CN101074153A - Jet-pump delivering building material-soil coagulating agent - Google Patents

Jet-pump delivering building material-soil coagulating agent Download PDF

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Publication number
CN101074153A
CN101074153A CNA2006100804751A CN200610080475A CN101074153A CN 101074153 A CN101074153 A CN 101074153A CN A2006100804751 A CNA2006100804751 A CN A2006100804751A CN 200610080475 A CN200610080475 A CN 200610080475A CN 101074153 A CN101074153 A CN 101074153A
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China
Prior art keywords
coagulating agent
weight
oxide
waste
soil
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Pending
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CNA2006100804751A
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Chinese (zh)
Inventor
李智
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Individual
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Individual
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Priority to CNA2006100804751A priority Critical patent/CN101074153A/en
Publication of CN101074153A publication Critical patent/CN101074153A/en
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    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
    • C04B28/34—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing cold phosphate binders
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/00034—Physico-chemical characteristics of the mixtures
    • C04B2111/00146—Sprayable or pumpable mixtures
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/00474—Uses not provided for elsewhere in C04B2111/00
    • C04B2111/00732—Uses not provided for elsewhere in C04B2111/00 for soil stabilisation
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2201/00—Mortars, concrete or artificial stone characterised by specific physical values
    • C04B2201/10—Mortars, concrete or artificial stone characterised by specific physical values for the viscosity
    • 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

Abstract

A jetted and pump-delivering soil coagulating agent material is harder. It reduces coagulating reactive speed and delays coagulation. Once it's deposited, soil coagulating agent liquid material can be its impact final structure.

Description

A kind ofly spray, pump delivering building material-soil coagulating agent
Technical field
The present invention relates to spray, the material of construction-soil coagulating agent of pumping specifically, this soil coagulating agent composition can keep low viscosity with time expand, so as with said composition with injection, be pumped into and comprise in the geology or artificial place that is difficult to arrive.
Background technology
The soil solidification technology is revolution that is with historically new significance on world's road construction history.Traditional mode of building the road is an incoming road material outside using in a large number in construction, by the construction technology of " physics-mechanics ", reaches the mode of every engineering mechanics index.The soil solidification technology is to rely on the unique chemical solidifying agent to be stirred in the soil of building the road, construction technology by " chemistry-physics ", change properties of physical mechanics of soil, thus build up have high strength, a kind of advanced person's of the highway pavement of high stability, high-bearing capacity technology.
Prevent the material loss of stability, to such an extent as to produce seepage.The material that also will make great efforts to make desire to handle combine with tackiness agent with formation solid bulk or waste structure and is used for burial or makes building products.For example, disclose in people's such as Frey the United States Patent (USP) 4432666, adopt tackiness agent and go his water-resistant adhesives processing waste to be considered to that environment is had destruction.Yet, tackiness agent instability under many circumstances, such as, when packing halogenide.
The shortcoming in the above-mentioned method of mentioning, all unfavorable formation flowable mixture of structure of the raw material in the commercially available aforesaid method (particularly oxide compound), the result, the reflection of heating becomes uncontrollable.Cause forming thick slurries.Make the finished product lack uniformity.And the rapid solidification time of gained pottery can not guarantee enough working hours.
Prior art formula can provide waste liquid to adapt to the firm of under different deposition conditions multiple waste material, and it has denseness prolongation, that also use or viscosity with present employing splashing device.This method also provides to be selected and the agreement of preparation recipe ingredient, needs prescription under the different viscosity situation with design.
Summary of the invention
The present invention not only provides a kind of prescription that comprises the soil coagulating agent material, this prescription be a kind of waste is used as can spray, the method for a kind of main body composition in the pumping peptizer.Be characterized in adopting additive to slow down reaction between the condensing agent component.Advantage is to have prolonged the time of operability and used obsolete up to now waste.
Also have, provide a kind of common commercially available oxygenate conversion is become a kind of component in the sprayable soil coagulating agent, burn oxide compound as it is characterized in that, then the oxide compound of calcination is mixed with paint.Advantage is to have reduced the oxide compound of calcination and the speed of reaction of other condensing agent components, thereby has prolonged the operable time of condensing agent before solidifying.
In brief, the invention provides the soil coagulating agent of injection, pumping, this soil coagulating agent can have been bought by market.
Description of drawings
Can understand the present invention best together with above-mentioned and other purpose and advantage by the detailed description of following illustrated inventive embodiments.
Fig. 1 produces the sprayable method synoptic diagram that solidify waste consistent with feature of the present invention.
Fig. 2 is sprayable X light diffracting analysis result of solidifying waste of the present invention.
Fig. 3 A and 3B are respectively suitable and microphotographs inappropriate oxide component in the CBPC prescription consistent with feature among the present invention.
Fig. 4 A and 4B are respectively the x-ray diffraction analytical resultss suitable and inappropriate oxide component that is used in the sprayable CBPC prescription of invention.
Fig. 5 is a determination number of determining the suitable oxide compound consistent with feature of the present invention.
Fig. 6 is the solubility curve figure of various oxide compounds consistent with feature of the present invention.
Embodiment
A kind of soil coagulating agent is added can spray, the method for the mixture of pumping, such mixture can be fixed on successively and comprise the place that is difficult to arrive.Equally, this mixture extensively is utilized and can builds the road on the spot, also combine with waste and encapsulate waste, particularly waste can not arrive or the situation in hazardous area under, as the sarcophagi of the nuclear power plant that pollutes, or waste leaks the place.Though this method has postponed the coagulation of phosphate ceramics, also reduced the overall viscosity of phosphate ceramics slurries or phosphate ceramics/waste slurries, be enough to allow slurries can be injected or other modes be transported to final place.At last, this method has prepared a kind of CBPC structure hard, that be difficult to permeate, and the resisting power of this CBPC structure can be contended with concrete, and, needn't heat in addition.
About thisly spray, the soil coagulating agent material of pumping.Thereby slow down congealing reaction speed, postpone to condense and solidify enough allow the soil coagulating agent material liquid that reacts can be injected or other modes be transported to and finally leave standstill the place.In case deposit soil coagulating agent material liquid solidifiable or become its closely knit final structure.Although adopted the admixture speed of response that slows down, it is harder than the product that adopts portland cement to produce that the finished product have been proved to be.General pressure surpasses 4,000 pounds per square inch.
Can spray, the making of the soil coagulating agent material of pumping is shown in numeral 10 among Fig. 1.In brief, oxide powder 12 mixes with phosphoric acid salt powder/solution 14 and pre-fractionated waste material 16 in first mixed processes 17 in varing proportions.
The granularity of waste material is suitable less than 200 microns.Can adopt multiple phosphate solution, this solution comprises the phosphoric acid salt of cation part, cationic moiety be selected from potassium, sodium, calcium, zirconium, iron, magnesium-ammonium with and combination.The concentration of suitable phosphate solution be the slurries that produced when combining with the component of enumerating below, a kind of liquid can be provided, the centipoise value of this liquid can be impelled and disperses easily.This phosphatic concentration can be water and KH 2PO 4Weight ratio about 0.66.
The mixing of oxide powder, phosphate solution and waste has produced first kind of mixture or slurries 18.Optionally, with before phosphate solution and waste material mix, oxide powder will carry out the pre-treatment of operation 11.Details are as follows for the oxide compound pretreatment process.
Suitable oxide compound: phosphoric acid salt: waste weight ratio scope is 1: 3.4: 1.45 to 1: 3.4: 6.6.When MgO is used as oxide compound, KH 2PO 4When being used as waste material as phosphatic and ash, specially suitable MgO: KH 2PO 4: the weight ratio of ash is 1: 3.4: 1.45.
In an exemplary sequence, slurries 18 are combined into second kind of mixture 21 with the additive that contains different insulating covering agents and water-retaining agent.But the different positions that additive can be in hybrid technique adds, such as, include but are not limited to the insulating covering agent of citric acid or boric acid, can before the mixing of oxide compound and phosphate solution and waste material, directly add in the oxide powder 12.Then, water-retaining agent as Sulfite lignin, can add after above-mentioned three kinds of components mix fully.
After additive mixed, water 22 joined in the mixture for preparing, and current aqueous liquid enters second kind of mixing step 23, produce a kind of homogeneity, active liquid 25, general mixing time is about 20 to 60 minutes.
Water adds when reaction process 24 beginnings.In reaction process 24, current active material 25 can be injected into the operation 26 of grout or other modes before final condensing occurs.The condensing of mixture 25, firm or solidify 28 can appearance in above-mentioned after adding water step 22 two hours.
A notable attribute of the inventive method is, heating outside not needing in finally the solidifying of reaction, injection, transportation and soil coagulating agent liquid.
Although the additive effect is to make the reaction liquid fluidization, the waste structural table that finally solidifies of gained reveals good properties.Such as, as shown in Figure 2, a kind of waste structure that mainly contains the trimagnesium phosphate potassium that is crystalline structure that this method provides, spike is represented crystalline structure among the figure.
The details of oxide compound preparation
Multiple oxide compound all is suitable as the powder among the present invention, and calcium oxide, sodium oxide, zirconium white, ferric oxide, magnesium oxide and combination thereof all are the startup powder that suits.
The contriver finds that the pre-treatment 11 of oxide compound can improve the flowability of final ceramic binder-waste mixture usually.Yet commercially available pre-treatment oxide compound can not reach its desired value when improving flowability.Be more suitable for, the invention method of calcination of Pi Luing can be produced a kind of tackiness agent with optimum performance (as high strength and low viscosity) herein.The product that adopts oxide compound pretreatment process 11 of the present invention to obtain has that solidification rate is about two hours even also be low heat release (as producing low heat) in condensing process, and the structure characteristics of homogeneous very.
In order to prepare suitable soil coagulating agent, oxide component should have following characteristic:
1. the granularity of average oxide particle should be at the 8-10 micron, and each particle should be closely knit, crystalline state, and does not contain amorphous covering.
2. the oxide particle that is adopted, the soil coagulating agent mixture should not produce a large amount of heats in mixing process.Equally, selected oxide particle can not make slurries send out thick.
3. the finished product should be homogeneous ceramics, and, should not in slurries, to form precipitation rapidly.Ultimate pressure is at least 3,500 pound per square inches.Product disconnects or bonded porosity accounts for monoblock volume formation or that solidify and should be less than 10% approximately.
For this reason, at the scene by final user or other people effect that adopt, the oxide compound pretreatment process.
Shown in the decision tree among Fig. 5, if become a kind of suitable component of the flowed soil coagulating agent that is used for waste, oxide compound must satisfy following three standards:
A) surface-area: powder surface is long-pending should be at 0.3-0.55m 2/ g, the inventor finds in addition, particle agglomeration and the surface-area that causes reduce the reaction between the inhibited oxidation thing and other reactants successively, with fast reaction speed, make slurries overheated when the above-mentioned scope of surface area ratio is big, and slurries are seethed with excitement.The surface-area of industrial suitable oxide compound is about 4m 2/ g.
B) morphological structure: under powerful microscope (as, 1500X), oxide surface should be the plane, and has streak to be indicated as crystalline structure.Fig. 3 A and 3B have described suitable and morphological structure improper sample respectively.
Except to oxide compound vision, the microscopy, the x-ray diffraction analysis also can be judged the effective crystalline structure in the oxide compound.For example, suitable oxide compound (Fig. 4 A) demonstrates spike, show it is crystalline structure, and inappropriate oxide compound (Fig. 4 B) demonstrates broad peak, shows to have amorphous substance.The amorphous substance qualitative response is fast, and produces unnecessary excessive heat in slurries.
C) solvability: the solvability of oxide compound in phosphoric acid solution also can judge it is suitable and inappropriate oxide compound, and usually, the solubleness of oxide compound is more little, the suitable more preparation soil coagulating agent that can flow, and such material will condense into the piece that is difficult to permeate.There is more MgO particle in the oxide compound of low solubility after making reaction, therefore, has more nucleus in reaction soln, and these nucleus can help to form independent hard central point, and increases the bulk strength of final waste structure.
Fig. 6 has showed the curve of two kinds of suitable oxide compounds (dotted line) and two kinds of inappropriate oxide compounds (solid line).As seen, make a kind of pH value of acid-oxide solution reach 8 needed weight, suitable oxide compound Duos 20% than inappropriate oxide compound.Initial foreign matter content in the suitable oxide compound does not influence its solubleness.For example, how soluble oxide compound among Fig. 5 (as suitable oxide compound) has the calcium contamination thing of different content, wherein a kind of oxide compound (analysis grade) calcic weight ratio is 0.05%, and another kind of suitable oxide compound (technology grade) calcic weight ratio is 0.45%.
The solubility test of oxide compound to be selected is carried out as follows, is made into H by deionized water 3PO 4Concentration is 5% 30ml solution, keeps whipped state by magnetic stirring apparatus or other modes, adds the MgO of 1 gram, makes the mixture for preparing to balance, record pH value.Add MgO again, each 1 gram is until balance.Last till that so always the pH value reaches 8.
The inventor finds that the method that a kind of preparation meets the oxide compound of above-mentioned A-C standard is by a kind of method for calcinating.If use commercially available MgO, this oxide compound must be such as previously mentioned, and at first granularity is between the 8-10 micron, and calcium contents is no more than 0.5% weight in the oxide compound.
In the stove, furnace temperature keeps 1,300 ℃ in case definite suitable calcium contents and grain graininess, oxide compound are packed into.Oxide compound can enter " preheating " stove, perhaps packs in the process that stove heats up gradually.The soaking of oxide compound or heat-up time are variant according to oxide raw material (and impurity) character.High-purity (analysis grade) the oxide compound soaking time is about one hour, and the oxide compound of technical grade purity needs three hours heat-up time approximately.
After the heating, sample cools off in stove, and the cooled oxide compound of result is generally agglomerating bulk, and such bulk must be ground to the 8-10 micron again.
Additive describes in detail
As previously mentioned, a prominent feature of the present invention is to use additive to stop reaction, therefore enlarges the usability of reaction solution 23.Additive comprises two kinds of components: insulating covering agent and water-retaining agent, or be water-removal agent.As previously mentioned, suitable insulating covering agent is to be selected from boric acid, citric acid and combination thereof.Covering component in the additive has the covering effect and makes oxide particle avoid exposing fully, or contacts with other reactants.
Suitable water-retaining agent comes the phosphatic polymerizable organic compound class of self-contained lignin.The effect of lignin phosphate compounds is to avoid very fast response of water and phosphoric acid salt, and in fact, these wood cellulose compounds can absorb any moisture to prevent the very fast hydration of phosphoric acid salt.The lignin phosphate compounds of alkalescence is preferred water-retaining agent, is selected from Sulfite lignin, lignin phosphoric acid salt and other hydroxyl organic compounds and combination thereof especially.The suitable lignosulfonic acid salt compound of one combination has: sodium lignosulfonate, calcium lignosulfonate, lignin sulfonic acid potassium and combination thereof.A kind of exemplary lignosulfonic acid salt compound is Daratard 17 TM, the weight percent that joins the additive in the last reaction solution can be different, and 0.5%-3.5% is proper.Usually, additive and first kind of mixture combination, additive: oxide compound: the phosphoric acid salt part by weight is at 1.83: 10.3: 35 to 2.1: 10.3: 34.
The inventor finds that the dehydrating effect of lignosulfonate/naphtalene sulfonate compound strengthens when having boric acid to exist, and the weight ratio of its mesoboric acid is similar with the weight ratio that is used in the Sulfite lignin.
Additive can be before the reaction of reaction process 24 any time or add during beginning, the exemplary results that obtains, as Fig. 1 indication like that, i.e. adding before adding water 22.
In one embodiment, the concrete ratio of every kind of component is as follows in the final sprayable product: basic oxide (12 weight %), phosphoric acid salt (4 weight %), floating dust (17 weight %), boric acid (1 weight %), Sulfite lignin (1 weight %) and water (29 weight %).The slurries of present embodiment have the denseness identical with milk, thereby easy pumping or formation grout, and after two to three hours, slurries are transformed into the intensive CBPC structure of hard.As shown in Figure 2, last structure is carried out the x-ray diffraction analysis, except aqueous trimagnesium phosphate potassium, also have remaining magnesium oxide to exist.
Because spray during less than 1,500 centipoise and the effect of injection can improve in viscosity, the insulating covering agent in the additive is suitable at the prescription of 0.5-3 weight % (containing insulating covering agent and water-retaining agent in the additive).
Several dissimilar base-materials can with can spray, the soil coagulating agent of pumping combines individually or jointly, forms the CBPC structure.These wastes include but not limited to clay, soil, red soil and combination thereof.It can be necessary that thing section is carried out classification, grinding or other pre-treatment.The size range of suitable waste material is between the 10-200 micron.
From following table 10 as can be seen because the denseness of the different slurries of the concentration of additive is also different.Table 1 has shown the viscosity centipoise value (cp) of weight concentration slurries when 0.5%-3.5% of the whole relatively slurries of additive.
The withered degree of CBPC gurry liquid during table 10 different additive concentration
Additive hardness concentration (weight %) Initial viscosity (centipoise) Waste particle＜200 micron weight % Setting time (minute) Finally (pound/square inch)
0.0 27,000 60 20 ＜8000
2.0 300 15 ＞190 ＞3000
2.5 3000 28 190 ＞3000
The slurries of gained/as described above, perhaps as the particle disposal that can spray, contain in the liquid of pumping, or as the sealing agent of firm other waste materials.For example, the slurries of allocating ash content into can be expelled to and make soil curing in the contaminated soil.Although the present invention is described by the embodiment that is described in detail, it is not that the invention scope that claims are limited forms restriction.

Claims (9)

  1. One kind can spray, pump delivering building material-soil coagulating agent, containing inorganic oxide, phosphoric acid salt and polymerization organic materials is alkaline Sulfite lignin, is selected from sodium lignosulfonate, calcium lignosulfonate, lignin sulfonic acid potassium and combination thereof.
  2. 2. the polymerized organics described in claim 1, the weight percent that accounts in composition is between 1% to 3%.
  3. Described in claim 1 polymerization organic materials and boric acid to be about 0.6: 1.25-1: part by weight between 1 combination.
  4. 4. described in claim 1. contain waste material in the soil coagulating agent at 15-20 weight %.
  5. 5. soil coagulating agent described in claim 1, wherein begin to mix surpass 1 hour after, soil coagulating agent viscosity is about 850-15, between 000 centipoise.Need not heat.Wherein the surface-area of inorganic oxide is at 0.3m 2/ g-0.55m 2Between/the g.
  6. 6. a kind ofly described in claim 1 spray, the base-material waste prescription of pumping, by weight,
    Contain 7-14% basic oxide, 25-40% phosphoric acid salt, 15-50% ash, 1-4% boric acid, 0.5-2% Sulfite lignin and 15-25% water.
  7. 7. a kind ofly described in claim 1 spray, the base-material waste prescription of pumping, by weight, contain 10% basic oxide, 35% phosphoric acid salt, 15% floating dust, 1.2% boric acid, 0.61% Sulfite lignin and 23% water.
  8. Described in claim 1 a kind of system each can spray, the method for the base-material waste of pumping, comprise, select inorganic oxide with surface-area and form standard that H2PO determines as solvent; Simultaneously, selected oxide compound is mixed first kind of mixture of formation with phosphate solution and waste; Again and the lignosulfonic acid salt compound is and boric acid with 1: 1-2: the part by weight combined hybrid between 1.In second kind of mixture, add entry, form a kind of activated mixture; Activated mixture is homogenized; And activated mixture is solidified.
  9. 9. the viscosity that described in claim 1, requires the homogenizing activated mixture at 200 centipoises between 1000 centipoises.
CNA2006100804751A 2006-05-17 2006-05-17 Jet-pump delivering building material-soil coagulating agent Pending CN101074153A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CNA2006100804751A CN101074153A (en) 2006-05-17 2006-05-17 Jet-pump delivering building material-soil coagulating agent

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Application Number Priority Date Filing Date Title
CNA2006100804751A CN101074153A (en) 2006-05-17 2006-05-17 Jet-pump delivering building material-soil coagulating agent

Publications (1)

Publication Number Publication Date
CN101074153A true CN101074153A (en) 2007-11-21

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CNA2006100804751A Pending CN101074153A (en) 2006-05-17 2006-05-17 Jet-pump delivering building material-soil coagulating agent

Country Status (1)

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