CN102887520B

CN102887520B - A kind of take vein quartz as the processing method that Raw material processing prepares 4N high purity quartz

Info

Publication number: CN102887520B
Application number: CN201210422811.1A
Authority: CN
Inventors: 汪灵; 党陈萍; 王艳; 李彩侠; 夏瑾卓
Original assignee: Chengdu Univeristy of Technology
Current assignee: Hubei Guoda New Materials Group Co.,Ltd.
Priority date: 2012-10-30
Filing date: 2012-10-30
Publication date: 2016-04-13
Anticipated expiration: 2032-10-30
Also published as: CN102887520A

Abstract

The present invention relates to a kind of take vein quartz as the method for Raw material processing 4N high purity quartz, with HCl+H ₂sO ₄+ HF is acidleach reagent, adopts secondary shrend and acidleach Optimization Technology, and the 1st is by vein quartz raw material crushing to-30mm, then screening is 5-30mm; 2nd is cleaning material and removes foreign material and impure material; 3rd is by material rapid shrend in room temperature distilled water after 1000 DEG C of roasting 0.5-2h; 4th is by drying materials and is crushed to-40 orders; 5th is by material rapid shrend in room temperature distilled water after 650 DEG C of roasting 1-3h; 6th is also sieve drying materials for 40-70 order, 70-140 order and-140 orders; 7th is that material acidleach is purified, and processing condition are: acidleach reagent HCl+H ₂sO ₄+ HF, HCl and H ₂sO ₄concentration 10-30%, HF concentration 5%, concentration 10-30%, solid-to-liquid ratio 1:2, temperature 60-150 DEG C, time 2-6h; 8th is that the common distilled water of material is cleaned 2 times, pure water cleaning 1-2 time; 9th is by drying materials, namely obtains the 4N high purity quartz of corresponding granularity.Successful, security is good, and technique is simple, and promote easily, economic results in society are remarkable.

Description

A kind of take vein quartz as the processing method that Raw material processing prepares 4N high purity quartz

Technical field

The present invention relates to a kind of take vein quartz as the method for Raw material processing 4N high purity quartz, take vein quartz as raw material, adopts HCl+H ₂sO ₄+ HF is acidleach reagent, and secondary shrend and acidleach Optimization Technology, purification processing w(SiO ₂) > 4N(99.99%), w(Fe) < 10 × 10 ^-6, particle diameter is respectively-40 orders, 40-70 order, 70-140 order and-140 object high purity quartzs, and being applicable to a kind of take vein quartz as the processing of the 4N high purity quartz of raw material.

Background technology

2.1 high purity quartz concepts

Quartz, chemical formula SiO ₂, be the general name of alpha-quartz (low quartz) and β-quartz (high quartz), when not adding explanation, often refer to alpha-quartz.Quartz is a kind of silicate minerals of hard, wear-resisting, stable chemical performance, is generally oyster white or colourless, translucent, hardness 7, property is crisp, without cleavage, and conchoidal fracture, oily luster, relative density 2.65, its electricity, calorifics and some mechanicalness all have obvious anisotropy.The stable chemical nature of quartz, be insoluble to acid (except HF), be slightly soluble in KOH solution, temperature of fusion 1710 ~ 1756 DEG C, namely becomes silica glass after cooling ^[1].

High purity quartz (high-purityquartz) is the main raw material of manufacture order crystal silicon, polysilicon, silica glass, optical fiber, solar cell, the contour performance materials of ic substrate ^[2].Glass sand is mainly used in the industries such as the unicircuit of silica glass and IC, and its expensive goods is widely used in extensive and super large-scale integration, optical fiber, laser, military and space industry ^[3].The importance of high purity quartz is also the preparation of polysilicon Pure Silicon Metal, makes it the critical materials becoming crystal silicon and solar photovoltaic industry thereof.Because these Relationships are to the long term growth of country, therefore, the strategic position of high purity quartz is extremely important, the processing technology of its high-end product by the U.S., Germany etc. monopolize, and restriction technologies and products export ^[3].

High purity quartz is the high-end quartz mineral raw produce adopting the processing of natural quartz mineral wealth, and its principal character is to SiO ₂purity requirement is high, allows metal ion and the inclusion hydroxyl (OH such as iron, titanium, chromium, zirconium, lithium, potassium, sodium hardly ^-) exist ^[4].At present, for the national standard that high purity quartz product is also ununified.Have by SiO ₂content > 3N be high purity quartz, and > 4N is ultra-pure quartz ^[5,6]; Have then by SiO ₂content is that 3N-5N is high purity quartz, and 6N-7N is ultra-pure quartz ^[4].Comprehensive forefathers' viewpoint ^[5-9]with current international technology level, Wang Ling etc. (2011) ^[10]propose high purity quartz universal, namely high purity quartz means w(SiO ₂)>=3N-5N, w(Fe) < 10 × 10 ^-6quartz.It should be noted that, in high-purity material, usually adopt N to represent purity ^[11].Therefore, Wang Ling etc. (2011) ^[10]propose to adopt N to represent SiO in high purity quartz ₂content or purity, namely 1N is w(SiO ₂)>=90%, 2N is w(SiO ₂)>=99%, 3N is w(SiO ₂)>=99.9%, so analogizes.

At present, according to the difference of product application, there is multiple kind in high purity quartz.One is be divided into 40-70 order and 70-140 object glass sand by granularity ^[5], and the varigrained high-purity ground quartz of < 140 object.As shown in table 1,40-70 order and 70-140 order glass sand product have to be applied more widely.One is by SiO ₂purity divides the glass sand/powder of 3N, 4N, 5N.As shown in table 2, SiO presses just in Unimin Corp. (US) of the U.S. (UNIMINU.S.Company) ₂purity defines IOTA high purity quartz series product.

Table 1 quartz sand product and specification (according to [5], slightly revising)

The primary quality measure (× 10 of Unimin Corp. (US) of table 2 U.S. high purity quartz IOTA series product ^-6) ^[3]

2.2 China's high purity quartz processing technology present situations

High purity quartz generally selects mineral crystal to be raw material, then after cleaning and Purification processing, just can reach quality index requirement.But worldwide, high grade quartz raw material is in short supply, and mineral crystal reserves reduce year by year, expensive, and tend to exhausted gradually ^[12-14].Therefore, other silicoide substitution of resources natural water spar is adopted to have extremely important practical significance.

As far back as 20 century 70s, abroad just begin one's study the technology utilizing quartz sand to prepare glass sand ^[15], U.S., moral, Deng developed country substitute in crystal material processing high purity quartz in searching and do a lot of work, and technical development is swift and violent.Such as, Japan the nineties in last century by Stato(1997) ^[16]and Kemmochi(1999) ^[17]transparent high purity quartz is isolated respectively from particulate pegmatite ^[2,14].High purity quartz is then found in vein quartz, metaquartzite by Germany and Russia ^[14].The eighties in 20th century, PPCC company of the U.S. purifies quartz in the grouan in seashore Foxdale area, Britain northwest, SiO ₂content reaches 4N, and Fe impurity is less than 1 × 10 ^-6, other transition element are less than 5 × 10 ^-6, supply West Europe is as raw material of quartz glass.The nineties in last century, the sorting in the grouan in Na Zhou SprucePine area, North Carolina of Unimin Corp. (US) of the U.S., high purity quartz of purifying out, its SiO ₂content reaches more than 4N, and purity soprano reaches more than 5N, and quality product can meet the requirement of various transparency silica glass well.So far, the quartz sand product of U.S. You Niming developed into for the 6th generation, and total impurities content is less than 8 × 10 ^-6, transparency is optical grade, SiO ₂purity is just by 99.9992% to 99.9994% future development ^[2,15].Therefore, Unimin Corp. (US) of the U.S. is all in world lead level in high purity quartz processing technology, industrial scale and quality examination precision etc., and its IOTA series product price reaches 30-100 unit/kg, has almost monopolized world market ^[14].

Since late 1980s, China starts to have the research work of alternative mineral crystal to report successively, the raw material adopted mainly SiO ₂content at the vein quartz of about 2N, quartzite and quartzose sandstone etc., and generally adopts the method processing high purity quartzs such as acidleach, achieves first-stage success:

The first, vein quartz: due to the SiO of vein quartz ₂usually be greater than 2N, and compared with mineral crystal, its resource reserve is relatively abundant, so become the emphasis of research.Such as, Zhang Lingyan etc. (1996) describe with the different vein quartz rock of three kinds of lithologic characters for raw material, produce the possibility of 3N high purity quartz micro mist through flotation, acid treatment ^[18].Han Xianjing (1987) is with SiO ₂content be 99.60% vein quartz be raw material, purification processing 3N glass sand (40-70 order, 70-140 order) ^[5].Liu Ligen etc. (1996) are with SiO ₂content be 99.76% vein quartz be raw material, purification processing granularity is 80-140 object 4N high-purity ground quartz ^[13].Zhang Ming etc. (2004) disclose a kind of with SiO ₂content is the vein quartz of 99.0-99.6% is raw material, and purification processing granularity is the method for 800-2500 object 3N-4N high-purity ground quartz ^[19].

The second, quartzite: because quartzite resource reserve is abundanter, causes interest and the concern of people.Such as, field Venus (1999) is with SiO ₂content be 98.97% quartzite be raw material, purification processing granularity is less than 80 object 4N high-purity ground quartzs, and thinks that Task-size Controlling is very crucial, and granularity is greater than 80 orders and produces qualified glass sand by being difficult to ^[10].Li Yang (1998) is with SiO ₂content be 99.84% quartzite be raw material, purification processing 4N high-purity ground quartz (60-100 order, 100-150 order), and think that acidizer must use be ensure high-purity prerequisite adding of mixing acid, particularly HF ^[20].

3rd, quartzose sandstone and other: quartzose sandstone is one of main source of the industrial quartz sand silicoide raw materials such as glass, pottery, casting ^[21-22].Because quartzose sandstone resource is the most general, forefathers have also carried out the Beneficial of high purity quartz processing.Such as, Niu Fusheng etc. (2001) are with SiO ₂content be 98.78% quartzose sandstone be raw material, purification processing 3N glass sand ^[7].In addition, Zhang Dianfei (2006) discloses one with " silica " for raw material, and adopt hot acid to soak and cold blast (being put into suddenly 400-550 DEG C of High Temperature Furnaces Heating Apparatus from subzero 200-300 DEG C by material) etc. processes the method for 4N high-purity ground quartzs ^[23].Poplar sage to rush etc. (2009) and discloses and a kind ofly adopt " quartzy raw ore " and high-gradient magnetic separation and hot acid leaching etc. to process the method that granularity is the 4N high-purity ground quartz of 5-50 μm ^[24].

From introducing above, although China achieving certain progress, also having sizable gap compared with overall technology level and Unimin Corp. (US) of the U.S. etc., being mainly manifested in: (1) is from the SiO of product ₂purity is seen, China reaches 3N-4N and is also only limitted to powder, and granularity 40-70 order and 70-140 object glass sand are only limitted to 3N, and the 5N level product of Unimin Corp. (US) of the U.S. has realized industrialization generation.(2) from range of product, the tandem product also not meeting various purity and granularity requirements is at present produced.(3) from industrialized scale, there are tens of quartzy processing enterprises in the areas such as Lianyungang of Jiangsu, but its generation scale is generally all less than 1000t/a ^[3].Liu Guoku etc. (2007) think, Lianyungang Area is in the domestic highest level making waste glass sand with crystal at present, but in a large amount of suitability for industrialized production, due to the instability of the chemical content of its homogeneity and interior quality, in being suitable only for, low-grade silica glass ^[15].Therefore, generally speaking, China's glass sand technology backwardness relatively, also thoroughly do not solve the Technology problem extracting glass sand, the technical barrier of high-purity, low hydroxyl quartz raw material is not also captured ^[15], the technology of heavy industrialization is still immature ^[2].

2.3 vein quartzs and high purity quartz application advantage thereof

Nature generally can be referred to as siliceous raw material as the quartz mineral resource of industrial application, mainly contains vein quartz, quartzite, quartzose sandstone, konilite and natural siliceous sand ^[25]and the genetic type such as mineral crystal and grouan.From introducing above, mineral crystal is the traditional raw material of processing high purity quartz.But, the mineral crystal mineral deposit lean ore of China is many, rich ore is few, high-level reserves are few, mostly be accompanying mineral deposit, field conditions is poor, many with hand-sorting after exploitation, various places crystal foreign matter content difference is larger, unstable product quality, is difficult to the stdn supply realizing raw material, far can not reach the modern production requirement of high grade silica glass ^[14].

As mentioned above, vein quartz has become the main raw material of Germany and Russia's processing high purity quartz ^[14], prove that vein quartz is one of desirable raw mineral materials of processing high purity quartz.But for a long time, the industrial value of China's vein quartz does not cause the concern of people always.Its major cause: one be the glass very large with usage quantity, the silicoide resource of the conventional use such as pottery and molding sand compares, because vein quartz reserves are general relatively little, exploitation difficulty is comparatively large, and the industrial mineral be difficult to as these conventional use is used.One is the alternate resources as mineral crystal, due to the reason such as restriction of past purification processing technology, is difficult to reach industrial application requirement.

In fact, vein quartz is commonplace in the distribution of China, but due to above reason, very rare about vein quartz Research Literature at present; Also may be technical know-how reason, almost have no report about vein quartz feature and the research of high purity quartz processing relationship, at present also not based on vein quartz quality discrimination and the judgement criteria of high purity quartz purposes.From rare document: vein quartz (veinquartz) is formed by hydrothermalism, is almost all made up of quartz, compact mass constructs ^[25].It is a kind of magmatic hydrotherm mineral ore relevant with grouan, and its mineralogical composition is single, is all almost quartz, SiO ₂content is generally more than 99%, and deposit scale is generally little, and occurrence is steep.Vein quartz mainly originates in grouan or granite gneiss terrain, and ore body is irregular veiny, general several meters to tens meters of thickness, and length is generally tens meters to hundreds of rice, and width is generally several meters, and a mining area can form by wall scroll mineral ore or by many bar mineral ores ^[26].

Current, because high purity quartz is the high value added product with extremely important purposes, and demand increases just year by year, makes the industrial value of vein quartz radical change occur.According to applicant's early-stage Study understanding, be that the main advantage of raw mineral materials processing high purity quartz is with vein quartz: the first, because high purity quartz added value is high, import price reaches 30-100 unit/kg ^[14], absolute dosage is less, and the past is little ore deposit by traditional silicoide resource criterion, and nowadays press this novelty teabag standard of high purity quartz, some vein quartzs may be large ore deposits.The second, China's various places crystal foreign matter content difference is comparatively large, unstable product quality, be difficult to the stdn supply realizing raw material, and the origin cause of formation of same mining area vein quartz is substantially identical, ore quality is relatively stable, and the raw mineral materials stdn processing very high for specification of quality creates condition.In addition, compared with mineral crystal, its field conditions also tool has great advantage.3rd, according to the early-stage Study (as [10,21-22,27]) of applicant, expect to compare with other silicoide sources such as quartzites with quartzose sandstone, vein quartz is almost all made up of quartz, SiO ₂usually be greater than 2N, other foreign matter content is relatively less, in high purity quartz purifies application, show very large potentiality.

In a word, this novelty teabag of high purity quartz makes vein quartz become to have the mineral wealth that very essential industry is worth; The application advantage of vein quartz in high purity quartz is obvious, has a extensive future; Taking vein quartz as raw mineral materials processing high purity quartz will become one of important option that China breaks through in this crucial Application Areas acquisition of technology.

2.4 key technical problems involved in the present invention

In recent years, the emerging strategic industries development such as China's new forms of energy and novel material are very fast, and become the big producing countries such as crystal silicon, silica glass and unicircuit, high purity quartz demand increases just year by year.But China's high purity quartz all can not satisfy the demands in kind and scale, such as, produce the required high purity quartzs such as high-grade silica glass also to need from external high price import (30-100 unit/kg) ^[13], the silica glass that heavy caliber silica tube, high quality quartz pushrod and quartzy ingot and optical communication use also needs a large amount of import ^[14].What is more important, high purity quartz is in the source of silicon industrial chain, plays crucial restrictive function to related products and technology.Such as, up to now, China's crystal silicon and solar photovoltaic industry chain also imperfect, disappearance or short slab mainly in the upstream of industrial chain.According to pertinent data introduction, the silicon material of China's solar photovoltaic industry chain upstream and silicon ingot are produced and rely on external technology in for a long time, and high purity polycrystalline silicon and the main dependence on import of the trichlorosilane needed for production thereof.At present, HIGH-PURITY SILICON material has become the bottleneck of restriction China theCourse of PV Industry ^[24], its one of the main reasons immaturely with the high purity quartz technology needed for source may have direct relation.Also it is pointed out that carbothermic method is one of technological development direction of producing high purity polycrystalline silicon after the improved Siemens generally adopted at present, the purity of high purity quartz and carbon is proposed and is more strict with ^[25].Obviously, high purity quartz processing is by one of commanding elevation becoming this new and high technology.

But alarming, due to reasons such as technical know-hows, the high purity quartz processing technology information of open report is little, China is unclear to the ins and outs of developed country's relevant enterprises such as Unimin Corp. (US) of the U.S..If do not change China's high purity quartz state of the art, the development of closely-related new forms of energy and new material industry with it will be restricted.Research according to this seminar is familiar with, and the Chief technical problem that the present invention relates to is as follows:

(1) what acid was filled a prescription selects: as mentioned above, and forefathers generally adopt the method processing high purity quartzs such as acidleach.But, because the kind of sour reagent is also many, in addition because vein quartz is formed and the geologic function difference becoming the ore deposit later stage, there is larger difference in the ore texture of Different sources vein quartz, impure mineral, the character such as quartz mineral and inclusion thereof and feature, how selecting acid formula according to the character of vein quartz mineral and feature, is one of Chief technical problem of the present invention.

(2) optimization of acid leaching process condition: acidleach is purified and related to the processing condition such as raw meal particle size, acid concentration, solid-to-liquid ratio, acidleach temperature, leaching time, how being determined according to the character of vein quartz raw material and feature, is one of Chief technical problem of the present invention.

(3) optimization of other purifying technique condition: the major impurity of vein quartz raw material comprises mineral inclusion and impure mineral etc., how effectively to remove not only relevant with acid leaching process condition with acid formula, and it is relevant with techniques such as roasting hardening, how being determined according to the character of vein quartz mineral and feature, is also one of Chief technical problem of the present invention.

2.5 objects of the present invention

The object of the invention is, research is a kind of is raw material with vein quartz, purification processing w(SiO ₂) > 4N, w(Fe) < 10 × 10 ^-6, particle diameter is respectively-40 orders, 40-70 order, 70-140 order and-140 object high purity quartzs.Through retrieval, do not find that a kind of is raw material with vein quartz, purification processing w(SiO ₂) > 4N, w(Fe) < 10 × 10 ^-6, particle diameter is respectively bibliographical information or the patent application of-40 orders, 40-70 order, 70-140 order and-140 object high purity quartzs.

Reference

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Summary of the invention

3.1 test samples and main agents

The test sample that the present invention adopts is vein quartz raw ore, is creamy white, oily luster, compact mass.Table 3 is inductively coupled plasma emission spectrography (ICP-OES) detected results of test vein quartz raw ore sample, can find out: raw ore sample w(SiO ₂) > 2N, main trace element total amount average out to 975.99 × 10 ^-6; The total impurities of W03 raw ore is minimum, is 596.5 × 10 ^-6, W01 is 999.77 × 10 ^-6, the total impurities of W02 raw ore is maximum.In raw ore sample, objectionable constituent comprise Ca, Na, K, Fe, Al, Mg etc., and wherein Na, Ca, K, Fe, Al content is higher.

Before purification processing, raw ore working method is: quartz deposit raw material is crushed to-30mm by (1), and is 5-30mm by broken material sizing.(2) tap water is adopted to be that 5-30mm material cleans up by granularity.(3) foreign material in material and the impure as seen material of naked eyes are removed in picking.

ICP-OES detected result (wherein Si, the % of table 3 vein quartz raw ore; Other, × 10 ^-6)

Sample	Na	K	Mg	Ca	Ti	Mn	Fe	Ni	Zn	Cd	Al	P	Total	Si
															W01	399.8	76.51	33.03	243.24	1.01	8.6	180.2	0.13	1.23	0.29	55.73	-	999.77	99.90
W02	479.8	359.2	28.6	368.6	17.5	2	29.3	2	14	1.1	22.1	7.5	1331.7	99.87
															W03	29	38	51.5	201	11	1	82	9.5	2.4	0.2	163.5	-	596.5	99.94
On average	302.87	157.9	37.71	270.9	9.84	3.86	97.16	3.87	5.87	0.53	80.44	7.5	975.99	99.90

The Primary Chemical that the present invention tests employing is as shown in table 4.

Table 4 is purified and is tested Primary Chemical

Reagent name	Reagent purity	Reagent concentration	Manufacturer
				HCl	Top grade pure (GR)	36%-38%	Beijing Chemical Manufacture
H ₂SO ₄	Analytical pure (AR)	98%	Chengdu Ke Long chemical reagent factory
				HNO ₃	Analytical pure (AR)	65%-68%	Chengdu Ke Long chemical reagent factory
Oxalic acid	Analytical pure (AR)	Solid	Chengdu Ke Long chemical reagent factory
				Citric acid	Analytical pure (AR)	Solid	Chengdu Ke Long chemical reagent factory
HF	Analytical pure (AR)	40%	Chengdu associating chemical reagent institute
				Distilled water			Common distilled water

3.2 roasting shrends are purified and are tested

Roasting shrend can make material preferably with the combination such as the oxygen in air, assist in removing and can react with oxygen and the material that can gasify or distil.Meanwhile, raw ore compares capacity fragmentation after roasting shrend.Accordingly, first will clean and material roasting in chamber type electric resistance furnace after picking, maturing temperature 1000 DEG C, constant temperature time 0.5-2h(0.5h), then by the shrend in room temperature distilled water rapidly of roasting material.Then, material after shrend is dried in an oven, bake out temperature 105 DEG C, drying time 2h, then material drying is crushed to-40 orders.

The present invention carries out re-baking shrend test on above-mentioned working foundation, its method is: material roasting in chamber type electric resistance furnace respectively after sieving, after being warming up to design temperature (500 DEG C, 600 DEG C, 700 DEG C, 800 DEG C, 900 DEG C, 1000 DEG C), constant temperature 1-3h(2h again), then by the shrend in room temperature distilled water rapidly of roasting material, material after shrend is dried in an oven, bake out temperature 105 DEG C, drying time 2h.

Table 5 and Fig. 1 are that different secondary maturing temperature affects the ICP-OES detected result of test sample to vein quartz shrend refining effect, can find out: re-baking shrend has larger impact to refining effect, with raw ore total impurities 1331.7 × 10 ^-6compare (table 3, W02), the total impurities through different maturing temperature Water Quenching material all significantly decreases, especially minimum when 600-700 DEG C.Therefore, re-baking temperature is selected to be 650 DEG C.

Table 5 different secondary maturing temperature affects the ICP-OES detected result (× 10 of test sample to vein quartz shrend refining effect ^-6)

Maturing temperature (DEG C)	Na	K	Mg	Ca	Ti	Mn	Fe	Ni	Zn	Cd	Al	Total
													500	420.1	31.68	0.51	15.48	0.13	0.16	25.61	0.17	0.1	0.02	12.63	506.59
600	143.4	123.8	0.57	163	0.29	0.24	23.5	0.06	0.19	0.03	16.13	471.21
													700	240.2	111.7	0.55	85.6	0.28	0.17	29	0.07	0.06	0.01	13.45	481.09
800	243.5	320.9	7.6	138.5	0.21	3.08	48.16	0.06	0.02	0.02	25.69	787.74
													900	375.7	295.5	5.1	209.4	0.21	0.25	29.5	0.03	0.11	0.01	23.67	939.48
1000	436.3	328.8	19.9	181.5	0.14	1.51	24.5	0.03	0.26	0.02	17.97	1010.93

Note: roasting time is 2h, test sample is W02

3.3 acid formulas select test

Acidleach is the critical process of high purity quartz purification processing.Table 6 is high purity quartz purification processing acid formula and fundamental test condition thereof.Table 7 is by above test conditions and the acid formula of table 6 and the ICP-OES test result of test conditions purification processing high purity quartz thereof, can find out: compared with raw ore (table 3), and 7# acid formula achieves certain refining effect.Therefore, the present invention selects 7# acid formula (HCl+H ₂sO ₄+ HF) be acidleach reagent, and adopt table 6 acid formula to carry out systematic testing and optimization to acidleach purifying technique condition.

Table 6 high purity quartz purification processing acid formula and other fundamental test condition

Numbering

Acid formula

Purity

Concentration

Solid-to-liquid ratio

Acidleach temperature

Leaching time

Sample granularity

1#

Citric acid

Analytical pure AR

18%

1:2

50℃

2h

-40 orders

3#

HCl

Analytical pure AR

18%

1:2

50℃

2h

-40 orders

7#

HCl+H ₂SO ₄+HF

Analytical pure AR

HF5%+ other 18%

1:2

50℃

2h

-40 orders

The different acid formula of table 7 is to the ICP-OES test result (× 10 of vein quartz purification processing test ^-6)

Acid formula	Na	K	Mg	Ca	Ti	Mn	Fe	Ni	Zn	Cd	Al	Total
													1#	398	16.5	27	84.5	0.5	1	10	2.5	16.5	1.5	115	673.0
3#	315.5	42.5	11	66	113	1.5	1	3.5	4.5	0.5	135.5	694.5
													7#	383	138	32.5	35	1	1	36.5	4	2.5	1.5	29	664

3.4 acidleach purifying technique condition tests

The processing condition that the present invention adopts above test to determine, the factors such as further system thinking acidleach solid-to-liquid ratio, sour consumption, leaching time, acidleach temperature are on the impact of high purity quartz purification processing effect.Table 8 is high purity quartz purification processing experiment of process conditions of the present invention designs, is below test-results.

Table 8 high purity quartz acidleach purification processing experiment of process conditions designs

Content of the test	Acid formula	Other test conditions
			The relation of solid-to-liquid ratio and refining effect	3#	Solid-to-liquid ratio: 1:1,1:2,1:3,1:4,1:5
The relation of acid concentration and refining effect	1#	Acid concentration (%): 5,10,15,20,25,30,35,40
			The relation of leaching time and refining effect	1#	Leaching time (h): 2,4,6,8,10,12
The relation of acidleach temperature and refining effect	1#	Acidleach temperature (DEG C): 20,30,50,70,90
			The relation of sample granularity and refining effect	1#	Granularity (order): 30-40,40-70,70-140,140-200 ,-200

Note: leaching time 2h; Acidleach temperature 50 C; Sample granularity-40 order

(1) relation of acidleach solid-to-liquid ratio and refining effect

Solid-to-liquid ratio refers to material solids quality and pickling liquid mass ratio.Solid-to-liquid ratio test method is: 5 solid-to-liquid ratio test points such as design 1:1,1:2,1:3,1:4,1:5, respectively granularity being dried quartz sand 10g for-40 objects adds in 250ml beaker, with 3# acid for acidleach reagent, acid concentration 18%, acidleach temperature 50 C, constant temperature and stirring 2h, carry out test analysis after cleaning, drying.

Table 9 and Fig. 2 are that acidleach solid-to-liquid ratio affects the ICP-OES test result of test sample to vein quartz impurity-eliminating effect, can find out: acidleach solid-to-liquid ratio is larger on refining effect impact.When solid-to-liquid ratio is respectively 1:3, when 1:4 and 1:5, foreign matter content is larger, and waste acid solution; Time solid-to-liquid ratio is 1:1, the easy evaporate to dryness of solution; And solid-to-liquid ratio is when being 1:2, total impurities is minimum (492.5 × 10 ^-6), than raw ore 1331.7 × 10 ^-6reduce 63.02%, save acid solution again, effect is ideal.

Table 9 different solid is than the ICP-OES Measurement results (× 10 of acidleach purification processing sample (W02) ^-6)

Solid-to-liquid ratio	Na	K	Mg	Ca	Ti	Mn	Fe	Ni	Zn	Cd	Al	Total
													1:1	102.5	60	10.5	241	9	6	42	2	1.5	0	27	501.5
1:2	196	5.5	7.5	230.5	8.5	6.5	15.5	0.5	2	0.5	19.5	492.5
													1:3	388	46	16.5	224.5	10	5	43	0	1.5	0	31.5	86.86
1:4	368.5	40.5	14	195	8	5.5	30.5	0	2	0	22.5	686.5
													1:5	218	38	7	272	11	7.5	28.5	0.5	2	0.5	27.5	612.5

Note: 3# acid, acid concentration 18%, acidleach humidity 50 DEG C, constant temperature churning time 2h

(2) relation of acid concentration and refining effect

This test method is: acidleach reagent is citric acid, and acid concentration is respectively 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, respectively granularity is dried quartz sand 10g for-40 objects and add in 250ml beaker, add 1# acid 20ml, acidleach temperature 50 C, constant temperature and churning time 2h, carry out test analysis after cleaning, drying.

Table 10 and Fig. 3 are that acid concentration is mixed to vein quartz the ICP-OES test result of effect test sample, and can find out: acidleach concentration has a significant effect to vein quartz impurity-eliminating effect, along with concentration increases, total impurities is trend parabolically.Concentration excessively rare (< 10%), impurity-eliminating effect is not obvious; When concentration is 20%, total impurities content is only 148 × 10 ^-6, impurity-eliminating effect is best; Excessive concentration (> 30%), impurity-eliminating effect is also not obvious, and foreign matter content increases along with the increase of concentration.Because excessive concentration not only can increase washing times, increase flat cost, and to equipment corrosion aggravation, and increase waste water treatment cost, be obviously worthless.Comprehensive other factors, choosing acid concentration is 20%.

The ICP-OES Measurement results (× 10 of table 10 different acid concentration acidleach purification processing sample (W02) ^-6)

Concentration (%)	Na	K	Mg	Ca	Ti	Mn	Fe	Ni	Zn	Cd	Al	Total
													5	10.5	81	1	99.5	1.5	1.5	8.5	3.5	2.5	0.5	12	222
10	41.5	52	0.5	99	1.5	1.5	3.5	4	6.5	0	12	222
													15	8.5	93.5	2	51.5	0.5	0.5	6	3.5	2.5	5	4.5	178
20	4.5	53	2	65.5	1.5	1	3	2.5	2	1	3.5	139.5
													25	20	74	2	40.5	2.5	3.5	8.5	1	5.5	0	27	184.5
30	4.5	54.5	2	57	0.5	17.5	15.5	3.5	2	0	15	172
													35	28	97	0.5	29	0.5	3	36.5	4	1	0.5	8	208
40	5	102.5	3	102.5	46	35.5	7	11	7.5	2	17	339

Note: 1# acid 20ml, 50 DEG C of constant temperature stir 2h

(3) relation of acidleach temperature and refining effect

In general, cold acid treatment needs the time long, and hot acid can accelerate the dissolving of impurity.This test method is: acidleach thermostat temperature is respectively 20 DEG C (room temperatures), 30 DEG C, 50 DEG C, 70 DEG C, 90 DEG C, respectively granularity is dried quartz sand 10g for-40 objects and add in 100ml beaker, add the 1# acid 20ml of 20% by 1:2 solid-to-liquid ratio, acidleach and stirring 2h, carry out test analysis after cleaning, drying.

Table 11 and Fig. 4 are that acidleach temperature affects the ICP-OES test result of test sample to vein quartz impurity-eliminating effect, can find out: acidleach temperature has a significant effect to vein quartz impurity-eliminating effect, hot acid is obviously better than cold acid, and along with temperature rising, total impurities content progressively downtrending is obvious, total impurities content minimum (103.5 × 10 90 DEG C time ^-6), so, select 90 DEG C for optimizing acidleach temperature.It should be noted that, should be noted that sealing in heating and thermostatic process, to reduce in the waste that causes of gasification and air impurity to the impact of quality.

The ICP-OES Measurement results (× 10 of table 11 different acidleach temperature purification processing sample (W02) ^-6)

Temperature (DEG C)	Na	K	Mg	Ca	Ti	Mn	Fe	Ni	Zn	Cd	Al	Total
													20	105	130	79.5	205	3.5	2	79.5	2	8.5	0.5	40	655.5
30	70	80	74	19.5	5.5	3	60.5	5	65.5	5	36	424
													50	33	81	51	62.5	3.5	4.5	92	1.5	8.5	0	57.5	395
70	22	79	0.5	46.5	1	1	0.25	2	3.5	0.5	20.5	176.75
													90	12	10.5	3	60	2	1	4	2	0.5	0.5	3.5	99

Note: the 1# acid 20ml of 20%, 50 DEG C of constant temperature stir 2h

(4) relation of leaching time and refining effect

Rational leaching time, can ensure that acid and impurity can react fully.This test method is: acidleach constant temperature time is respectively 2h, 4h, 6h, 8h, 10h, dry quartz sand 10g by granularity for-40 objects respectively and add in 100ml beaker, add the 1# acid formula 20ml of 20% by 1:2 solid-to-liquid ratio, thermostat temperature 50 DEG C, carries out test analysis after cleaning, drying.

Table 12 and Fig. 5 are that acidleach constant temperature time affects the ICP-OES test result of test sample to vein quartz impurity-eliminating effect, can find out: acidleach constant temperature has a significant effect to quartz sand impurity-eliminating effect.Along with the increase of leaching time, total impurities content is reduction trend substantially, and when constant temperature time is 2h, total impurities content obviously reduces (397 × 10 ^-6); When constant temperature time is 4h, total impurities content reduces rapidly (190 × 10 ^-6); When constant temperature time is respectively 6h, 8h, total impurities content is little.Therefore, acidleach constant temperature time is selected to be 4h.It should be noted that, in acidleach thermostatic process, should note stirring, to increase the contact area of the chance that acid solution and quartz particles show to contact, augmenting response, improve acidleach effect.

The ICP-OES Measurement results (× 10 of table 12 different acidleach constant temperature time purification processing sample (W02) ^-6)

Constant temperature time (h)	Na	K	Mg	Ca	Ti	Mn	Fe	Ni	Zn	Cd	Al	Total
													2	33	81	51	62.5	3.5	4.5	92	3.5	4.5	0	57.5	393
4	19.5	79.5	3.5	39	3	2	5	1.5	4.5	0.5	26	184
													6	19.5	69	7.5	62.5	2.5	3	16.5	2	9.5	0	15	207
8	54	13.5	5.5	80.5	2.5	3.5	19.5	2.5	15	1	1	198.5
													10	363.5	89.5	11	55.5	1.5	2	13.5	3.5	9	5	36	590
12	21	59.5	3.5	54.5	0	0	15	4.5	3	0.5	4	165.5

Note: the 1# acid 20ml of 20%, thermostat temperature 50 DEG C

(5) relation of test sample granularity and refining effect

According to different application, there is certain requirement to the granularity of high purity quartz.Therefore, granularity is one of important technology index of high purity quartz product.This test method is: granularity is respectively 30-40 order, 40-70 order, 70-140 order, 140-200 order ,-200 orders, add in 100ml beaker by varigrained oven dry quartz sand 10g respectively, the 1# acid 20ml of 20% is added by solid-to-liquid ratio 1:2, constant temperature time 2h, thermostat temperature 50 DEG C, carries out test analysis after cleaning, drying.

Table 13 and Fig. 6 are that granularity affects the ICP-OES test result of test sample to vein quartz impurity-eliminating effect, and can find out: when granularity is 30-40 order, total impurities content is the highest by (817.5 × 10 ^-6), its reason may be, because particle is comparatively large, the objectionable impurities of granule interior fails fully to expose, and have impact on acidleach refining effect; When granularity < 40 order, the content of total impurities reduces rapidly; When granularity is 40 ~-200 order, corresponding granularity total impurities change is little, therefore, can select suitable granularity according to purposes.The present invention is according to current market demand situation, and the high purity quartz granularity of Choice and process is respectively-40 orders, 40-70 order, 70-140 order ,-140 orders etc.

The ICP-OES test result (× 10 that table 13 different grain size affects vein quartz impurity-eliminating effect ^-6)

Sample (order)	Na	K	Mg	Ca	Ti	Mn	Fe	Ni	Zn	Cd	Al	Total
													30-40	23.5	112.5	3	400	3.5	2	27.5	11	0	0.5	20	603.5
40-70	264.5	1.4	5	92.5	0.5	7	20.5	7.5	6	0	27.5	432.4
													70-140	258	1.5	1	182	9	4.5	24	12.5	5	1	18	516.5
140-200	287	1.5	3.5	53	4	2	45.5	16	2	0.5	20.5	435.5
													-200	325	0.6	0.5	46.5	0.5	4.5	22	3.5	10.5	0.5	13	427.1

Note: the 1# acid 20ml of 20%, 50 DEG C of constant temperature stir 2h

3.5 acidleach purification Optimizing Technicals

According to above test, can sum up with vein quartz is raw material, the Optimizing Technical of acidleach purification processing high purity quartz, that is: raw meal particle size-40 order or 40-70 order or 70-140 order or 140-200 order, and acid formula is HCl+H ₂sO ₄+ HF, HCl and H ₂sO ₄concentration 10-30%, HF concentration 5%, solid-to-liquid ratio 1:2, acidleach temperature 90 DEG C, acidleach and stirring 4h.

3.6 high purity quartz complete processing steps

According to above experimental study, the present invention is raw material with vein quartz, with HCl+H ₂sO ₄+ HF is acidleach reagent, adopts secondary shrend and acidleach Optimization Technology, purification processing w(SiO ₂) > 4N, w(Fe) < 10 × 10 ^-6, granularity is respectively-40 orders, 40-70 order, 70-140 order and-140 object high purity quartzs, and its complete processing is undertaken by following 9 steps:

(1) coarse crushing and screening: by vein quartz raw material crushing to-30mm, then be 5-30mm by broken material sizing;

(2) cleaning and picking: adopting tap water to clean granularity is 5-30mm material, and then macroscopic foreign material and impure material are removed in picking;

(3) bakes to burn the article shrend: by the roasting in chamber type electric resistance furnace of picking material, constant temperature 0.5-2h after temperature rises to 1000 DEG C, then by the shrend in room temperature distilled water rapidly of roasting material;

(4) dry with in small, broken bits: dried in an oven by material after shrend, bake out temperature 105 DEG C, drying time 2h, then crushes material to-40 orders;

(5) re-baking shrend: by-40 order material roastings in chamber type electric resistance furnace, maturing temperature 650 DEG C, constant temperature time 1-3h, then by the shrend in room temperature distilled water rapidly of roasting material;

(6) dry and screening: material after shrend is dried in an oven, bake out temperature 105 DEG C, drying time 2h, then material drying is sieved as 40-70 order, 70-140 order and-140 orders;

(7) acidleach is purified: acidleach purification-40 orders, 40-70 order, 70-140 order and-140 object materials respectively, processing condition are: acidleach reagent is HCl+H ₂sO ₄+ HF, HCl and H ₂sO ₄concentration 10-30%, HF concentration 5%, solid-to-liquid ratio 1:2, acidleach temperature 60-150 DEG C, acidleach and churning time 2-6h;

(8) clean: material after acidleach is cleaned 2 times with common distilled water respectively, more respectively with pure water cleaning 1-2 time;

(9) dry: dried in an oven respectively by cleaning material, bake out temperature 105 DEG C, drying time 2h, namely obtains respectively w(SiO ₂) > 4N, w(Fe) < 10 × 10 ^-6, particle diameter is respectively-40 orders, 40-70 order, 70-140 order and-140 object high purity quartzs.

Four, technical superiority

The present invention is raw mineral materials with vein quartz, with HCl+H ₂sO ₄+ HF is acidleach reagent, adopts secondary shrend and acidleach Optimization Technology, purification processing w(SiO ₂) > 4N, w(Fe) < 10 × 10 ^-6, granularity is respectively-40 orders, 40-70 order, 70-140 order and-140 object high purity quartzs, and defining a kind of take vein quartz as the method for Raw material processing 4N high purity quartz.The present invention has successful, security is good, technique is simple, apply advantage and the advantages such as easy, of many uses, economic results in society are remarkable, is embodied in:

(1) successful.the present invention take vein quartz as raw material, can purification processing w(SiO ₂) > 4N, w(Fe) < 10 × 10 ^-6, particle diameter is respectively-40 orders, 40-70 order, 70-140 order and-140 object high purity quartzs.

(2) security is good.the present invention adopts secondary hardening and acidleach Optimization Technology, and purification processing 4N high purity quartz, has safe reliability.

(3) technique is simple.9 processing steps of the present invention are good, simple to operate continuously, and work is convenient.

(4) apply easily.present invention process is simple, easy to operate, and easily study support is held and applied.

(5) of many uses, economic results in society are remarkable.high purity quartz is the important source material that crystal silicon, silica glass and ic substrate material etc. are produced, and has consequence and effect at the emerging strategic industries such as new forms of energy and novel material.The efficiency utilization that the present invention can be China's vein quartz mineral wealth provides technical support, promote China's high purity quartz processing technology progress and apply the emerging strategic industries such as relevant new forms of energy and novel material to high purity quartz to develop, have broad application prospects and significant economic results in society.

Five, accompanying drawing explanation

Fig. 1: different secondary maturing temperature is on the impact of vein quartz shrend refining effect.

Fig. 2: acidleach solid-to-liquid ratio is on the impact of vein quartz impurity-eliminating effect.

Fig. 3: acidleach concentration affects vein quartz impurity-eliminating effect.

Fig. 4: acidleach temperature affects vein quartz impurity-eliminating effect.

Fig. 5: acidleach constant temperature time is on the impact of vein quartz impurity-eliminating effect.

Fig. 6: granularity is on the impact of vein quartz impurity-eliminating effect.

Six, embodiment

Example 1: a kind of take vein quartz as the method for Raw material processing 4N high purity quartz

This example take vein quartz as raw material, with HCl+H ₂sO ₄+ HF is acidleach reagent, adopts secondary shrend and acidleach Optimization Technology, purification processing w(SiO ₂) > 4N, w(Fe) < 10 × 10 ^-6, granularity is respectively-40 orders, 40-70 order, 70-140 order and-140 object high purity quartzs, and its complete processing is undertaken by following 9 steps:

Table 14 is that the granularity adopting vein quartz (L01) to obtain for raw material and this case method is respectively-40 orders, and the ICP-OES detected result of 40-70 order, 70-140 order and-140 object high purity quartz samples, can find out: corresponding size sample w(SiO ₂) > 4N, w(Fe) < 10 × 10 ^-6, reached the technical requirement of 4N high purity quartz.

ICP-OES detected result (wherein Si, the % of table 14 different grain size 4N high purity quartz sample; Other, × 10 ^-6)

Sample	Na	K	Mg	Ca	Ti	Mn	Fe	Ni	Zn	Cd	Al	Pb	Total	Si
															-40 orders	34.02	3.42	0.39	5.51	0.44	0.04	2.47	0	0.215	0	10.5	0.24	57.245	99.9943
40-70 order	14.12	4.77	0.22	3.04	0.29	0	7.89	0.045	0.64	0.055	8.13	0.14	39.33	99.9961
															70-140 order	15.47	4.25	0.355	1.41	0.325	0.08	2.22	0.1	0.48	0.03	8.1	0.05	32.86	99.9967
-140 orders	21.77	3.35	0.515	8.82	0.545	0.07	2.88	2.22	0.655	0.01	8.97	0.165	49.95	99.9950

Note: 7# acid formula (HCl+H ₂sO ₄+ HF); Vein quartz raw ore sample is numbered L01

Express one's thanks to

This work is national human resources division students abroad scientific and technological activities preferentially funds (No. [2010] 32, Chuan Ren society letter), state natural sciences fund (50974025), country's public welfare industry scientific research specific project expenditure project problem (201011005-5), " 15 " State Commission for Restructuring the Economic Systems main project problem (2004BA810B02) and center for doctors of institution of higher education of Ministry of Education of the state fund (20095122110015) subsidize.

Claims

1. being a method for Raw material processing 4N high purity quartz with vein quartz, is raw material with vein quartz, with HCl+H ₂sO ₄+ HF is acidleach reagent, adopts secondary shrend and acidleach Optimization Technology, purification processing w(SiO ₂) > 4N, w(Fe) < 10 × 10 ^-6, granularity is respectively 40-70 order, 70-140 order and-140 object high purity quartzs, and its complete processing is undertaken by following 9 steps:

(7) acidleach is purified: acidleach purification 40-70 order, 70-140 order and-140 object materials respectively, processing condition are: acidleach reagent is HCl+H ₂sO ₄+ HF, HCl and H ₂sO ₄concentration 10-30%, HF concentration 5%, solid-to-liquid ratio 1:2, acidleach temperature 60-150 DEG C, acidleach and churning time 2-6h;

(9) dry: dried in an oven respectively by cleaning material, bake out temperature 105 DEG C, drying time 2h, namely obtains respectively w(SiO ₂) > 4N, w(Fe) < 10 × 10 ^-6, particle diameter is respectively 40-70 order, 70-140 order and-140 object high purity quartzs.