CN104671705B - A kind of artificial stone utilizing two alkaline process brine sludges to manufacture - Google Patents
A kind of artificial stone utilizing two alkaline process brine sludges to manufacture Download PDFInfo
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- CN104671705B CN104671705B CN201510047489.2A CN201510047489A CN104671705B CN 104671705 B CN104671705 B CN 104671705B CN 201510047489 A CN201510047489 A CN 201510047489A CN 104671705 B CN104671705 B CN 104671705B
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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
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/91—Use of waste materials as fillers for mortars or concrete
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Abstract
The invention belongs to field of environment protection and solid waste resource recovery utilizes technical field, particularly to the two this kind of solid slags of alkaline process brine sludge that will produce during salt making enterprises bittern purifying, prepare the technology of artificial stone.The present invention is by two alkaline process brine sludge pre-treatments slightly, as inorganic filler, is applied to prepare artificial stone, and strictly controls CaCO in two alkaline process brine sludges3Mass content be 90～96.5%, NaCl mass content is 0.5～1.5%, Mg (OH)2Mass content is 0.5～1.5%, CaSO4Mass content be 1.5～4%, the mass content of other impurity is 1.0～3.0%, artificial stone can be played invigoration effect, saves the consumption of the quartz sand as reinforcement material.
Description
Technical field
The invention belongs to field of environment protection and solid waste resource recovery utilizes technical field, particularly to by salt making enterprises salt
The two this kind of solid slags of alkaline process brine sludge produced in purification process, prepare the technology of artificial stone.
Background technology
Bittern purifying technique is that Salt Industry improves purified salt product purity, reduces impurity content in salt, improves product salt whiteness
One critical process, is to improve the salt making enterprises effective time, extension device service life, reduces a weight of energy resource consumption
Want operation；It is to improve comprehensive resource utilization rate, is used in one of important measures of salt chemical engineering production；It is that Salt Industry reduces production
One of important channel of cost.
Two alkaline process bittern purifyings are to utilize soda (Na2CO3) by the Ca in salt2+With CaCO3Precipitation form removes, and utilizes and burns
Alkali (NaOH) is by the Mg in salt2+, with Mg (OH)2Precipitation removes.The fundamental reaction formula of two alkaline process is as follows:
Ca2++CO3 2-→CaCO3↓
2OH-+Mg2+→Mg(OH)2↓
From the reaction mechanism mechanism of reaction, after two alkaline reactions, brine sludge main component is CaCO3, additionally possibly together with a small amount of NaCl, Mg (OH)2
And CaSO4。
Artificial stone, with resin and filler as Main Ingredients and Appearance, is added initiator, accelerator, dyestuff etc. and is collectively formed complete artificial
Stone.Polymethyl methacrylate (PMMA) and unsaturated polyester resin etc. are mainly had for producing the resin of artificial stone.According to
The difference of product category, purposes and character, filler accounts for the 55%-80% of formula total amount, and they are typically inorganic matter, artificial
Stone is not chemically reactive, but is to increase product strength.It is aluminium hydroxide and carbonic acid that optimum is used as the material of artificial stone filler
Calcium powder.Calcium carbonate is a kind of white crystal or powder, and the artificial stone produced with it has the solid texture of stone material, and carbonic acid
Calcium class Ore is more cheap than aluminium hydroxide, is now widely used artificial stone filler.
Summary of the invention
The technical problem to be solved is: provides one to use two alkaline process brine sludges to originate as calcium carbonate, prepares artificial stone
Technical scheme.When two alkaline process brine sludges are used as raw material use, it is not necessary to the most carefully cleaned, retain to a certain extent
NaCl, Mg (OH) in addition to the calcium carbonate in two alkaline process brine sludges2And CaSO4Trace substance, it has been investigated that, when in calcium carbonate
With certain content doping NaCl, Mg (OH)2And CaSO4During this 3 kinds of trace substances, the artificial stone of follow-up preparation can be played
Certain invigoration effect, such that it is able to save the consumption of quartz sand in artificial stone preparation process.
The concrete technical scheme that the present invention uses is: a kind of artificial stone utilizing two alkaline process brine sludges to manufacture, each component of artificial stone is by weight
Amount number is calculated as,
Wherein, as the two alkaline process brine sludges in calcium carbonate source, in artificial stone preparation process, serve as inorganic filler, and play fall
The effect of low cost.After two alkaline reactions terminate, brine sludge is 20～80 μm through washing, dry, be crushed to grain diameter, and
And in water-washing process, (by removing or by the way of interpolation) controls CaCO in two alkaline process brine sludges3Mass content be 90～
96.5%, NaCl mass content is 0.5～1.5%, Mg (OH)2Mass content is 0.5～1.5%, CaSO4Mass content be
1.5～4%, the mass content of other impurity (silicon dioxide) is 1.0～3.0%, shows after deliberation, when trace substance in brine sludge
Content within the above range time, can farthest to preparation artificial stone play invigoration effect；
Resin plays the effect of binding agent, can inorganic filler and quartz sand be combined, and generates fine and close and intensity is big after hardening
Artificial stone, above-mentioned resin is the one in unsaturated-resin, epoxy resin, polymethyl methacrylate and polyurethane resin
Or two or more hybrid resin；
Quartz sand plays the effect of skeleton, and the compressive strength of artificial stone, bending strength, Mohs' hardness and expansion can be greatly improved
The performance indications such as coefficient, above-mentioned quartz sand be 26～40 mesh quartz sands, 40～90 mesh quartz sand, 90～100 mesh quartz sand,
One or more in 325 mesh quartz sands；
The effect of accelerator, can improve activity of curing reaction, reduces solidification temperature, accelerates curing reaction speed, improves solidification
Physical performance, reduces cost etc., above-mentioned accelerator be cobalt system, vanadium system or the organic salt of manganese systems metal, tertiary amines, quaternary amine or
Mercaptan；
In the molecule of coupling agent, there is the reactive group that can combine with inorganic material (such as quartz, calcium carbonate, metal etc.) simultaneously
And the reactive group combined with organic material (such as synthetic resin etc.), inorganic filler and quartz sand dispersibility and bonding can be improved
Property, thus stablize the quality of artificial stone, and boundary strength and the performance of artificial stone can also be improved, above-mentioned coupling agent is organic
One or more mixture in silane coupler or titanate coupling agent；
The effect of firming agent, can cross-link with matrix resin, form netted space polymers, composite aggregate envelope at net
Among shape body, making line style resin become tough and tensile build solid, above-mentioned firming agent is ethylenediamine, diethylentriamine, benzene diformazan
Amine, m-diaminobenzene., diamino diphenyl sulfone, beta-hydroxyethyl ethylenediamine, imidazoles, 2-methylimidazole, maleic anhydride, neighbour
One or more mixture in phthalate anhydride, poly-Azelaic Acid acid anhydride, sebacic dihydrazide；
Above-mentioned pigment is titanium dioxide, micaceous iron oxide, chrome yellow, barba hispanica, cadmium red, cadmium yellow, lithopone, white carbon black, ferrum oxide
One or more mixture in red, iron oxide green and iron oxide yellow.
Present invention also offers the preparation technology of a kind of above-mentioned artificial stone:
First preparing two alkaline process brine sludges: after two alkaline reactions terminate, brine sludge through washing, dry, be crushed to grain diameter is
20～80 μm, and in water-washing process, control CaCO in two alkaline process brine sludges3Mass content be 90～96.5%, NaCl matter
Amount content is 0.5～1.5%, Mg (OH)2Mass content is 0.5～1.5%, CaSO4Mass content be 1.5～4%, other
The mass content of impurity (referring mainly to silicon dioxide) is 1.0～3.0%, and remaining preparation technology is:
(1) batch mixing: by formula, by above-mentioned two alkaline process brine sludges and other component mix homogeneously；
(2) compacting: the mixed material obtained in step (1) is poured molding, or mixed by what step (1) obtained
It is compressing that material after conjunction is transferred to vacuum press,
In vacuum press, set vacuum less than or equal to-0.09mpa；
(3) curing conservation: compressing sheet material in step (2) is moved to baking and curing in high hot house,
Curing operation is divided into primary solidification and rear solidification, and ambient temperature during primary solidification is maintained at 40～100 DEG C, primary solidification
Time 1～3h；Ambient temperature during rear solidification is maintained at 80 DEG C～140 DEG C, rear curing time 2～8h；
(4) demoulding, fixed thick, polish, pack, obtain finished product.
According to technique scheme, the present invention compared with prior art has following advantages and an effect:
The present invention, by two alkaline process brine sludge pre-treatments slightly, as inorganic filler, is applied to prepare artificial stone, is turned waste into wealth by brine sludge,
Achieving recycling of brine sludge resource, two alkaline process brine sludges are greatly reduced relative to other inorganic fillers such as Paris white, cost, add
The cost of artificial stone can be reduced after entering artificial stone；
Two alkaline process brine sludges, as artificial stone filler, can improve the presentation quality of artificial stone, reduces the pore in artificial stone and crackle,
In the water-washing process of pre-treatment, control CaCO in two alkaline process brine sludges3Mass content be 90～96.5%, NaCl mass content
It is 0.5～1.5%, Mg (OH)2Mass content is 0.5～1.5%, CaSO4Mass content be 1.5～4%, other impurity is (main
Silicon dioxide to be referred to) mass content be 1.0～3.0%, artificial stone can be played invigoration effect, save as reinforcement material
The consumption of quartz sand；
The artificial stone production method that the present invention provides, the artificial stone quality made is through country's stone testing Spot detection, indices
Being satisfied by DB44/T 768-2010 " resin type artificial slabstone " standard, artificial stone quality prepared by two alkaline process brine sludges is qualified.
Detailed description of the invention
Below by instantiation, the present invention is described further, and the description below is only to play explanation effect, not in it
Appearance is defined.
In each embodiment, the composition of raw materials of artificial stone is as shown in table 1:
Table one: two alkaline process brine sludge prepares artificial stone formula
Brine sludge used in embodiment 1 embodiment 5 in table 1, after two alkaline reactions terminate, through the most simply washing,
Drying, being crushed to grain diameter is 20～80 μm, and all in water-washing process, controls CaCO in brine sludge3Mass content be
90～96.5%, NaCl mass content is 0.5～1.5%, Mg (OH)2Mass content is 0.5～1.5%, CaSO4Quality contain
Amount is 1.5～4%, and the mass content of other impurity (silicon dioxide) is 1.0～3.0%；And it is used in comparative example 14
Brine sludge, through repeatedly washing, or washing degree is not enough, and the content of the most all or part of trace substance is not above-mentioned
In the range of.In table 1, the concrete composition of brine sludge employed in each embodiment, comparative example is as shown in table 2:
Table 2: the concrete composition of brine sludge employed in each embodiment, comparative example in table 1
In table 1, the grating of quartz employed in each embodiment, comparative example is 26～40 mesh quartz sands: 40～90 mesh quartz sands:
90～100 mesh quartz sands: 325 mesh quartz sands=4:1:1:2；
In table 1, in each embodiment, comparative example, the preparation technology of artificial stone is:
According to each embodiment, the ingredient proportion of comparative example, resin, pigment, accelerator, coupling agent, firming agent are put into resin
High-speed stirred in agitator tank, disperses 30min；In de-airing mixer, add the two alkaline process brine sludges handled well and quartz sand expected admittedly,
And it is uniform in in-tank mixing；Then the liquid materials such as scattered resin are transferred in solid material, continue mixing to uniformly.
By mixed material vacuum cloth, entering vacuum press, first vibration dispersion, the pore during then vacuum extracts material out is (true
Reciprocal of duty cycle-0.05MPa), suppress 7min with 50T pressure simultaneously.Material after compacting proceeds to high temperature molecule stablize in room and dry surely
Fixed so that it is solidification, ambient temperature during primary solidification is maintained at 80 DEG C, time 2h；Ambient temperature during rear solidification temperature keeps
At 100 DEG C, time 3h.Artificial slabstone carries out after solidification the demoulding, fixed thickness, and through polishing, packaging prepares finished product.
Table 3: in table 1 in each embodiment, comparative example, two alkaline process brine sludges prepare artificial stone quality measurements
Note: 1: in compressive strength detection, sample is with reference to GB/T 18601-2009/6.4.2 process, folded after using cutting polishing
The method adding bonding reaches given size, and wherein after freeze-thaw cycle, compressive strength sample number of freezing and thawing is 10 times.
2: resistance to chemical attack classification is as follows:
C4Level: corrode through the acid of 8h ± 30min or alkali, gloss percent retension more than 80% (allow wherein to have one
60%～80%).
C3Level: acid and 1h ± 5min alkali through 8h ± 30min corrode, and gloss percent retension is 60%～80%.
C2Level: through alkali and 1h ± 5min acid attack of 8h ± 30min, gloss percent retension is 60%～80%.
C1Level: acid or alkali through 8h ± 30min corrode, and gloss percent retension is below 60%.
Claims (9)
1. one kind utilizes the artificial stone that two alkaline process brine sludges manufacture, it is characterised in that: each component of described artificial stone is counted by weight
Be,
Wherein, in two described alkaline process brine sludges, CaCO3Mass content be 90～96.5%, NaCl mass content be 0.5～
1.5%, Mg (OH)2Mass content is 0.5～1.5%, CaSO4Mass content be 1.5～4%, the mass content of other impurity
It is 1.0～3.0%.
Utilize the artificial stone that two alkaline process brine sludges manufacture the most as claimed in claim 1, it is characterised in that: described resin is insatiable hunger
With one or more hybrid resins in resin, epoxy resin, polymethyl methacrylate and polyurethane resin.
Utilize the artificial stone that two alkaline process brine sludges manufacture the most as claimed in claim 1, it is characterised in that: described accelerator is cobalt
System, vanadium system or the organic salt of manganese systems metal, tertiary amines, quaternary amine or mercaptan.
Utilize the artificial stone that two alkaline process brine sludges manufacture the most as claimed in claim 1, it is characterised in that: described coupling agent is for having
One or both mixture in machine silane coupling agent and titanate coupling agent.
Utilize the artificial stone that two alkaline process brine sludges manufacture the most as claimed in claim 1, it is characterised in that: described firming agent is second
Diamidogen, diethylentriamine, benzene dimethylamine, m-diaminobenzene., diamino diphenyl sulfone, beta-hydroxyethyl ethylenediamine, imidazoles, 2-first
In base imidazoles, maleic anhydride, phthalic anhydride, poly-Azelaic Acid acid anhydride, sebacic dihydrazide one or more
Mixture.
Utilize the artificial stone that two alkaline process brine sludges manufacture the most as claimed in claim 1, it is characterised in that: described pigment is titanium white
Powder, micaceous iron oxide, chrome yellow, barba hispanica, cadmium red, cadmium yellow, lithopone, white carbon black, iron oxide red, iron oxide green and ferrum oxide
One or more mixture in Huang.
7. the preparation method of the artificial stone as described in any one of claim 1 to 6, it is characterised in that: the step of described method is,
(1) batch mixing, is uniformly mixed described each component under vacuum or normal pressure；
(2) compacting, pours molding by the mixed material obtained in step (1), or mixed by obtain in step (1)
It is compressing that material after conjunction is transferred to vacuum press；
(3) curing conservation, moves to baking and curing in high hot house by compressing sheet material in step (2)；
(4) demoulding, fixed thick, polishing.
8. the preparation method of artificial stone as claimed in claim 7, it is characterised in that: the vacuum press described in step (2)
In, set vacuum less than or equal to-0.09MPa.
9. the preparation method of artificial stone as claimed in claim 7, it is characterised in that: the curing operation described in step (3)
Being divided into primary solidification and rear solidification, ambient temperature during described primary solidification is maintained at 40～100 DEG C, the primary solidification time 1～3h；
Ambient temperature during described rear solidification is maintained at 80 DEG C～140 DEG C, rear curing time 2～8h.
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Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108059173A (en) * | 2018-01-09 | 2018-05-22 | 大连润琳科技有限公司 | Milk of lime desanding and method of comprehensive utilization |
| CN108483986B (en) * | 2018-04-03 | 2020-09-18 | 临海市朵纳卫浴有限公司 | Wear-resistant mildew-proof composite material wash basin and preparation method thereof |
| CN110092610A (en) * | 2019-05-24 | 2019-08-06 | 武汉工程大学 | The method for preparing artificial stone using the high alumina salt slurry that aluminium foil corrosion is formed |
| CN110451849A (en) * | 2019-08-02 | 2019-11-15 | 黄永西 | A kind of artificial stone formula and preparation method thereof |
| CN112707681A (en) * | 2019-10-25 | 2021-04-27 | 丁国兴 | Artificial stone slab and preparation method thereof |
| CN114409349B (en) * | 2021-12-31 | 2023-02-24 | 北京润鸣环境科技有限公司 | Salty mud curing material and preparation method and application thereof |
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| CN101642926A (en) * | 2009-08-28 | 2010-02-10 | 上海贵雅橱柜有限公司 | Artificial stone with photocatalysis |
| WO2011148389A1 (en) * | 2010-05-28 | 2011-12-01 | Gosakan Aravamudan | Ornamentation of quartz resin composites |
| CN102898799A (en) * | 2011-11-03 | 2013-01-30 | 苏州拓博琳新材料科技有限公司 | Biobased artificial stone and production process thereof |
| CN103553436A (en) * | 2013-10-21 | 2014-02-05 | 岑巩县宏宇新型材料有限责任公司 | Artificial quartz plate and production method thereof |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101642926A (en) * | 2009-08-28 | 2010-02-10 | 上海贵雅橱柜有限公司 | Artificial stone with photocatalysis |
| WO2011148389A1 (en) * | 2010-05-28 | 2011-12-01 | Gosakan Aravamudan | Ornamentation of quartz resin composites |
| CN102898799A (en) * | 2011-11-03 | 2013-01-30 | 苏州拓博琳新材料科技有限公司 | Biobased artificial stone and production process thereof |
| CN103553436A (en) * | 2013-10-21 | 2014-02-05 | 岑巩县宏宇新型材料有限责任公司 | Artificial quartz plate and production method thereof |
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