CN101760614A - Leaching method of nickel-containing ore - Google Patents

Leaching method of nickel-containing ore Download PDF

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Publication number
CN101760614A
CN101760614A CN200810238839A CN200810238839A CN101760614A CN 101760614 A CN101760614 A CN 101760614A CN 200810238839 A CN200810238839 A CN 200810238839A CN 200810238839 A CN200810238839 A CN 200810238839A CN 101760614 A CN101760614 A CN 101760614A
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nickel
calcium
ore
sulfate
hydroxide
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CN200810238839A
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CN101760614B (en
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王魁珽
刘金山
陆业大
高保军
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China ENFI Engineering Corp
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China ENFI Engineering Corp
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/20—Recycling

Abstract

The invention provides a leaching method of a nickel-containing ore, comprising the following steps: A) mixing the nickel-containing ore with sulfuric acid solution and performing sulfuric acid leaching to obtain leaching solution which contains nickel sulfate; B) purifying the leaching solution to obtain nickel sulfate solution; C) mixing the nickel sulfate solution with calcium oxide and/or calcium hydroxide and calcium sulfate which is used as the seed crystal to generate calcium sulfate precipitation and nickel hydroxide precipitation; and D) separating the calcium sulfate from the nickel hydroxide. In the invention, metallic elements can be recovered from the nickel-containing ore with low cost and low pollution, thereby realizing the recycle of resources, producing the calcium sulfate (plaster) incidentally, lowering production cost and lightening environmental pollution.

Description

The leaching method of nickel-containing ore
Technical field
The present invention relates to wet method smelting process, especially relate to the leaching method of nickel-containing ore.
Background technology
Ore smelting is traditionally undertaken by pyrometallurgical smelting process.Developed wet process smelting technique in recent years.Because hydrometallurgy can reduce the pollution to environment effectively, and can be suitable for multiple different ore deposit, therefore replace pyrometallurgical smelting just gradually.
Present wet method smelting process adopts sulphuric acid solvent extraction method more, the multiple metallic element that can leach in the ore to be contained.If can not reclaim, will be great waste, and some composition in the leach liquor also may damage to human body to these metallic elements.When for example nickel-containing ore being leached, can produce the solution that contains single nickel salt in a large number, traditional treatment process is that the solution that will contain single nickel salt carries out heating evaporation, obtains nickel sulfate hexahydrate crystal.But the shortcoming of this treatment process is the cost height, and efficient is low, need to consume a large amount of energy, and the purity of resulting nickel sulfate hexahydrate crystal is low.
A kind of method that reclaims the nickel cobalt from the solution that contains nickel is disclosed among the Chinese patent application CN101094926A, this method comprises: use immiscible organic solvent to handle described solution optionally to absorb most cobalt, the remaining solution that contains nickel, the described solution of nickel that contains that neutralizes is so that described nickel is precipitated as nickel hydroxide.In this patent application, need to use a large amount of organic solvents, easily environment is caused secondary pollution.And at this method kind needs use resin column, so the production cost height, be unsuitable for large-scale industrial application.
Summary of the invention
Purpose of the present invention is intended to one of solve the aforementioned problems in the prior at least.
For this reason, thus one object of the present invention is to propose the low-cost leaching method that a kind of granularity that can increase calcium sulfate better reclaims the nickel-containing ore of nickel.
Leaching method according to the nickel-containing ore of the embodiment of the invention may further comprise the steps: A) nickel-containing ore is mixed with sulphuric acid soln and carry out sulfuric acid and leach to obtain containing the leach liquor of single nickel salt; B) described leach liquor is purified obtain nickel sulfate solution; C) mix with described nickel sulfate solution and calcium oxide and/or calcium hydroxide and as the calcium sulfate of crystal seed, to generate calcium sulfate precipitation and nickel hydroxide precipitate; And D) separating calcium sulphate and nickel hydroxide.
The nickel-containing ore leaching method can reclaim the metallic element in the nickel-containing ore according to an embodiment of the invention.Simultaneously owing to the calcium sulfate that exists in the reaction system of single nickel salt and calcium hydroxide as crystal seed, therefore, the granularity of the calcium sulfate that generates in can the augmenting response process, thereby help later separation calcium sulfate and nickel hydroxide precipitate, therefore, the present invention can reclaim metallic element with low-cost, oligosaprobic mode from nickel-containing ore, reach the recycling of resource, and attached product calcium sulfate (gypsum), reducing production costs alleviates environmental pollution.
In the leaching method of the nickel-containing ore of one embodiment of the present of invention, described nickel sulfate solution and calcium oxide and/or calcium hydroxide and mix as the calcium sulfate of crystal seed and to comprise at first calcium oxide and/or calcium hydroxide are mixed with calcium sulfate as crystal seed then join described nickel sulfate solution in the mixture of calcium oxide and/or calcium hydroxide and calcium sulfate.The present inventor finds at first calcium oxide and/or calcium hydroxide are mixed with calcium sulfate as crystal seed, add nickel sulfate solution again, can improve the reaction efficiency of follow-up single nickel salt and calcium hydroxide, and can further improve difference on calcium sulfate and the nickel hydroxide precipitate granularity, and then can improve separation efficiency.
In nickel-containing ore leaching method according to an embodiment of the invention, described sulfuric acid leaches to the oxygen enrichment normal pressure leaches or the leaching of oxygen enrichment high pressure, can promote the efficient that sulfuric acid leaches like this.
In nickel-containing ore leaching method according to an embodiment of the invention, described nickeliferous ore is a nickel ore concentrate.Owing in nickeliferous concentrate sulfuric acid leaches, can produce the solution of a large amount of sulfur acid nickel, the effect of therefore low-cost recovery nickel technology in the industrial application that nickel ore concentrate sulfuric acid leaches is better.
In the nickel-containing ore leaching method of one embodiment of the present of invention, described purification comprises at least a in the iron removed in the leach liquor, copper, the cobalt, thus, not only can reclaim compositions such as iron, copper, cobalt, and reclaimed the nickel in the ore, both reduced pollution, again recycle resource.
In nickel-containing ore leaching method according to an embodiment of the invention, as the calcium sulfate of crystal seed by alkali-metal vitriol and calcium oxide and/or calcium hydroxide reaction preparation.The resulting like this calcium sulfate as crystal seed can make easier being attached on it of calcium sulfate in the nickel sulfate solution, generates the precipitation of larger particle, thereby separates with nickel hydroxide precipitate easilier.
According to further embodiment, alkali-metal vitriol is sodium sulfate, can save cost like this.
In nickel-containing ore leaching method according to an embodiment of the invention, as the calcium sulfate of crystal seed is to obtain calcium sulfate and nickel hydroxide, separating calcium sulphate and nickel hydroxide then by nickel sulfate solution and calcium oxide and/or calcium hydroxide reaction, and isolating calcium sulfate is washed acquisition.Can save alkali-metal vitriol like this, save cost.
In nickel-containing ore leaching method according to an embodiment of the invention, further comprise with separating the nickel hydroxide that obtains and make the nickel goods, can utilize further nickel hydroxide like this, improve the economic worth that reclaims.
Additional aspect of the present invention and advantage part in the following description provide, and part will become obviously from the following description, or recognize by practice of the present invention.
Description of drawings
Fig. 1 is the schema of the leaching method of nickel-containing ore according to an embodiment of the invention;
Fig. 2 is the schema of the leaching method of nickel-containing ore according to another embodiment of the present invention;
Fig. 3 is the schema of the leaching method of nickel-containing ore according to another embodiment of the present invention;
Fig. 4 is the schema of the leaching method of nickel-containing ore according to another embodiment of the present invention;
Fig. 5 is the schema of the leaching method of nickel-containing ore according to another embodiment of the present invention.
Embodiment
Describe embodiments of the invention below in detail, the example of described embodiment is shown in the drawings, is exemplary below by the embodiment that is described with reference to the drawings, and only is used to explain the present invention, and can not be interpreted as limitation of the present invention.
Need to prove that term " calcium oxide and/or calcium hydroxide " is meant and can uses calcium oxide (unslaked lime) also can use calcium hydroxide (white lime) in the present invention, also can add the mixture of the two.In actually operating, can water assimilation of quicklime using (CaO), thus obtaining milk of lime, principal reaction is CaO+H 2O=Ca (OH) 2, the mixture of milk of lime as calcium oxide and calcium hydroxide used.
In addition, term " valuable metal " (valuable metals) is meant in the raw material of extracting metals in the present invention, except that main metal, has other metals of recovery value.In general, whether a certain metal has recovery value, depend on the use value of this metal, the expense and the commodity price thereof of recovery needs, for example, germanium in the plumbous zinc ore is not before semi-conductor industry is risen, the value that reclaims is also little, and has become to have very much the metal of recovery value after the 1950's.Main metal content is lower in the heavy metallic mineral that has, and not necessarily has extraction value, but other valuable metals more for a long time, takes all factors into consideration, and then has extraction value.Sometimes, according to certain concrete social condition such as war etc., and when certain metal had specific demand,, also reclaim possibly even temporarily not too reasonable economically.In a word, the notion that " valency is arranged " is not unalterable in the present invention.
Fig. 1 shows the schema of the leaching method of nickel-containing ore according to an embodiment of the invention.According to shown in Figure 1, at first nickel-containing ore joined and carry out the sulfuric acid leaching in the sulphuric acid soln to obtain containing the leach liquor of single nickel salt; Described leach liquor purified obtain nickel sulfate solution; Then, mix with resulting nickel sulfate solution and calcium oxide and/or calcium hydroxide and as the calcium sulfate of crystal seed, to generate calcium sulfate precipitation and nickel hydroxide precipitate, the principal reaction that is taken place is:
NiSO 4+Ca(OH) 2＝Ni(OH) 2↓+CaSO 4↓；
At last, separating calcium sulphate and nickel hydroxide.
As previously mentioned,, leach in the leach liquor, and can reclaim multiple valuable metal, for example iron, copper, cobalt by purifying by the metallic element in the nickel-containing ore is leached by sulfuric acid.In addition, after adding calcium oxide and/or calcium hydroxide, single nickel salt in the nickel sulfate solution and calcium hydroxide reaction generate calcium sulfate precipitation and nickel hydroxide precipitate.Yet the particle of calcium sulfate precipitation and nickel hydroxide precipitate is all very little, and the granularity difference is smaller, and more specifically, calcium sulfate precipitation is a crystalline form, and nickel hydroxide is a gel, and nickel hydroxide is coated on the calcium sulfate, so the two is difficult to separate.
In addition, if do not add calcium sulfate as crystal seed in advance in nickel sulfate solution, nickel hydroxide has limited the further increase of calcium sulfate granularity, thereby has further increased separating difficulty.According to embodiments of the invention, owing to exist as crystalline calcium sulfate in the reaction system of single nickel salt and calcium hydroxide, calcium sulfate can be with CaSO 4XH 2The crystallized form of O (x is about 2/3) is precipitated out, therefore react in the sedimentary process that generates calcium sulfate and nickel hydroxide at single nickel salt and calcium hydroxide, calcium sulfate precipitation can be formed on the crystal seed, thereby the granularity of calcium sulfate precipitation can further increase, promptly form the calcium sulfate precipitation of volume particle size, be convenient to separating between follow-up calcium sulfate and the nickel hydroxide precipitate thus.
The source of the employed in the present invention calcium sulfate as crystal seed is not restricted, both can be the ready-made calcium sulfate of buying from the market, also can be the calcium sulfate that obtains by independent chemical reaction, the product calcium sulfate that also can be in this technology to be generated.
With reference to figure 2, in one embodiment of the invention, be to use calcium sulfate precipitation that alkali-metal vitriol and calcium oxide and/or calcium hydroxide reaction generated in that to separate the back resulting as the calcium sulfate of crystal seed, the principal reaction that is taken place is:
Na 2SO 4+Ca(OH) 2＝CaSO 4+2NaOH。The contriver finds that the calcium sulfate that uses this method to obtain can obviously increase the granularity of calcium sulfate as crystal seed.In addition, in a further embodiment, employed alkali-metal vitriol is sodium sulfate, because the cost of sodium sulfate is low, and the sodium hydroxide that is generated is solvable, therefore when can being convenient to separation of hydrogen sodium oxide and calcium sulfate, has reduced cost.
With reference to figure 3, in one embodiment of the invention, as the calcium sulfate of crystal seed is to obtain calcium sulfate with nickel hydroxide, separating calcium sulphate and nickel hydroxide, obtain after the calcium sulfate after separating is washed then by nickel sulfate solution and calcium oxide and/or calcium hydroxide reaction, do not need extra independent preparation calcium sulfate crystal seed like this and saved alkali-metal vitriol, therefore further saved to produce and produced this.For example, can to being mixed with calcium oxide and/or calcium hydroxide, the part of sulfuric acid nickel solution obtain calcium sulfate and nickel hydroxide precipitate earlier, from this solution, isolate calcium sulfate and nickel hydroxide then, and the calcium sulfate precipitation that obtains is washed the calcium sulfate that obtains as crystal seed.
In addition, at the beginning of technological process, the calcium sulfate of buying from market can be mixed with nickel sulfate solution as crystal seed, then by reaction, separate the crystal seed of use after obtaining calcium sulfate and just can be used as.
In the present invention, can add calcium oxide (unslaked lime), also can add calcium hydroxide (white lime), also can add the mixture of the two.Particularly, can water assimilation of quicklime using (CaO), thus obtaining milk of lime, principal reaction is CaO+H 2O=Ca (OH) 2More specifically, unslaked lime adds less water to be made its heating, aquation, is paste, and after thermopositive reaction finished substantially, thin up was sized mixing, and can prolong digestion time under the situation of time permission.When using commercial lime, except that prolonging digestion time, also need to sieve, to remove unreacted residue.
It will be understood by those skilled in the art that promptly and milk of lime can be joined in the nickel sulfate solution, also nickel sulfate solution can be joined in the milk of lime.With reference to figure 5, in one embodiment of the invention, nickel sulfate solution and calcium oxide and/or calcium hydroxide and to mix as the calcium sulfate of crystal seed be by at first calcium oxide and/or calcium hydroxide being mixed with calcium sulfate slurry as crystal seed add in resulting mixture then that nickel sulfate solution carries out.The contriver finds at first calcium oxide and/or calcium hydroxide are mixed with calcium sulfate as crystal seed, add nickel sulfate solution again, can improve the reaction efficiency of follow-up single nickel salt and calcium hydroxide, and can further improve difference on calcium sulfate and the nickel hydroxide precipitate granularity, and then can improve separation efficiency.In a further embodiment, nickel sulfate solution is added drop-wise in calcium oxide and/or calcium hydroxide and the mixture as the calcium sulfate of crystal seed, can improve whole effect so widely.
Because it is big that the granularity of the size ratio nickel hydroxide of calcium sulfate is wanted, and owing to the calcium sulfate that in the reaction system of single nickel salt and calcium hydroxide, exists as crystal seed, with do not add crystal seed and compare, therefore the granulometric facies of the calcium sulfate precipitation that is generated can further increase and can easily calcium sulfate be separated with nickel hydroxide according to two kinds of sedimentary granular size differences for the granularity of nickel hydroxide.
In addition, in one embodiment of the invention, in order to obtain the higher nickel hydroxide of purity, and prolonged preservation, isolated nickel hydroxide is washed and dry.Washings can adopt deionized water, can prevent that like this nickel hydroxide suspension from flocculating.
With reference to figure 4, in one embodiment of the invention, separate the nickel hydroxide that obtains and to be used to prepare the nickel goods.With reference to figure 3, in one embodiment of the invention, as previously mentioned, the calcium sulfate that separation is obtained can be used as crystal seed and turns back in the reaction system after removing the impurity (as nickel hydroxide) on surface through washing.In addition, resulting calcium sulfate can also be used to prepare sulfuric acid.
The sulfuric acid extract technology that is adopted among the present invention is not subjected to any restriction.For example, leaching can be leached or the leaching of oxygen enrichment high pressure for the oxygen enrichment normal pressure.Leaching process comprises that fine grinding contains nickel ore concentrate; Carry out pulp with the nickel ore concentrate that contains of sulphuric acid soln after to fine grinding; Concentrate after the pulp joined leach in the container, wherein leaching temperature in the container, to be controlled to be 90 ℃-100 ℃, pressure be normal pressure, and aerating oxygen leaches so that carry out the oxygen enrichment normal pressure in leaching container simultaneously.
In further embodiment of the present invention, nickel sulfate solution is the solution of sulphuric leachate through obtaining after purifying, and promptly reclaims other compositions in (removal) leach liquor earlier, reclaims the nickel that exists with the single nickel salt form in the waste liquid again.Term " purification " can be to remove at least a in iron in the sulphuric leachate, copper, the cobalt in the present invention, but the present invention is not limited to remove mentioned component.Because the purification in the sulfuric acid leaching process is known for those of ordinary skill in the art, gives unnecessary details no longer in detail here.
Although illustrated and described embodiments of the invention, for the ordinary skill in the art, be appreciated that without departing from the principles and spirit of the present invention and can carry out multiple variation, modification, replacement and modification that scope of the present invention is by claims and be equal to and limit to these embodiment.

Claims (9)

1. the leaching method of a nickel-containing ore may further comprise the steps:
A) nickel-containing ore is mixed with sulphuric acid soln carry out acidleach to obtain the leach liquor of sulfur acid nickel;
B) described leach liquor is purified obtain nickel sulfate solution;
C) mix with described nickel sulfate solution and calcium oxide and/or calcium hydroxide and as the calcium sulfate of crystal seed, to generate calcium sulfate precipitation and nickel hydroxide precipitate; And
D) separating calcium sulphate and nickel hydroxide.
2. the leaching method of nickel-containing ore according to claim 1, it is characterized in that, described nickel sulfate solution and calcium oxide and/or calcium hydroxide and mix as the calcium sulfate of crystal seed and to comprise at first calcium oxide and/or calcium hydroxide are mixed with calcium sulfate as crystal seed then join described nickel sulfate solution in the mixture of calcium oxide and/or calcium hydroxide and calcium sulfate.
3. the leaching method of nickel-containing ore according to claim 1 is characterized in that, described acidleach is leached for the oxygen enrichment normal pressure or the oxygen enrichment high pressure leaches.
4. the leaching method of nickel-containing ore according to claim 1 is characterized in that, described nickeliferous ore is a nickel ore concentrate.
5. the leaching method of nickel-containing ore according to claim 4 is characterized in that, described purification comprises at least a in the iron removed in the leach liquor, copper, the cobalt.
6. the leaching method of nickel-containing ore according to claim 1 is characterized in that, as the calcium sulfate of crystal seed by alkali-metal vitriol and calcium oxide and/or calcium hydroxide reaction preparation.
7. the leaching method of nickel-containing ore according to claim 6 is characterized in that, described vitriol is sodium sulfate.
8. the leaching method of nickel-containing ore according to claim 1, it is characterized in that, as the calcium sulfate of crystal seed is to obtain calcium sulfate and nickel hydroxide, separating calcium sulphate and nickel hydroxide by nickel sulfate solution and calcium oxide and/or calcium hydroxide reaction, and isolating calcium sulfate is washed acquisition.
9. the leaching method of nickel-containing ore according to claim 1 is characterized in that, further comprises with separating the nickel hydroxide that obtains making the nickel goods.
CN2008102388393A 2008-12-02 2008-12-02 Leaching method of nickel-containing ore Active CN101760614B (en)

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103468978A (en) * 2013-08-15 2013-12-25 中国恩菲工程技术有限公司 Method for extracting scandium from lateritic nickel ore sulfuric acid leaching solution
CN103468980A (en) * 2013-08-15 2013-12-25 中国恩菲工程技术有限公司 Method for extracting scandium from lateritic nickel ore
CN103468972A (en) * 2013-08-15 2013-12-25 中国恩菲工程技术有限公司 Treatment method for comprehensive recycling of scandium and nickel cobalt from lateritic nickel ore
CN103468979A (en) * 2013-08-15 2013-12-25 中国恩菲工程技术有限公司 Method for recycling scandium from lateritic nickel ore smelted iron aluminum slag
CN106636654A (en) * 2016-12-31 2017-05-10 山东飞源科技有限公司 Method for recycling metal nickel from fluorine-containing electrolysis fused salt
CN109234526A (en) * 2018-11-26 2019-01-18 中国恩菲工程技术有限公司 The processing method of lateritic nickel ore

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DE1263316B (en) * 1965-04-07 1968-03-14 Internat Nickel Company Of Can Process for the production of nickel, nickel compounds and / or ferronickel from iron-containing, oxydic-silicate nickel ores
US5650057A (en) * 1993-07-29 1997-07-22 Cominco Engineering Services Ltd. Chloride assisted hydrometallurgical extraction of metal
US6440194B1 (en) * 2000-11-21 2002-08-27 Fenicem Minerals Inc. Recovery of precious metals from metal alloys produced aluminothermically from base metal smelter slag
CN1240857C (en) * 2003-11-03 2006-02-08 潘继红 Extraction of nickle oxide from serpentine by sulfuric acid leaching out

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103468978A (en) * 2013-08-15 2013-12-25 中国恩菲工程技术有限公司 Method for extracting scandium from lateritic nickel ore sulfuric acid leaching solution
CN103468980A (en) * 2013-08-15 2013-12-25 中国恩菲工程技术有限公司 Method for extracting scandium from lateritic nickel ore
CN103468972A (en) * 2013-08-15 2013-12-25 中国恩菲工程技术有限公司 Treatment method for comprehensive recycling of scandium and nickel cobalt from lateritic nickel ore
CN103468979A (en) * 2013-08-15 2013-12-25 中国恩菲工程技术有限公司 Method for recycling scandium from lateritic nickel ore smelted iron aluminum slag
CN103468979B (en) * 2013-08-15 2016-02-24 中国恩菲工程技术有限公司 The method of scandium is reclaimed from smelting laterite-nickel ores iron aluminium slag
CN103468972B (en) * 2013-08-15 2016-02-24 中国恩菲工程技术有限公司 The treatment process of red soil nickel ore synthetical recovery scandium and nickel cobalt
CN103468978B (en) * 2013-08-15 2016-03-30 中国恩菲工程技术有限公司 A kind of method carrying scandium from laterite nickel ore by sulfuric acid leaching liquid
CN103468980B (en) * 2013-08-15 2016-04-13 中国恩菲工程技术有限公司 A kind of red soil nickel ore extracts the method for scandium
CN106636654A (en) * 2016-12-31 2017-05-10 山东飞源科技有限公司 Method for recycling metal nickel from fluorine-containing electrolysis fused salt
CN106636654B (en) * 2016-12-31 2019-04-26 山东飞源科技有限公司 The method of metallic nickel is recycled from fluorine-containing electrolysis fused salt
CN109234526A (en) * 2018-11-26 2019-01-18 中国恩菲工程技术有限公司 The processing method of lateritic nickel ore
CN109234526B (en) * 2018-11-26 2020-11-03 中国恩菲工程技术有限公司 Treatment method of laterite-nickel ore

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