Be lower than 100ppm; naturally filter is done; throw out moves into the interior solid-to-liquid ratio of retort and adds water at 1: 2; add saturated soda ash filter back liquid and be heated to 48 ℃ of insulations 60 minutes at 1: 1.07 by sulphur carbon mol ratio; static state is incubated half an hour and promptly gets alkali formula acyl group zirconium carbonate slurry; this slurry is put into rinse bath, and overflow is washed and was moved in the retort in 15 minutes, adds [H
+]: 45 ℃ of the sulphuric acid soln constant temperature of 0.9mol/L kept 35 minutes to pH4.5, high reactivity carbonic acid zirconium slurry, this slurry is put into the drip washing of rinse bath suction filtration, until SO
4 2-Till 50ppm, the zirconium carbonate centrifuge dehydration of filter back got the zirconium carbonate finished product in ten minutes.Process concentrates cover and washes sodium-chlor, sodium sulfate strong solution, gets technical grade sodium-chlor and reuse sodium sulfate byproduct of the present invention.
Embodiment 4:
Purity is soluble in water greater than 98% chlorine oxygen zirconium, the solid-liquid weight ratio is filtered at 1: 3.5, the clear filtrate of zirconium is pumped in the retort, add content and pressed zirconium sulphur mol ratio 1: 0.55 greater than 98%1: 1 sulfuric acid, control temperature rise rate 0.5 ℃/min heat to 95 ℃, static insulation 60 minutes, the zirconium basic sulphate mixed slurry, slurry is put into rinse bath, and overflow is washed to slurry C l
-Be lower than 100ppm; naturally filter is done; throw out moves into the interior solid-to-liquid ratio of retort and adds water at 1: 2; add saturated bicarbonate of ammonia filter back liquid and be heated to 45 ℃ of insulations 60 minutes at 1: 1.08 by sulphur carbon mol ratio; static state is incubated half an hour and promptly gets alkali formula acyl group zirconium carbonate slurry; this slurry is put into rinse bath, and overflow is washed and was moved in the retort in 15 minutes, adds [H
+]: 45 ℃ of the sulphuric acid soln constant temperature of 0.8mol/L kept 30 minutes to pH4.0, high reactivity carbonic acid zirconium slurry, this slurry is put into the drip washing of rinse bath suction filtration, until SO
4 2-less than till the 50ppm, the zirconium carbonate centrifuge dehydration of filter back got the zirconium carbonate finished product in ten minutes.The process vacuum reclaims hydrogenchloride as industrial hydrochloric acid, and the evaporation concentration cover is washed high vitriol oil sodium solution, gets reuse sodium sulfate byproduct of the present invention.
Embodiment 5:
Purity is soluble in water greater than 98% chlorine oxygen zirconium, the solid-liquid weight ratio is filtered at 1: 4.0, the clear filtrate of zirconium is pumped in the retort, add content and pressed zirconium sulphur mol ratio 1: 0.58 greater than 98%1: 1 sulfuric acid, control temperature rise rate 0.5 ℃/min heat to 98 ℃, static insulation 80 minutes gets the zirconium basic sulphate mixed slurry, and overflow is washed to slurry C l
-Be lower than 100ppm; naturally filter is done; throw out moves into the interior solid-to-liquid ratio of retort and adds water at 1: 2; add saturated sodium bicarbonate filter back liquid and be heated to 50 ℃ of insulations 70 minutes at 1: 1.1 by sulphur carbon mol ratio; static state is incubated half an hour and promptly gets alkali formula acyl group zirconium carbonate slurry; this slurry is put into rinse bath, and overflow is washed and was moved in the retort in 15 minutes, adds [H
+]: 45 ℃ of the sulphuric acid soln constant temperature of 1.0mol/L kept 40 minutes to pH6.0, high reactivity carbonic acid zirconium slurry, this slurry is put into the drip washing of rinse bath suction filtration, until SO
4 2-Till 50ppm, the zirconium carbonate centrifuge dehydration of filter back got the zirconium carbonate finished product in ten minutes.The process vacuum reclaims hydrogenchloride as industrial hydrochloric acid, and the evaporation concentration cover is washed high vitriol oil sodium solution, gets reuse sodium sulfate byproduct of the present invention.
Embodiment 6:
Purity is soluble in water greater than 98% chlorine oxygen zirconium, the solid-liquid weight ratio is filtered at 1: 3.8, the clear filtrate of zirconium is pumped in the retort, add content and pressed zirconium sulphur mol ratio 1: 0.56 greater than 98%1: 1 sulfuric acid, control temperature rise rate 0.5 ℃/min heat to 96 ℃, static insulation 70 minutes gets the zirconium basic sulphate mixed slurry, and overflow is washed to slurry C l
-Be lower than 100ppm; naturally filter is done; throw out moves into the interior solid-to-liquid ratio of retort and adds water at 1: 2; add saturated bicarbonate of ammonia filter back liquid and be heated to 48 ℃ of insulations 60 minutes at 1: 1.05 by sulphur carbon mol ratio; static state is incubated half an hour and promptly gets alkali formula acyl group zirconium carbonate slurry; this slurry is put into rinse bath, and overflow is washed and was moved in the retort in 15 minutes, adds [H
+]: 45 ℃ of the sulphuric acid soln constant temperature of 0.9mol/L kept 40 minutes to pH7.0, high reactivity carbonic acid zirconium slurry, this slurry is put into the drip washing of rinse bath suction filtration, until SO
4 2-Till 50ppm, the zirconium carbonate centrifuge dehydration of filter back got the zirconium carbonate finished product in ten minutes.The process vacuum reclaims hydrogenchloride as industrial hydrochloric acid, and the evaporation concentration cover is washed high vitriol oil sodium solution, gets reuse sodium sulfate byproduct of the present invention.
The above only is a preferred implementation of the present invention, should be pointed out that for those skilled in the art, under the prerequisite that does not break away from the principle of the invention, can also make some improvement, and these improvement also should be considered as protection scope of the present invention.
Claims (5)
1. high-purity high-activity alkali formula acyl group zirconium carbonate is characterized in that structural formula is:
2. the preparation method of the described high-purity high-activity alkali formula acyl group zirconium carbonate of claim 1 is characterized in that may further comprise the steps:
(1) eight hydration zirconium oxychlorides and sodium sulfate are pressed zirconium sulphur mol ratio 1: 0.55-0.6 and mixed, be dissolved in after the mixing in 45-50 ℃ the water, solid-to-liquid ratio 1: 4.5-5.5 filters, and heat temperature raising be incubated 60-80 minute to 95-98 ℃, must alkali formula acyl group zirconium sulfate mixed slurry;
(2) the alkali formula acyl group zirconium sulfate slurry that step (1) is obtained is put in the settling bath, with 50-55 ℃ water overflow washing, Cl in alkali formula acyl group zirconium sulfate slurry
-Be lower than 100ppm, naturally filter do alkali formula acyl group zirconium sulfate throw out;
(3) the alkali formula acyl group zirconium sulfate throw out that step (2) is obtained moves to and adds water to solid-to-liquid ratio 1: 2 in the retort, add saturated soda ash solution again and be heated to 45-50 ℃ of insulation 50-70 minute by sulphur carbon mol ratio 1: 1.05-1.10, get alkali formula acyl group zirconium carbonate slurry, washed 15 minutes with 45-50 ℃ water overflow, filter is done naturally;
(4) the alkali formula acyl group zirconium carbonate that step (3) is obtained [H
+]: the sulphuric acid soln activation of 0.8-1.0mol/L, 45 ℃ of constant temperature are regulated acidity and are made pH be stabilized in 3.5-7.0 maintenance 30-40 minute, filter drip washing SO in alkali formula acyl group zirconium carbonate
4 2-Less than 50ppm, centrifuge dehydration gets alkali formula acyl group zirconium carbonate finished product.
3. the production method of high-purity high-activity alkali formula acyl group zirconium carbonate according to claim 2 is characterized in that: eight hydration zirconium oxychloride content are greater than 98% in the step 1), and sodium sulphate content is greater than 98%; The mixed solution control temperature rise rate of eight hydration zirconium oxychlorides and sodium sulfate is 0.5 ℃/min.
4. the preparation method of the described high-purity high-activity alkali formula acyl group zirconium carbonate of claim 1 is characterized in that may further comprise the steps:
(1) eight hydration zirconium oxychlorides are soluble in water, solid-to-liquid ratio 1: 3.5-4.0 filters, and presses zirconium sulphur mol ratio 1: 0.55-0.6 and adds 1: 1 sulphuric acid soln, and 1: 1 sulphuric acid soln wherein is meant that sulfuric acid mixes with the water equal-volume; Heat temperature raising is incubated 60-80 minute to 95-98 ℃, gets alkali formula acyl group zirconium sulfate mixed slurry;
(2) the alkali formula acyl group zirconium sulfate slurry that step (1) is obtained is put in the settling bath, with 50-55 ℃ water overflow washing, Cl in alkali formula acyl group zirconium sulfate slurry
-Be lower than 100ppm, naturally filter do alkali formula acyl group zirconium sulfate throw out;
(3) the alkali formula acyl group zirconium sulfate throw out that step (2) is obtained moves to and adds water to solid-to-liquid ratio 1: 2 in the retort, add saturated soda ash solution again and be heated to 45-50 ℃ of insulation 50-70 minute by sulphur carbon mol ratio 1: 1.05-1.1, get alkali formula acyl group zirconium carbonate slurry, washed 15 minutes with 45-50 ℃ water overflow, filter is done naturally;
(4) the alkali formula acyl group zirconium carbonate that step (3) is obtained [H
+] the sulphuric acid soln activation of 0.8-1.0mol/L, 45 ℃ of constant temperature are regulated acidity and are made pH be stabilized in 3.5-7.0 to keep 30-40 minute, and filtered drip washing SO in alkali formula acyl group zirconium carbonate
4 2-Less than 50ppm, centrifuge dehydration gets alkali formula acyl group zirconium carbonate finished product.
5. the production method of high-purity high-activity alkali formula acyl group zirconium carbonate according to claim 4; it is characterized in that: eight hydration zirconium oxychloride content are greater than 98% in the step 1); sulfuric acid content is 0.5 ℃/min greater than 98%, eight hydration zirconium oxychloride and sulfuric acid mixture liquid control temperature rise rate.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103203212A (en) * | 2013-04-28 | 2013-07-17 | 湖南科技大学 | Preparation method and application of polymeric phosphorus ferric aluminum sulfate flocculating agent |
| CN108128804A (en) * | 2017-12-23 | 2018-06-08 | 淄博广通化工有限责任公司 | Industrial carbonic acid zirconium of the good stable storing of purity high activity and preparation method thereof |
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| CN108128804A (en) * | 2017-12-23 | 2018-06-08 | 淄博广通化工有限责任公司 | Industrial carbonic acid zirconium of the good stable storing of purity high activity and preparation method thereof |
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Application publication date: 20110713 |