CN1329295C - Method for preparing sodium metasilicate by discharched waste liquid from production of zirconium oxychloride - Google Patents
Method for preparing sodium metasilicate by discharched waste liquid from production of zirconium oxychloride Download PDFInfo
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- CN1329295C CN1329295C CNB031139388A CN03113938A CN1329295C CN 1329295 C CN1329295 C CN 1329295C CN B031139388 A CNB031139388 A CN B031139388A CN 03113938 A CN03113938 A CN 03113938A CN 1329295 C CN1329295 C CN 1329295C
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Abstract
The present invention relates to a method for preparing sodium metasilicate by discharged waste liquid from the production of zirconium oxychloride, which comprises the following procedures in sequence: raw material pretreatment, reaction, crystallization, separation, drying and screening. A main raw material is waste water discharged from the production of zirconium oxychloride and containing 5 to 15 wt% of sodium oxide and 2 to 10 wt% of silicon dioxide. The procedures of raw material pretreatment comprise: agitation after being heated, deposition after being cooled, secondary filtration and evaporating concentration in sequence. The total weight percentage of the concentration of the sodium oxide and the silicon dioxide in a concentrated solution entering the reaction procedure after pretreatment is from 25 to 50%. The heating temperature in the procedure of the raw material pretreatment is from 90 to 98 DEG C, the agitating time is from12 to 18 minutes, the cooling depositing temperature is from 45 to 55 DEG C, the depositing time is from 3.5 to 4.5 hours, and the evaporation temperature is from 100 to 120 DEG C. The method has the advantages of simple and feasible method, novel component of raw materials, sufficient resource utilization, stable product quality, low cost and no secondary waste discharge. In particular, the method can effectively treat the waste water discharged from the production of the zirconium oxychloride, protect ecological environment and reduce the production cost of zirconium oxychloride.
Description
Technical field the present invention relates to the preparation of alkalimetal silicate, relates in particular to a kind of basic zirconium chloride that utilizes and produces the method that waste discharge prepares Starso.
The background technology Starso be sodium oxide with the silicon oxide molecule number than the crystal water glass that equals 1, molecular formula is Na
2OSiO
2XH
2O.Market sale mainly contain five water, anhydrous and three kinds of form Starsos of nine water, in the molecular formula X be 5 respectively, O or 9.Be the principal item of water-soluble silicate, be widely used as forming process of ceramics auxiliary agent, washing auxiliary detergent, spinning sizing agent, also be used for cardboard manufacturing, frie retardant coating, refining of petroleum and food antiseptic etc.The preparation method of existing Starso generally responds, crystallization, separation, drying, screening operation.The pretreatment process that main difference is raw material and raw material is different.With sodium hydroxide and industrial metasilicate is raw material, and product cost is higher relatively; And adopt the technical process of calcination process potassium felspar sand long, and the equipment complexity, the aftertreatment expense is many, and product cost is corresponding also higher.As for blow crystallization process, one-time prilling method, spray-drying process and the solution crystal process divided according to formed product, preceding a kind of efficient is low, and product appearance is poor, place easy moisture absorption caking, be unsuitable for scale production in batches, back three kinds of common defects are cost height, all are necessary further improvement.
Basic zirconium chloride is the basic material of zirconates, zirconium product, and it is used and demand constantly growth, but discharge in the production process with sodium oxide (Na
2O), silicon-dioxide (SiO
2) be the sig water waste water treatment of main component, seriously restricting the production-scale expansion of basic zirconium chloride.So far do not see as yet that having with sodium oxide, silicon-dioxide is that the sig water waste water of main component is the reported in literature that main raw material prepares Starso.
Summary of the invention is for administering the waste water of basic zirconium chloride production discharging, remedy the defective of existing metasilicate sodium product preparation method, the present invention proposes a kind of basic zirconium chloride that utilizes and produces the method that waste discharge prepares five water or anhydrous sodium metasilicate, the present invention also proposes a kind of basic zirconium chloride that utilizes and produces the method that waste discharge prepares non-hydrate sodium metasilicate, and the technical scheme of employing is as follows respectively:
This basic zirconium chloride that utilizes is produced the method that waste discharge prepares five water or anhydrous sodium metasilicate, and raw materials pretreatment, reaction, crystallization, separation, drying and screening operation are arranged successively, it is characterized in that:
Main raw material is the waste water that basic zirconium chloride production is discharged, and wherein the concentration of sodium oxide is 5～15% by weight percentage, silica concentration is 2～10% by weight percentage.
The raw materials pretreatment operation has heated and stirred, cooling-sedimentation, secondary filtration and evaporation concentration successively, and entering in the concentrated solution of reaction process through pre-treatment that sodium oxide and silica concentration add up to by weight percentage is 25～50%.
Heating temperature is 90～98 ℃ in the above-mentioned raw materials pretreatment operation, and churning time is 12～18 minutes, and the cooling-sedimentation temperature is 45～55 ℃, and the settling time is 3.5～4.5 hours, and vaporization temperature is 100～120 ℃.
Above-mentioned reaction process is batching, heating, stirring reaction operation, determine that by concentrated solution sodium oxide, dioxide-containing silica the adding modulus is 2.21 water glass, mix with above concentrated solution, the sodium oxide concentration of adjusted reaction solution is 20～25% by weight percentage, silica concentration is 8～15% by weight percentage, Heating temperature is 55～65 ℃, reaction times is 0.5～1.0 hour, and the silica concentration of above-mentioned water glass is good with 〉=25%.
Above-mentioned Crystallization Procedure, be successively reduce temperature to 50～60 ℃, add nucleator and nucleation-accelerant, stirring, at the uniform velocity cooling, sedimentation Crystallization Procedure, cooling rate is 5～8 ℃/hour, and crystallization time is 1～2 hour, and nucleator is crystal seed metasilicate pentahydrate sodium or crystal seed anhydrous sodium metasilicate.
Above-mentioned separation circuit is the solid-liquid centrifugal separation process.
Above-mentioned drying process is crystallization wet stock air seasoning operation in fluidized-bed, and drying temperature is 60～70 ℃, and by control fluidized-bed running speed, making the dry materials time is 5～10 minutes.
The sieve size of above-mentioned screening operation≤12 orders.
This further feature of utilizing basic zirconium chloride production waste discharge to prepare the method for five water or anhydrous sodium metasilicate is:
Above-mentioned nucleation-accelerant can be a Sodium dodecylbenzene sulfonate, also can be sodium lauryl sulphate, can also be the polyethylene glycol type nonionogenic tenside.
This basic zirconium chloride that utilizes is produced the method that waste discharge prepares non-hydrate sodium metasilicate, and raw materials pretreatment, reaction, crystallization, separation circuit are arranged successively, it is characterized in that:
Main raw material is the waste water that basic zirconium chloride production is discharged, and wherein the concentration of sodium oxide is 5～15% by weight percentage, silica concentration is 2～10% by weight percentage.
The raw materials pretreatment operation has heated and stirred, cooling-sedimentation, secondary filtration and evaporation concentration successively, and entering in the concentrated solution of reaction process through pre-treatment that sodium oxide and silica concentration add up to by weight percentage is 25～50%.
Heating temperature is 90～98 ℃ in the above-mentioned raw materials pretreatment operation, and churning time is 12～18 minutes, and cooling temperature is 45～55 ℃, and the settling time is 3.5～4.5 hours, and vaporization temperature is 100～120 ℃.
Above-mentioned reaction process is batching, heating, stirring reaction operation, determine that by concentrated solution sodium oxide, dioxide-containing silica the adding modulus is 2.21 water glass and solid sodium hydroxide, mix with above concentrated solution, the sodium oxide concentration of adjusted reaction solution is 18～24% by weight percentage, silica concentration is 16～24% by weight percentage, Heating temperature is 45～60 ℃, reaction times is 0.5～1.0 hour, and the silica concentration of above-mentioned water glass is good with 〉=25%.
Above-mentioned Crystallization Procedure be successively reduce temperature to 35～50 ℃, add nucleator and nucleation-accelerant, stirring, at the uniform velocity cooling, sedimentation crystallization, cooling rate is 5～8 ℃/hour, crystallization time is 1～2 hour, nucleator is the crystal seed non-hydrate sodium metasilicate.
Above-mentioned separation circuit is the solid-liquid centrifugal separation process.
This further feature of utilizing basic zirconium chloride production waste discharge to prepare the method for non-hydrate sodium metasilicate is:
Above-mentioned nucleation-accelerant can be a Sodium dodecylbenzene sulfonate, also can be sodium lauryl sulphate, can also be the polyethylene glycol type nonionogenic tenside.
The present invention's beneficial effect against existing technologies is; the inventive method is rationally utilized the waste water that discharges in the basic zirconium chloride production process; successively through raw materials pretreatment; reaction; crystallization; separate; dry; the screening operation prepares five water or anhydrous sodium metasilicate; or successively through raw materials pretreatment; reaction; crystallization; separation circuit prepares non-hydrate sodium metasilicate; it is simple and feasible to have method; the feed composition novelty; the utilization of resources is abundant; constant product quality; cost is corresponding lower; the advantage of no secondary waste discharge; especially can effectively administer the waste water of basic zirconium chloride production discharging; preserve the ecological environment, reduce the basic zirconium chloride production cost.Test shows, with the waste water that production equipment was discharged of producing 20000 tons of basic zirconium chlorides per year is main raw material, adopt the inventive method can produce 30000 tons of Starsos (in metasilicate pentahydrate sodium) per year, and every performance index of finished product are stable, can satisfy washing auxiliary detergent, forming process of ceramics, spinning sizing agent preferably, the requirement of cardboard manufacturing, frie retardant coating, refining of petroleum and food antiseptic etc.
Embodiment utilizes basic zirconium chloride to produce the method that waste discharge prepares Starso
Embodiment 1
Basic zirconium chloride is produced 1.00 kilograms of waste discharge weight, sodium oxide in this waste water, silica concentration are respectively 6.25%, 2.55% by weight percentage, being heated to 95 ± 2 ℃ stirred 15 minutes, be cooled to 50 ℃ afterwards, sedimentation 4 hours, the waste water of cooling process is filtered in plate-and-frame filter press, and the clear liquid after the filtration is 0.25 kilogram in 105～115 ℃ of concentration and evaporations to weight, and sodium oxide, silica concentration are respectively 25.0%, 10.2% at this moment.
Add again and contain sodium oxide 14.0%, silicon-dioxide 30.0%, 0.025 kilogram of the industrial metasilicate of modulus 2.21, mix with above concentrated solution, adjusted reaction solution concentration is a sodium oxide 24.0%, silica 1 2.0%, be mixed and heated to 60 ± 5 ℃, stirring reaction 0.5 hour, crystal seed metasilicate pentahydrate sodium 0.2 gram that adds 0.1～0.2 millimeter when being cooled to 55 ℃, Sodium dodecylbenzene sulfonate 0.001 gram, the control temperature fall time is 2 hours in the stirring, the crystal solution temperature is at the uniform velocity reduced to 40～42 ℃, isolate 0.078 kilogram of wet solid materials with centrifugation apparatus, the solid materials that will wet again drops in the fluidized bed dryer, with 70 ℃ of warm air dryings 5～10 minutes, after sieving 0.5～1 millimeter of granularity, contain sodium oxide 29.5%, 0.075 kilogram of the metasilicate pentahydrate sodium finished product of silicon-dioxide 28.5%.Centrifugation apparatus is isolated to contain 0.197 kilogram in the mother liquor of sodium oxide 22.27%, silicon-dioxide 5.90%, returns the batching reactive system and continues to use.
Embodiment 2
Basic zirconium chloride is produced 1.00 kilograms of waste discharge weight, sodium oxide in this waste water, silica concentration are respectively 6.25%, 2.55% by weight percentage, being heated to 95 ± 2 ℃ stirred 15 minutes, be cooled to 50 ℃ afterwards, sedimentation 4 hours, with filtering in the plate-and-frame filter press, the clear liquid after the filtration is 0.25 kilogram in 105～115 ℃ of concentration and evaporations to weight with the waste water of cooling process, and this moment, sodium oxide, silica concentration were respectively 25.0%, 10.2%.
Add again and contain sodium oxide 14.0%, silicon-dioxide 30.0%, 0.057 kilogram of 0.30 kilogram of the industrial metasilicate of modulus 2.21 and 90.0% industrial sodium hydroxide (folding sodium oxide content 69.75%), mix with above concentrated solution, adjusted reaction solution concentration is a sodium oxide 23.77%, silica 1 9.0%, weight is 0.607 kilogram, non-hydrate sodium metasilicate crystal seed 2 grams that add 0.1～0.2 millimeter when being cooled to 45 ℃, Sodium dodecylbenzene sulfonate 0.01 gram, the control temperature fall time is 1 hour in the stirring, the crystal solution temperature is at the uniform velocity reduced to 35 ℃, isolate with centrifugation apparatus and contain sodium oxide 21.90%, 0.410 kilogram of the non-hydrate sodium metasilicate finished product of silicon-dioxide 21.20%.0.190 kilogram in the mother liquor that contains sodium oxide 28.46%, silicon oxide 14.31% returns the batching reactive system and continues to use.
Claims (4)
1, a kind of basic zirconium chloride that utilizes is produced the method that waste discharge prepares five water or anhydrous sodium metasilicate, and raw materials pretreatment, reaction, crystallization, separation, drying and screening operation are arranged successively, it is characterized in that:
11 main raw materials are the waste water that basic zirconium chloride production is discharged, and wherein the concentration of sodium oxide is 5～15% by weight percentage, silica concentration is 2～10% by weight percentage;
12 raw materials pretreatment operations have heated and stirred, cooling-sedimentation, secondary filtration and evaporation concentration successively, and entering through pre-treatment that sodium oxide in the concentrated solution of reaction process and silica concentration add up to by weight percentage is 25～50%;
Heating temperature is 90～98 ℃ in the 13 above-mentioned raw materials pretreatment operations, and churning time is 12～18 minutes, and the cooling-sedimentation temperature is 45～55 ℃, and the settling time is 3.5～4.5 hours, and vaporization temperature is 100～120 ℃;
14 above-mentioned reaction process are batching, heating, stirring reaction operation, the adding modulus is 2.21 water glass, mix with above concentrated solution, the sodium oxide concentration of adjusted reaction solution is 20～25% by weight percentage, silica concentration is 8～15% by weight percentage, Heating temperature is 55～65 ℃, reaction times is 0.5～1.0 hour, the silica concentration of above-mentioned water glass 〉=25%;
15 above-mentioned Crystallization Procedure, be successively reduce temperature to 50～60 ℃, add nucleator and nucleation-accelerant, stirring, at the uniform velocity cooling, sedimentation Crystallization Procedure, cooling rate is 5～8 ℃/hour, and crystallization time is 1～2 hour, and nucleator is crystal seed metasilicate pentahydrate sodium or crystal seed anhydrous sodium metasilicate;
16 above-mentioned separation circuits are solid-liquid centrifugal separation process;
17 above-mentioned drying processes are crystallization wet stock air seasoning operations in fluidized-bed, and drying temperature is 60～70 ℃, and by control fluidized-bed running speed, making the dry materials time is 5～10 minutes;
Sieve size≤12 orders of 18 above-mentioned screening operations.
2, the basic zirconium chloride that utilizes as claimed in claim 1 is produced the method that waste discharge prepares five water or anhydrous sodium metasilicate, and it is characterized in that: above-mentioned nucleation-accelerant is Sodium dodecylbenzene sulfonate, sodium lauryl sulphate or polyethylene glycol type nonionogenic tenside.
3, a kind of basic zirconium chloride that utilizes is produced the method that waste discharge prepares non-hydrate sodium metasilicate, and raw materials pretreatment, reaction, crystallization, separation circuit are arranged successively, it is characterized in that:
31 main raw materials are the waste water that basic zirconium chloride production is discharged, and wherein the concentration of sodium oxide is 5～15% by weight percentage, silica concentration is 2～10% by weight percentage;
32 raw materials pretreatment operations have heated and stirred, cooling-sedimentation, secondary filtration and evaporation concentration successively, and entering through pre-treatment that sodium oxide in the concentrated solution of reaction process and silica concentration add up to by weight percentage is 25～50%;
Heating temperature is 90～98 ℃ in the 33 above-mentioned raw materials pretreatment operations, and churning time is 12～18 minutes, and cooling temperature is 45～55 ℃, and the settling time is 3.5～4.5 hours, and vaporization temperature is 100～120 ℃;
34 above-mentioned reaction process are batching, heating, stirring reaction operation, the adding modulus is 2.21 water glass and solid sodium hydroxide, mix with above concentrated solution, the sodium oxide concentration of adjusted reaction solution is 18～24% by weight percentage, silica concentration is 16～24% by weight percentage, Heating temperature is 45～60 ℃, reaction times is 0.5～1.0 hour, the silica concentration of above-mentioned water glass 〉=25%;
35 above-mentioned Crystallization Procedure be successively reduce temperature to 35～50 ℃, add nucleator and nucleation-accelerant, stirring, at the uniform velocity cooling, sedimentation crystallization, cooling rate is 5～8 ℃/hour, crystallization time is 1～2 hour, nucleator is the crystal seed non-hydrate sodium metasilicate;
36 above-mentioned separation circuits are solid-liquid centrifugal separation process.
4, the basic zirconium chloride that utilizes as claimed in claim 3 is produced the method that waste discharge prepares non-hydrate sodium metasilicate, and it is characterized in that: above-mentioned nucleation-accelerant is Sodium dodecylbenzene sulfonate, sodium lauryl sulphate or polyethylene glycol type nonionogenic tenside.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB031139388A CN1329295C (en) | 2003-03-16 | 2003-03-16 | Method for preparing sodium metasilicate by discharched waste liquid from production of zirconium oxychloride |
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| CNB031139388A CN1329295C (en) | 2003-03-16 | 2003-03-16 | Method for preparing sodium metasilicate by discharched waste liquid from production of zirconium oxychloride |
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| CN1329295C true CN1329295C (en) | 2007-08-01 |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1047067A (en) * | 1989-05-09 | 1990-11-21 | 兰州大学 | The preparation method of non-hydrate sodium metasilicate |
| CN1131125A (en) * | 1995-03-16 | 1996-09-18 | 石家庄开发区汉森科技发展有限公司 | Sodium metasilicate pentahydrate and preparation method thereof |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1047067A (en) * | 1989-05-09 | 1990-11-21 | 兰州大学 | The preparation method of non-hydrate sodium metasilicate |
| CN1131125A (en) * | 1995-03-16 | 1996-09-18 | 石家庄开发区汉森科技发展有限公司 | Sodium metasilicate pentahydrate and preparation method thereof |
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Denomination of invention: Method for preparing sodium metasilicate by discharched waste liquid from production of zirconium oxychloride Effective date of registration: 20180115 Granted publication date: 20070801 Pledgee: China the Great Wall asset management Limited by Share Ltd. Guangdong branch Pledgor: GUANGDONG ORIENT ZIRCONIC IND SCI & TECH CO.,LTD. Registration number: 2018990000034 |
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Date of cancellation: 20210111 Granted publication date: 20070801 Pledgee: China the Great Wall asset management Limited by Share Ltd. Guangdong branch Pledgor: GUANGDONG ORIENT ZIRCONIC IND SCI & TECH Co.,Ltd. Registration number: 2018990000034 |
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