CN1526529A - A burn-free brick made from oilfield sludge and its production method - Google Patents

A burn-free brick made from oilfield sludge and its production method Download PDF

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CN1526529A
CN1526529A CNA031390536A CN03139053A CN1526529A CN 1526529 A CN1526529 A CN 1526529A CN A031390536 A CNA031390536 A CN A031390536A CN 03139053 A CN03139053 A CN 03139053A CN 1526529 A CN1526529 A CN 1526529A
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curing agent
cement
sludge
river sand
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CN1226120C (en
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岳云龙
杨中喜
吴波
陶文宏
宋廷寿
隋肃
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University of Jinan
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Abstract

The present invention relates to no-baking brick, and is especially no-baking brick made of oil field sludge and its production process. The no-baking brick of the present invention is produced with the following material and through mixing and extrusion in extruder: oil field sludge 30-60 wt%, river sand 15-40 wt%, cement 15-30 wt%, flyash 0-35 wt% and curing agent 1-8 wt%. The no-baking brick of the present invention has high strength, no pollution and simple production process, and the present invention solves the problem of pollution and exhaust of oil field sludge.

Description

Baking-free brick prepared from oil field sludge and production method thereof
(I) in the field of technology
The invention relates to a baking-free brick and a production method thereof, in particular to a baking-free brick prepared from oil field sludge and a production method thereof.
(II) background of the invention
Oil-well muds are blood of oil drilling engineering, and with the development of the oil industry, the yield of the oil-well muds is increasing, and the oil-well muds generally contain a large amount of substances such as heavy metals, oils, alkalis and chemicals (including organic matters) which are extremely harmful to human beings, livestock and the environment. If the mud is discarded after use, the substances can seriously pollute the environment, harm the life and the body health of people and influence the growth and development of animals and plants if the mud is not treated.
The treatment and application of the oily sludge are the problems which are difficult to solve in the treatment process of the oily sewage. The technologies of oily sludge treatment and sludge comprehensive utilization by adopting biotechnology, physical and chemical methods and the like in western europe and the united states have been used for decades, the main processes comprise sludge concentration, conditioning, dehydration, harmless solidification, heat treatment, biological treatment, high-temperature treatment and the like, wherein the researches on biological treatment, disposal technology, high-temperature technology and solidification technology for drying oily sludge are more important, and as the oily sludge is an organic matter taking petroleum hydrocarbons as a main organic component, the biological treatment and disposal technology is to reduce the harm of the oily sludge to the environment by degrading the petroleum hydrocarbons by using microorganisms; the high-temperature treatment technology is used forrecovering hydrocarbon substances from the oily sludge by utilizing heat energy, and the process is carried out under a closed condition, so that the pollution to the surrounding environment can be reduced; the solidification treatment method is mainly characterized in that a certain composition of a curing agent is added into the oil field sludge to cause certain physical and chemical reactions, so that the water and a part of toxic substances in the oil field sludge are solidified and have certain strength so as to be convenient for stacking or storing.
In the aspect of comprehensive utilization of the oily sludge, the main utilization direction is the research of building materials, namely, the oil field sludge is taken as a main raw material, and a certain process is adopted to produce the ecological building materials, so that the oil field sludge is recycled, the waste is changed into the valuable, and a certain value is created for the society. On the other hand, the method solidifies toxic substances in the oil field sludge, prevents pollution of the oil field sludge, protects the ecological environment, prevents underground water from being polluted and harms personal safety, accords with national policies and industrialization policies, and is a sustainable development technology.
At present, China is more suitable for treating the oil field sludge by utilizing a solidification technology. However, in the prior art, the curing strength can not meet the requirements of building bricks on one hand, and can not meet the requirements of ecological building materials on the other hand, and the alkalinity, toxicity and radioactivity tests of the prior art do not meet the building material standards.
Disclosure of the invention
In order to overcome the defects, the invention provides the baking-free brick which is prepared from the oil field sludge and has high strength and meets the ecological environment-friendly requirement, and the production method thereof.
The invention is realized by the following measures:
a baking-free brick prepared from oil field sludge is prepared from the raw materials (by weight proportion) through mixing, and extruding with press,
oil field sludge: 30 to 60 percent
River sand: 15 to 40 percent of
Cement: 15 to 30 percent of
Fly ash: 0 to 35 percent
Curing agent: 1 to 8 percent
The curing agent is prepared from the following raw materials in parts by weight:
sulphoaluminate salt: 15% -25% of calcium stearate: 0 to 10 percent
Calcium chloride: 0-25% calcium acetate: 0 to 15 percent
Fluorite: 0-10% gelatin: 5 to 10 percent of
Gypsum: 10% -25% of lime: 10 to 30 percent
0 to 5 percent of acrylic resin
The baking-free brick of the invention comprises the following raw materials in parts by weight:
oil field sludge: 30 to 50 percent of
River sand: 15 to 30 percent of
Cement: 15 to 25 percent
Fly ash: 10 to 30 percent
Curing agent: 2 to 6 percent
The curing agent is prepared from the following raw materials in parts by weight,
sulphoaluminate salt: 15% -25% of calcium stearate: 0 to 10 percent
Calcium chloride: 10% -25% of calcium acetate: 0 to 15 percent
Fluorite: 4% -10% gelatin: 5 to 10 percent of
Gypsum: 10% -25% of lime: 10 to 30 percent
0 to 5 percent of acrylic resin
In order to improve the curing effect, the baking-free brick of the invention is also added with a core material accounting for 8-10% of the curing agent by weight, wherein the core material comprises the following raw materials in parts by weight:
CaO MgO Fe2O3 SiO2 Al2O3 Al2(SO4)4 Na2CO3 FeSO4 MgSO4
5-10 5-10 5-10 6-15 8-15 2-20 10-20 5-20 5-20
the production method of the baking-free brick comprises the following steps,
1) adding appropriate amount of water into oil field sludge, river sand, cement, fly ash and curing agent, and mixing
The mixture is uniform and the mixture is uniform,
2) the slurry is filled into a die, the pressure of 500-700KN is applied on a press machine for pressing and forming,
demoulding and drying to obtain the finished product.
The curing mechanism of the present invention will now be further described:
the research utilizes testing means such as a D/max-rA type X-ray diffractometer, an S-2500 type scanning electron microscope and the like to research the curing mechanism of the baking-free bricks of the oil field sludge building.
X-ray diffraction analysis
As shown in figure 1, the main crystal phase-calcite in the sludge raw material is rarely seen in the cured baking-free brick, and besides quartz in the river sand as the filler, more minerals such as ettringite, calcium silicate hydrate, calcium carbonate aluminate, calcium aluminate hydrate and the like are seen.
2. Electron microscopy analysis
Scanning electron micrographs are shown in fig. 2 and fig. 3, fig. 2 is an electron micrograph of the laan oil field sludge baking-free brick cured for 7 days, fig. 3 is an electron micrograph of the oil field sludge baking-free brick cured for 28 days, and comparing fig. 2 and fig. 3, it can be found that the structure of fig. 2 is loose, and the solid particles are less in cementing and bonding minerals and are generally only hydration products of cement, namely calcium silicate hydrate; fig. 3 shows a compact structure, and various needle-shaped, rod-shaped and sheet-shaped cementing substances are filled among solid particles, and most of the cementing substances are minerals such as ettringite, calcium carbonate aluminate and calcium aluminate hydrate, which are formed by the combined action of curing agents, cement and some components in the le' an oilfield sludge.
3. Study of curing mechanism
From the above X-ray diffraction analysis and electron microscopic analysis, it is known that there are two main parts, C in cement, which play a role in solidification during the whole solidification process of oilfield sludge3S、C2S and other minerals are hydrated to form hydrated calcium silicate, and the action can be represented by a formula (5-1): (formula 5-1)
Secondly, calcium carbonate in the sludge of the oil field and C in the cement3A reacts to form acicular calcium carbonate aluminate (C)3A·3CaCO3·32H2Oand C3A·CaCO3·12H2O) its action can be represented by formulas 5-2 and 5-3: (formula 5-2) (formula 5-3)
Finally, the curing agent, the cement and the aluminum ions, the sulfate ions, the calcium ions and the like in the oil field sludge act together to form the ettringite.
1) The effect of cement
The cement and the waste mud are mixed with water and then have hydration reaction in cement hydrate, and the Calcium Silicate Hydrate (CSH) with the cementing effect is the main component which has the greatest contribution to the strength. Studies of cement chemistry have shown that:
(1) hydrated Calcium Silicate (CSH) produced in the liquid phase has a substantially constant Ca/S ratio, and Ca/Si is about 1.2. The thermodynamic equilibrium equation generated by CSH can be written as:
(2) liquid phase original Ca/Si, OH-The ratio of Si influences the type of hydration product when the original Ca/Si, OH of the liquid phase-When the ratio/Si is smaller, the silicic acid gel without the binding effect occupies a larger proportion in the hydration product along with the original Ca/Si, OH of the solution-The increase in the ratio/Si increases the proportion of CSH in the hydration product. From the thermodynamic equilibrium equation, liquid phase Ca2+、OH-Reduction of Ca (OH) in the pore water of cement2Under unsaturated conditions, the slurry must absorb a large amount of Ca necessary for the formation of CSH in order to achieve saturation adsorption2+、OH-This results in a decrease in the amount of CSHproduced. In the process of forming cement soil, the slurry is coupled with OH-,Ca2+The absorption and cement hydration of (2) release Ca (OH)2Are performed simultaneously. Early mud to OH-,Ca2+The large amount of absorption may result in the original Ca/Si, OH of the cement pore water-The ratio of Si is too low, so that the amount of silicic acid gel without binding capacity in the cement hydration product is increased, and OH is further consumed-、Ca2+The production amount of CSH is further reduced. Slurry pair OH-,Ca2+The higher the absorption amount of (A), OH in the cement pore water-,Ca2+The lower the concentration, the less CSH is produced by hydration of the cement in the cement soil. The curing agent contains minerals with high calcium content such as lime, gypsum, etc. so that Ca (OH)2Ca in supersaturated concentration to form CSH gel2+And OH-The concentration is sufficiently high so that the bonding effect of the curing agent is good. In addition, the active material slag is greatly mixed to replace part of cement, and Ca (OH)2After the reaction is carried out, more hydrates such as CSH gel are generated and the strength of the hydrates is continuously developed.
2) The action of the curing agent
The oil field sludge sample has weak interparticle connection, and a large amount of pore water causes the strength of the sample to be low, so that the strength of the sample is improved, an ideal curing agent has double functions of cementing particles and filling pores, and experimental research shows that cement is used as the curing agent, main hydrate of the cement is hydrated calcium silicate, CSH has strong cementing capacity, loose sample particles can be cemented into a whole, but the efficiency of filling the pores is low, CSH gel is generated between the sample particles and particles, the CSH gel is attached to the pore walls of the pores of the sample, the pore wall sample is cemented into a whole, but the effect of filling the pores is weak, and a large amount of pores still exist. Although CSH enhances the interparticle connection, the curing strength is improved to a certain extent; however, it cannot compensate for the strength loss caused by the voids in the specimen, and the curing strength is not ideal. The curing agent contains gypsum, and when the curing agent is hydrated, the gypsum reacts with aluminum-containing phase to generate a large amount of ettringite besides the same reaction as that of cement. The ettringite is a needle-like crystal under certain conditions, and the solid phase volume of the ettringite can be increased by about 120 percent in the crystal forming process. On one hand, the ettringite exists, and on the other hand, the ettringite fills partial pores due to the expansion of the solid phase volume of the ettringite, so that the amount of the pores of the test body is reduced; on the other hand, larger needle-like crystals are generated in the pores, are mutually crossed to form a space structure together with calcium silicate hydrate, and are supported and filled in the pores with higher efficiency to thin the pore size distribution of a solidified body, and researches on porous materials show that: the strength of a material is inversely related to its amount of porosity, with less porosity giving a higher strength. When the pore volume is the same, the smaller the average pore diameter is, the higher the strength is, the pore volume in the solidified soil is reduced, the average pore diameter in the solidified body is reduced, the pores between the particles are connected through the CSH gel, compared with the case of no curing agent is added, the strength of the sample is greatly increased due to the generation of the CSH gel, the curing agent not only generates a large amount of CSH gel, but also generates a plurality of fine needle-shaped stones, the ettringite is mutually crossed with calcium silicate hydrate, and the two stones interact with each other, so that the curing effect of the curing agent is better.
From the above analysis, it can be seen that what plays a role in curing in the baking-free brick of the oilfield sludge building is the result of the combined action of the curing agent, the cement and the oilfield sludge.
In conclusion, the baking-free brick has high strength and no pollution, and meets the requirements of ecological environment protection; the problems of pollution and discharge of sludge in the oil field are solved; the production method has the advantages of simple process and convenient manufacture.
(IV) description of the drawings
FIG. 1 is an X-ray diffraction pattern of the baking-free brick of the present invention
FIG. 2 is an electron micrograph of a baking-free brick of the present invention cured for 7 days
FIG. 3 is an electron micrograph of a non-fired brick of the present invention cured for 28 days
(V) detailed description of the preferred embodiments
1. Example 1
The raw material mixture ratio of the embodiment is 30% of oil field sludge, 40% of river sand, 26% of cement and 4% of curing agent.
Wherein, the curing agent is prepared by mixing the following raw materials in parts by weight:
sulphoaluminate salt: 22% calcium stearate: 5 percent of
Calcium chloride: 20% of calcium acetate: 0
Fluorite: 0 gelatin: 5 percent of
Gypsum: 20% of lime: 18 percent of
Acrylic resin 0
Core material: 10 percent of
Wherein the core material is prepared from the following components in parts by weightThe raw materials are mixed to obtain:
CaO MgO Fe2O3 SiO2 Al2O3 Al2(SO4)4 Na2CO3 FeSO4 MgSO4
10 8 10 8 10 5 12 19 18
the production method comprises the following steps:
after the oil field sludge, the river sand, the cement and the curing agent are uniformly mixed, the mud slurry is filled into a die, the pressure of 550KN is applied to a press machine for pressing and forming, and the finished product is prepared after demoulding and drying.
According to the experimental method of the building materials specified by the national standard, the physical size, the volume weight, the water absorption rate, the mechanical properties (compression strength and rupture strength), the freezing resistance, the alkalinity content, the toxicity and the radioactivity of the baking-free brick are tested according to the standard of GB11945-89 autoclaved sand-lime brick and the standard of JC239-77 fly ash brick.
1) And (3) testing physical properties: physical size 240 x 116 x 52 cubic mm, capacity 2.17g/cm3The water absorption was 2.45%.
2) Mechanical properties: the average compressive strength of the steel plate after 28 days is 48.07Mpa, and the average flexural strength of the steel plate after 28 days is 12.26 Mpa.
3) And (3) freezing resistance test: every ten baking-free bricks are combined into a group, after 15 times of freeze-thaw cycles, the average compressive strength of the bricks is 46.43MPa, and the dry mass loss of a single brick is 1.13%.
4) Testing the alkali content: adding distilled water until the distilled water overflows the baking-free brick body, and heating to boil for 2-3 hours. After cooling, the pH value of the distilled water is 7-8, the distilled water is alkalescent, and no blooming phenomenon is caused.
5) And (3) toxicity testing: adding distilled water into the baking-free brick according to a certain proportion, oscillating and soaking for 8 hours, standing overnight, filtering by using 0.45-micron filter paper, taking filter residue as first leaching solution, adding distilled water into the filter residue according to the same proportion, soaking for multiple times according to the same method, and then compactingThe results are shown in the following table:
number of immersion times CODcr(mg/L) pH value Cr2+,Pb2+,Zn2+
1 2.14 7.5 Not measured out
2 0.89 7.0 Not measured out
3 0.30 6.0 Not measured out
4 0.25 5.5 Not measured out
6) And (3) radioactivity testing: the test is carried out by adopting an FD-3007K-A type pocket-sized radiometer, the radiation dose rate is 0.14uSV/h, and the radiation dose per month is 15.3 uSV. The radioactivity of the radiation is close to the radiance and radiation dose of the atmosphere.
The test results show that all the performances of the baking-free brick greatly exceed the national relevant standards of building bricks.
2. Example 2
The raw materials of the embodiment comprise 35% of oilfield sludge, 20% of river sand, 20% of cement, 24% of fly ash and 1% of curing agent.
Wherein, the curing agent is prepared by mixing the following raw materials in parts by weight:
sulphoaluminate salt: 15% calcium stearate: 2 percent of
Calcium chloride: 10% of calcium acetate: 15 percent of
Fluorite: 10% gelatin: 9 percent of
Gypsum: 10% of lime: 25 percent of
Acrylic resin 4%
After the oil field sludge, river sand, cement, fly ash and curing agent are uniformly mixed, the mud material is filled into a die, the pressure of 650KN is applied on a press machine for pressing and forming, and the finished product is prepared after demoulding and drying.
The performance test results are: the average compressive strength of the steel plate after 28 days is 16.66MPa, and the flexural strength of the steel plate after 28 days is 5.65 MPa. The mechanical property of the material can still meet the relevant national standard. Other properties were substantially the same as in example 1.
3. Example 3
The raw material mixture ratio of the embodiment is 55% of oil field sludge, 20% of river sand, 18% of cement and 7% of curing agent.
Wherein, the proportion of the curing agent is as follows:
sulphoaluminate salt: 20% calcium stearate: 5 percent of
Calcium chloride: 15% of calcium acetate: 10 percent of
Fluorite: 0 gelatin: 5 percent of
Gypsum: 15% of lime: 10 percent of
Acrylic resin 0 monoethylene glycol 5%
5 percent of sucrose
Core material: 10 percent of
Wherein the core material consists of the following raw materials in percentage by weight: CaO MgO Fe2O3SiO2Al2O3Al2(SO4)4Na2CO3FeSO4MgSO45 5 6 15 12 20 20 7 10
The production method comprises the following steps: after the oil field sludge, river sand, cement, fly ash and curing agent are uniformly mixed, the mud material is filled into a die, the pressure of 650KN is applied on a press machine for pressing and forming, and the finished product is prepared after demoulding and drying.
The performance test results are: the average compressive strength of the steel plate after 28 days is 35.26Mpa, and the flexural strength of the steel plate after 28 days is 8.65 Mpa. The mechanical property of the material can still meet the relevant national standard. Other properties were substantially the same as in example 1.
4. Example 4
The raw materials of the embodiment comprise 30% of oilfield sludge, 26% of river sand, 25% of cement, 16% of fly ash and 3% of curing agent.
The production method comprises the following steps: after the oil field sludge, river sand, cement, fly ash and a curing agent are uniformly mixed, the mud material is put into a die, the pressure of 700KN is applied on a press machine for pressing and forming, and the finished product is prepared after demoulding and drying.
The compounding ratio of the curing agent was the same as in example 3.
The performance test results are: the average compressive strength of the steel plate after 28 days is 25.28Mpa, and the flexural strength of the steel plate after 28 days is 7.25 Mpa. The mechanical property of the material can still meet the relevant national standard. Other properties were substantially the same as in example 1.

Claims (5)

1.一种利用油田污泥制成的免烧砖,其特征在于:主要是由如下重量配比的原料混合后,用压机挤压而成,1. A burn-free brick made of oilfield sludge is characterized in that: it is mainly formed by mixing the raw materials in the following weight ratio and extruding with a press, 油田污泥: 30-60%Oilfield sludge: 30-60% 河沙:     15-40%River sand: 15-40% 水泥:     15-30%Cement: 15-30% 粉煤灰:   0-35%Fly ash: 0-35% 固化剂:   1-8%Curing agent: 1-8% 所述的固化剂含有下述重量配比的原料:Described solidifying agent contains the raw material of following weight ratio: 硫铝酸盐:  15%-25%    硬脂酸钙:0-10%Sulfoaluminate: 15%-25% Calcium Stearate: 0-10% 氯化钙:    0-25%       醋酸钙:  0-15%Calcium chloride: 0-25% Calcium acetate: 0-15% 萤石:      0-10%       明胶:    5%-10%Fluorite: 0-10% Gelatin: 5%-10% 石膏:      10%-25%    石灰:    10%-30%Gypsum: 10%-25% Lime: 10%-30% 丙烯酸树脂  0-5%Acrylic resin 0-5% 2.根据权利要求1所述的免烧砖,其特征在于:所述原料的重量配比为:2. The burn-free brick according to claim 1, characterized in that: the weight ratio of the raw materials is: 油田污泥: 30-50%Oilfield sludge: 30-50% 河沙:     15-30%River sand: 15-30% 水泥:     15-25%Cement: 15-25% 粉煤灰:   10-30%Fly ash: 10-30% 固化剂:   2-6%Curing agent: 2-6% 所述的固化剂主要是由下述重量配比的原料制成,Described solidifying agent is mainly made of the raw material of following weight ratio, 硫铝酸盐:  15%-25%    硬脂酸钙:  0-10%Sulfoaluminate: 15%-25% Calcium Stearate: 0-10% 氯化钙:    10%-25%    醋酸钙:    0-15%Calcium chloride: 10%-25% Calcium acetate: 0-15% 萤石:      4%-10%     明胶:      5%-10%Fluorite: 4%-10% Gelatin: 5%-10% 石膏:      10%-25%    石灰:      10%-30%Gypsum: 10%-25% Lime: 10%-30% 丙烯酸树脂  0-5%Acrylic resin 0-5% 3.根据权利要求1或2所述的免烧砖,其特征在于:所述的固化剂还加入占固化剂重量百分比为8-10%的核心料,其中核心料的原料重量配比为: CaO  MgO  Fe2O3  SiO2  Al2O3   Al2(SO4)4     Na2CO3    FeSO4    MgSO4 5-10  5-10  5-10  6-15  8-15   2-20     10-20    5-20    5-20
3. The unburned brick according to claim 1 or 2, characterized in that: the curing agent is also added with a core material accounting for 8-10% by weight of the curing agent, wherein the raw material weight ratio of the core material is: CaO MgO Fe2O3 _ SiO 2 Al 2 O 3 Al 2 (SO 4 ) 4 Na 2 CO 3 FeSO 4 MgSO4 5-10 5-10 5-10 6-15 8-15 2-20 10-20 5-20 5-20
4.一种权利要求1或2所述的免烧砖的生产方法,其特征在于:包括以下步骤,4. A production method of the unburned brick according to claim 1 or 2, characterized in that: comprising the following steps, a)将油田污泥、河沙、水泥、粉煤灰、固化剂混合均匀,制得泥浆料;a) mixing oilfield sludge, river sand, cement, fly ash, and curing agent evenly to prepare mud slurry; b)将泥浆料装入模具,在压力机上施以500-700KN的压力压制成型,脱模,干燥,制成成品。b) Put the mud material into a mold, apply a pressure of 500-700KN on a press to form it, demold it, and dry it to make a finished product. 5.一种权利要求3所述的免烧砖的生产方法,其特征在于:包括以下步骤,5. A production method of the unburned brick according to claim 3, characterized in that: comprising the following steps, a)将油田污泥、河沙、水泥、粉煤灰、固化剂混合均匀,制得泥浆料;a) mixing oilfield sludge, river sand, cement, fly ash, and curing agent evenly to prepare mud slurry; b)将泥浆料装入模具,在压力机上施以500-700KN的压力压制成型,脱模,干燥,制成成品。b) Put the mud material into a mold, apply a pressure of 500-700KN on a press to form it, demold it, and dry it to make a finished product.
CN 03139053 2003-09-22 2003-09-22 A burn-free brick made from oilfield sludge and its production method Expired - Fee Related CN1226120C (en)

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CN106277952A (en) * 2016-07-22 2017-01-04 杭州聚城环保科技有限公司 A kind of mud is utilized to prepare non-burning brick method
CN108484081A (en) * 2018-04-19 2018-09-04 宁波纯恒固废科技有限公司 A kind of oily sludge is non-burning brick and preparation method thereof
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CN104556601A (en) * 2014-12-30 2015-04-29 韩京龙 Comprehensive utilization method of oil field drilling sludge
CN104556601B (en) * 2014-12-30 2016-06-01 韩京龙 The not Application way of oil-containing oil drilling mud
CN106277952A (en) * 2016-07-22 2017-01-04 杭州聚城环保科技有限公司 A kind of mud is utilized to prepare non-burning brick method
CN106277952B (en) * 2016-07-22 2019-10-01 杭州聚城金建环保技术有限公司 A method of it is prepared using sludge non-burning brick
CN108484081A (en) * 2018-04-19 2018-09-04 宁波纯恒固废科技有限公司 A kind of oily sludge is non-burning brick and preparation method thereof
CN108484081B (en) * 2018-04-19 2020-12-29 宁波纯力固废科技有限责任公司 Oily sludge baking-free brick and preparation method thereof
CN108640606A (en) * 2018-05-30 2018-10-12 王雪峰 A kind of composite sludge is non-burning brick
CN111423190A (en) * 2020-05-26 2020-07-17 新疆科力新技术发展股份有限公司 Baking-free brick prepared from oilfield silicon mud and coal ash and preparation method thereof

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