CN108046284A - Oil-based drill cuttings pyrolysis ash content is the zeolite preparation method and product of raw material - Google Patents
Oil-based drill cuttings pyrolysis ash content is the zeolite preparation method and product of raw material Download PDFInfo
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- CN108046284A CN108046284A CN201810011878.3A CN201810011878A CN108046284A CN 108046284 A CN108046284 A CN 108046284A CN 201810011878 A CN201810011878 A CN 201810011878A CN 108046284 A CN108046284 A CN 108046284A
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
- C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/16—Alumino-silicates
- B01J20/18—Synthetic zeolitic molecular sieves
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/16—Nitrogen compounds, e.g. ammonia
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- Processing Of Solid Wastes (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
Abstract
The invention belongs to solid waste resource utilization fields, and in particular to a kind of method that water treatment industry artificial zeolite is prepared using shale gas drilling well oil-based drill cuttings pyrolysis ash content as raw material.The preparation method comprises the following steps：S01, will be dried for standby after oil-based drill cuttings pyrolysis ash content sieving；S02, aluminum contained compound and alkali are added in into pyrolysis ash content, is sufficiently mixed, grinds, obtain mixed-powder；S03, mixed-powder is roasted, obtains alkali and melt clinker；It after S04, alkali melt clinker cooling to room temperature, is mixed with water, mixture is stirred at room temperature, is aged；After S05, ageing, mixture Crystallizing treatment will be aged；S06, after crystallization product solution is cooled to room temperature, filter simultaneously crystal is washed and is dried to get zeolite.This method not only facilitates the discharge for reducing shale gas exploration and development process solid waste polluter, can also realize its recycling, has environmental protection and economic dual value.
Description
Technical field
The invention belongs to solid waste resource utilization fields, and in particular to a kind of oil-based drill cuttings pyrolysis ash content is raw material.
Background technology
A certain number of oil-based drill cuttings mud can be generated in shale gas well drilling process, since oily sludge has been arranged
Enter《National Hazard waste register》, it is therefore necessary to harmless treatment is carried out to oily sludge.Thermal desorption skill is used in the prior art
Art, the oils vaporization that oil-based drill cuttings is made to be heated contained condense recycling oil water mixture by cooling system, and remaining solid waste is with ash content
Residue form output, and these ash content residues are usually that road construction is used for as solid mineral material, prepares the side such as building materials
Face.
SiO in typical drilling cuttings pyrolysis ash content2、Al2O3, CaO content be respectively 55.4%, 7.8% and 7.2%, with fine coal
Ash is respectively provided with similar chemical composition with volcanic ash, is expected to the raw material as artificial zeolite.
The content of the invention
One aspect of the invention is related to is pyrolyzed zeolite preparation method of the ash content as raw material using oil-based drill cuttings,.The method pin
To oil-based drill cuttings pyrolysis ash content physics and chemistry feature and design, have it is easy to operate, production efficiency is high, can realize solid waste
Recycling recycle the features such as.To achieve these goals, the technical scheme is that：Specifically, it is described with oil
Base drilling cuttings pyrolysis ash content is the zeolite preparation method of raw material, is comprised the following steps：
S01, will be dried for standby after oil-based drill cuttings pyrolysis ash content sieving；
S02, aluminum contained compound and alkali are added in into pyrolysis ash content, is sufficiently mixed, grinds, obtain mixed-powder；
S03, mixed-powder is roasted, obtains alkali and melt clinker；
It after S04, alkali melt clinker cooling to room temperature, is mixed with water, mixture is stirred at room temperature, is aged；
After S05, ageing, mixture Crystallizing treatment will be aged；
S06, after crystallization product solution is cooled to room temperature, filter simultaneously crystal is washed and is dried to get zeolite.
The source of the oil-based drill cuttings is not particularly limited, and can generally utilize the oil base generated during shale gas exploitation
Drilling cuttings is as raw material.Specifically, oil-base mud is pyrolyzed, obtains oil-based drill cuttings, at 800~1000 DEG C by oil-based drill cuttings
It roasts to mass conservation, is then cooled to room temperature, obtain pyrolysis ash content, cross 200 mesh sieves, it is spare；
In step S01 as raw material pyrolysis ash content into it is point as shown in table 1, pass through X-ray fluorescence spectra (XRF)) survey
Examination obtains.
Table 1
| SiO2(%) | 55.44 | P(ppm) | 353.7 | Nd(ppm) | 371.5 |
| Al2O3(%) | 7.83 | S(ppm) | 21099.0 | F(ppm) | 1500.0 |
| Fe2O3(%) | 2.04 | Cl(ppm) | 6566.5 | ||
| MgO (%) | 1.80 | Ti(ppm) | 26241.9 | ||
| CaO (%) | 7.20 | Zn(ppm) | 402.6 | ||
| Na2O (%) | 0.82 | Sr(ppm) | 3780.5 | ||
| K2O (%) | 1.79 | Ba(ppm) | 95333.9 |
Specifically, the aluminum contained compound is selected from aluminium hydroxide and/or aluminium oxide；The alkali be selected from sodium hydroxide and/
Or potassium hydroxide.
Preferably, the calcination temperature of step S03 is 800~1000 DEG C.
Preferably, in step S04, Al (OH)3Addition be so that Al/Si ratios are 1:1；NaOH is according to ash content:
NaOH=1:0.5~1:2 mass ratio adds in.The specific addition of each raw material can measure object element content by XRF,
It is determined according to actual conditions.
Preferably, the calcination temperature again of step S05 is 600~700 DEG C, roasting time is 100~150min.
Preferably, in step S04, the water is deionized water；The alkali melts clinker with deionized water according to 3:1~
15:1 mass ratio mixing.
Preferably, in step S05, the Crystallizing treatment carries out in stainless steel cauldron, the temperature of the Crystallizing treatment
Spend for 60 DEG C~150 DEG C, time be 2~for 24 hours.
The present invention further provides a kind of artificial zeolite, the artificial zeolite is pyrolyzed ash content as original by foregoing oil-based drill cuttings
The zeolite preparation method of material is prepared.The zeolite stable quality, ammonia nitrogen adsorbs suitable for high-salt wastewater.
The beneficial effects of the present invention are：
(1) the present invention provides the recycling recoverying and utilizing method of this solid waste of oil-based drill cuttings, not only facilitate and subtract
The discharge of few shale gas exploration and development process contamination substance, can also realize its recycling, have environmentally friendly and economy dual
Value.
(2) present invention is pyrolyzed the physicochemical property of ash content for oil-based drill cuttings, proposes targetedly reaction condition, can be effective
Synthesis of artificial zeolite, the simple controllable, product yield high of process.
(3) artificial zeolite quality provided by the invention is good, especially suitable for ammonia nitrogen in sewage ion-exchange treatment, will pollute
Object is converted into the product of processing pollutant, has vast potential for future development.
Description of the drawings
In order to illustrate more clearly about the embodiment of the present invention or technical scheme of the prior art, below to embodiment or existing
Attached drawing is briefly described needed in technology.It should be evident that the accompanying drawings in the following description is only the present invention's
Some embodiments, for those of ordinary skill in the art, without creative efforts, can also be according to this
A little attached drawings obtain other attached drawings.
Fig. 1 is the XRD spectrum of the oil-based drill cuttings pyrolysis ash content of embodiment 1.
Fig. 2 is the SEM figures of the oil-based drill cuttings pyrolysis ash content of embodiment 1.
Fig. 3 is the SEM figures of the zeolite of the oil-based drill cuttings pyrolysis ash content synthesis of embodiment 1.
Specific embodiment
Below in conjunction with the embodiment of the present invention, technical scheme is clearly and completely described.Based on this
Embodiment in invention, the every other reality that those of ordinary skill in the art are obtained without creative efforts
Example is applied, belongs to the scope of protection of the invention.
Embodiment 1
Using the oil-based drill cuttings that Fuling shale gas producing region shale gas exploitation obtains as raw material.
Oil-based drill cuttings are put into nickel crucible, high-temperature roasting is carried out until mass conservation with 800 DEG C in Muffle furnace.It will
Pyrolysis ash content after roasting carries out natural cooling, and after the completion of to be cooled, XRF measure is carried out to each element proportion in ash content,
Its essential element is as shown in table 2.
Table 2
| Element species | Si | Al | Ca |
| Mass percent | 25.87% | 4.15% | 5.14% |
20g is taken to be pyrolyzed ash content, adds in 8.21g aluminium hydroxides to adjust Si/Al=1, is adding in 10g sodium hydroxides, fully
It after mixing, grinding, is positioned in nickel crucible, roasts 120min in muffle furnace with 650 DEG C, after reaction natural cooling,
Taking-up alkali melts clinker and is ground from crucible.
100g alkali is melted clinker mix in the beaker of 500mL with 100g deionized waters, and in room temperature, 200rpm
The lower ageing of stirring is for 24 hours；After completing ageing, liquid ageing mixture is transferred in the stainless steel cauldron of 1L, in 60 DEG C, 1atm
Lower crystallization 2h.It after crystallization, treats that solution is cooled to room temperature, takes out solution, the crystal of acquisition is filtered, is washed, overnight
It is dry.
The XRD spectrum and SEM figures difference of oil-based drill cuttings pyrolysis ash content are as illustrated in fig. 1 and 2.The SEM figure such as Fig. 3 of product Zeolite
It is shown.
Embodiment 2
On the basis of embodiment 1, the dosage of sodium hydroxide is adjusted to 20g, remaining is constant.
Embodiment 3
On the basis of embodiment 1, the dosage of sodium hydroxide is adjusted to 30g, remaining is constant.
Embodiment 4
On the basis of embodiment 1, the dosage of sodium hydroxide is adjusted to 40g, remaining is constant.
Embodiment 5
On the basis of embodiment 1, crystallization temperature is changed into 80 DEG C, remaining is constant.
Embodiment 6
On the basis of embodiment 1, crystallization temperature is changed into 100 DEG C, remaining is constant.
Embodiment 7
On the basis of embodiment 1, crystallization temperature is changed into 120 DEG C, remaining is constant.
Embodiment 8
On the basis of embodiment 1, crystallization temperature is changed into 80 DEG C, remaining is constant.
Embodiment 9
On the basis of embodiment 1, crystallization time is changed into 4h, remaining is constant.
Embodiment 10
On the basis of embodiment 1, crystallization time is changed into 6h, remaining is constant.
Embodiment 11
On the basis of embodiment 1, crystallization time is changed into 12h, remaining is constant.
Embodiment 12
On the basis of embodiment 1, crystallization time is changed into for 24 hours, remaining is constant.
The above description is merely a specific embodiment, but protection scope of the present invention is not limited thereto, any
Those familiar with the art in the technical scope disclosed by the present invention, can readily occur in change or replacement, should all contain
Lid is within protection scope of the present invention.Therefore, protection scope of the present invention should be based on the protection scope of the described claims.
Claims (9)
1. oil-based drill cuttings pyrolysis ash content is the zeolite preparation method of raw material, which is characterized in that is comprised the following steps：
S01, will be dried for standby after oil-based drill cuttings pyrolysis ash content sieving；
S02, aluminum contained compound and alkali are added in into pyrolysis ash content, is sufficiently mixed, grinds, obtain mixed-powder；
S03, mixed-powder is roasted, obtains alkali and melt clinker；
It after S04, alkali melt clinker cooling to room temperature, is mixed with water, mixture is stirred at room temperature, is aged；
After S05, ageing, mixture Crystallizing treatment will be aged；
S06, after crystallization product solution is cooled to room temperature, filter simultaneously crystal is washed and is dried to get zeolite.
2. preparation method according to claim 1, which is characterized in that the aluminum contained compound be selected from aluminium hydroxide and/or
Aluminium oxide.
3. preparation method according to claim 1, which is characterized in that the alkali is selected from sodium hydroxide and/or potassium hydroxide.
4. preparation method according to claim 1, which is characterized in that in step S02, Al (OH)3Addition be so that
Al/Si ratios are 1:1.
5. preparation method according to claim 1, which is characterized in that in step S02, NaOH is according to ash content:NaOH=1:
0.5~1:2 mass ratio adds in.
6. preparation method according to claim 1, which is characterized in that the calcination temperature of step S03 is 600~700 DEG C, roasting
The burning time is 100~150min.
7. preparation method according to claim 1, which is characterized in that in step S04, the water is deionized water；It is described
Alkali melts clinker with deionized water according to 3:1~15:1 mass ratio mixing.
8. preparation method according to claim 1, which is characterized in that in step S05, the Crystallizing treatment is anti-in stainless steel
Answer in kettle and carry out, the temperature of the Crystallizing treatment is 60 DEG C~150 DEG C, the time be 2~for 24 hours.
9. artificial zeolite, which is characterized in that the artificial zeolite passes through claim 1~9 any one of them oil-based drill cuttings heat
Solution ash content is prepared for the zeolite preparation method of raw material.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111013527A (en) * | 2019-11-26 | 2020-04-17 | 中国矿业大学(北京) | Method for preparing heavy metal cadmium adsorption fixing agent from oil shale ash and coal ash |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105036151A (en) * | 2015-08-14 | 2015-11-11 | 商洛学院 | Methodof producing zeolite molecular sieve by utilizing tailings |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105036151A (en) * | 2015-08-14 | 2015-11-11 | 商洛学院 | Methodof producing zeolite molecular sieve by utilizing tailings |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111013527A (en) * | 2019-11-26 | 2020-04-17 | 中国矿业大学(北京) | Method for preparing heavy metal cadmium adsorption fixing agent from oil shale ash and coal ash |
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| TA01 | Transfer of patent application right |
Effective date of registration: 20191225 Address after: 408000, 6 Feng Feng Road, Xincheng District, Fuling District, Chongqing, China Applicant after: Sinopec Chongqing Fuling Shale Gas Exploration and Development Co., Ltd. Applicant after: China Petrochemical Co., Ltd. Address before: 408000, 6 Feng Feng Road, Xincheng District, Fuling District, Chongqing, China Applicant before: Sinopec Chongqing Fuling Shale Gas Exploration and Development Co., Ltd. Applicant before: Institute of Urban Environment, Chinese Academy of Sciences |
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Address after: 100728 No. 22 North Main Street, Chaoyang District, Beijing, Chaoyangmen Patentee after: China Petroleum & Chemical Corp. Patentee after: SINOPEC CHONGQING FULING SHALE GAS EXPLORATION AND DEVELOPMENT Co.,Ltd. Address before: 408000 No. 6 Hefeng Avenue, Fuling District, Chongqing Patentee before: SINOPEC CHONGQING FULING SHALE GAS EXPLORATION AND DEVELOPMENT Co.,Ltd. Patentee before: China Petroleum & Chemical Corp. |
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