CN113880127A - Method for producing nano calcium carbonate by using tail gas generated by treating waste - Google Patents
Method for producing nano calcium carbonate by using tail gas generated by treating waste Download PDFInfo
- Publication number
- CN113880127A CN113880127A CN202111321589.1A CN202111321589A CN113880127A CN 113880127 A CN113880127 A CN 113880127A CN 202111321589 A CN202111321589 A CN 202111321589A CN 113880127 A CN113880127 A CN 113880127A
- Authority
- CN
- China
- Prior art keywords
- calcium carbonate
- treatment
- nano calcium
- tail gas
- producing nano
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 title claims abstract description 158
- 229910000019 calcium carbonate Inorganic materials 0.000 title claims abstract description 78
- 239000002699 waste material Substances 0.000 title claims abstract description 44
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 20
- 239000013078 crystal Substances 0.000 claims abstract description 40
- 238000009284 supercritical water oxidation Methods 0.000 claims abstract description 27
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid group Chemical group C(CC(O)(C(=O)O)CC(=O)O)(=O)O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 33
- 238000003763 carbonization Methods 0.000 claims description 31
- 239000002002 slurry Substances 0.000 claims description 28
- 230000032683 aging Effects 0.000 claims description 26
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 23
- 239000000920 calcium hydroxide Substances 0.000 claims description 21
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 21
- 239000003795 chemical substances by application Substances 0.000 claims description 20
- 239000002270 dispersing agent Substances 0.000 claims description 20
- 238000005516 engineering process Methods 0.000 claims description 19
- 239000011259 mixed solution Substances 0.000 claims description 19
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 18
- 238000001035 drying Methods 0.000 claims description 18
- 238000000926 separation method Methods 0.000 claims description 17
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid group Chemical group S(O)(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 16
- 230000005587 bubbling Effects 0.000 claims description 14
- 238000002425 crystallisation Methods 0.000 claims description 13
- 230000008025 crystallization Effects 0.000 claims description 13
- 239000000243 solution Substances 0.000 claims description 13
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 9
- 229920002125 Sokalan® Polymers 0.000 claims description 9
- 239000003513 alkali Substances 0.000 claims description 9
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 9
- 239000004584 polyacrylic acid Substances 0.000 claims description 9
- 229920000193 polymethacrylate Polymers 0.000 claims description 9
- 229910052708 sodium Inorganic materials 0.000 claims description 9
- 239000011734 sodium Substances 0.000 claims description 9
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 9
- 235000008733 Citrus aurantifolia Nutrition 0.000 claims description 8
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 8
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical group [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 8
- 235000011941 Tilia x europaea Nutrition 0.000 claims description 8
- 239000008103 glucose Substances 0.000 claims description 8
- 239000004571 lime Substances 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 8
- 239000008267 milk Substances 0.000 claims description 8
- 210000004080 milk Anatomy 0.000 claims description 8
- 235000013336 milk Nutrition 0.000 claims description 8
- 238000001179 sorption measurement Methods 0.000 claims description 8
- 238000005507 spraying Methods 0.000 claims description 8
- 238000002360 preparation method Methods 0.000 claims description 7
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 6
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 6
- 239000002131 composite material Substances 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 150000007524 organic acids Chemical class 0.000 claims description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 4
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 2
- 150000001720 carbohydrates Chemical class 0.000 claims description 2
- YRIUSKIDOIARQF-UHFFFAOYSA-N dodecyl benzenesulfonate Chemical compound CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 YRIUSKIDOIARQF-UHFFFAOYSA-N 0.000 claims description 2
- 229940071161 dodecylbenzenesulfonate Drugs 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 229920005646 polycarboxylate Polymers 0.000 claims description 2
- 239000007921 spray Substances 0.000 claims description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 abstract description 82
- 239000001569 carbon dioxide Substances 0.000 abstract description 41
- 229910002092 carbon dioxide Inorganic materials 0.000 abstract description 37
- 238000000034 method Methods 0.000 abstract description 19
- 230000000694 effects Effects 0.000 abstract description 18
- 238000006243 chemical reaction Methods 0.000 abstract description 14
- 239000002245 particle Substances 0.000 abstract description 12
- 230000008901 benefit Effects 0.000 abstract description 6
- 230000008092 positive effect Effects 0.000 abstract description 6
- 230000009286 beneficial effect Effects 0.000 abstract description 4
- 239000007789 gas Substances 0.000 description 57
- 230000000052 comparative effect Effects 0.000 description 13
- 229910021392 nanocarbon Inorganic materials 0.000 description 9
- 239000010705 motor oil Substances 0.000 description 7
- 239000010913 used oil Substances 0.000 description 7
- 238000001914 filtration Methods 0.000 description 6
- 230000001965 increasing effect Effects 0.000 description 5
- 239000012535 impurity Substances 0.000 description 4
- 230000009471 action Effects 0.000 description 3
- 238000005054 agglomeration Methods 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 239000002920 hazardous waste Substances 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 230000000668 effect on calcium Effects 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 230000005764 inhibitory process Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 230000005476 size effect Effects 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 239000000411 inducer Substances 0.000 description 1
- 239000000976 ink Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000010815 organic waste Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000565 sealant Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000606 toothpaste Substances 0.000 description 1
- 229940034610 toothpaste Drugs 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F11/00—Compounds of calcium, strontium, or barium
- C01F11/18—Carbonates
- C01F11/182—Preparation of calcium carbonate by carbonation of aqueous solutions and characterised by an additive other than CaCO3-seeds
- C01F11/183—Preparation of calcium carbonate by carbonation of aqueous solutions and characterised by an additive other than CaCO3-seeds the additive being an organic compound
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F11/00—Compounds of calcium, strontium, or barium
- C01F11/18—Carbonates
- C01F11/181—Preparation of calcium carbonate by carbonation of aqueous solutions and characterised by control of the carbonation conditions
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/54—Particles characterised by their aspect ratio, i.e. the ratio of sizes in the longest to the shortest dimension
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Geology (AREA)
- Inorganic Chemistry (AREA)
- Nanotechnology (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Crystallography & Structural Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
Abstract
The invention relates to a method for producing nano calcium carbonate by using tail gas generated by treating wastes, which aims to adjust the production process and parameters of nano calcium carbonate according to the characteristics of the tail gas generated by treating the wastes by a supercritical water oxidation method, so that the generated nano calcium carbonate crystals have more uniform particle size and the performance of the nano calcium carbonate is more excellent under the conditions of high-concentration carbon dioxide and high-temperature reaction; meanwhile, the method reduces the emission of carbon dioxide, has a positive effect on relieving greenhouse effect, increases the benefit, and reduces the cost input of waste treatment, thereby being beneficial to enlarging the treatment scale of waste and reducing the pollution of waste to the environment.
Description
Technical Field
The invention relates to the field of waste recycling and comprehensive utilization, in particular to a method for producing nano calcium carbonate by utilizing tail gas generated by waste treatment.
Background
Supercritical Water Oxidation (SCWO) technology is a technology capable of realizing deep Oxidation treatment of various organic wastes, and takes Supercritical Water as a reaction medium to completely oxidize organic matters into clean H through homogeneous Oxidation reaction2O、CO2And N2Etc., converting S, P etc. into stable compounds of highest valence salts, and oxidizing heavy metals intoTechniques for stabilizing the presence of a solid phase in ash. The supercritical water oxidation technology is adopted to treat the hazardous waste, has the advantages of high efficiency, low energy consumption and no secondary pollution, and is one of the best technologies for treating the hazardous waste.
However, with the increasing greenhouse effect in recent years, the sustainable development of environment and economy is facing a serious challenge, and CO is2Is a main greenhouse gas recognized in the world to cause global warming and reduces CO2The emission and the alleviation of the greenhouse effect are widely recognized by the international society. The gas phase product of supercritical water oxidation technology is CO2Predominantly mixed gas, CO2The content of (A) exceeds 50%, therefore, CO in gas phase products after the waste is treated by supercritical water oxidation technology2Performing recovery treatment to reduce CO2The discharge amount is reduced, the greenhouse effect is relieved, waste can be changed into valuable, and the treatment cost of waste is reduced, so that the method has a positive effect on large-scale treatment of hazardous waste.
The nano calcium carbonate is a novel superfine solid powder material developed in the 80 s of the 20 th century, the crystal structure and the surface electronic structure of the nano calcium carbonate are changed due to the superfine property of nano calcium carbonate particles, the quantum size effect, the small size effect, the surface effect and the macroscopic quantum effect which are not possessed by common calcium carbonate are generated, and the nano calcium carbonate is widely applied to industries such as rubber, plastics, papermaking, chemical building materials, printing ink, coating, toothpaste, sealant, adhesive and the like, so that CO generated by treating wastes by using a supercritical water oxidation technology is used for preparing the novel superfine solid powder material2Can effectively reduce CO when used for preparing nano calcium carbonate2The greenhouse effect is relieved. However, the carbon dioxide gas generated by treating the waste by the supercritical water oxidation technology has the characteristics of high temperature, high pressure and high concentration, so that the existing technical method for preparing nano calcium carbonate by using the carbon dioxide gas is directly adopted to prepare the nano calcium carbonate, and the prepared nano calcium carbonate has the defects of poor dispersibility, poor granularity uniformity, high equipment requirement, poor universality and the like, thereby seriously limiting the large-scale application of preparing the nano calcium carbonate by using the carbon dioxide gas generated by treating the waste by the supercritical water oxidation technology.
Disclosure of Invention
The invention provides a method for producing nano calcium carbonate by utilizing tail gas generated by treating wastes according to the characteristic of the tail gas generated by treating the wastes by a supercritical water oxidation method, aiming at the defect of poor uniformity of the granularity of the nano calcium carbonate prepared by adopting the carbon dioxide gas generated by treating the wastes by the supercritical water oxidation technology, and the method can be used for pertinently adjusting the production process and parameters of the nano calcium carbonate, so that the generated nano calcium carbonate crystals have more uniform granularity under the conditions of high-concentration carbon dioxide and high-temperature reaction, and the performance of the nano calcium carbonate is more excellent; meanwhile, the method reduces the emission of carbon dioxide, has a positive effect on relieving greenhouse effect, increases the benefit, and reduces the cost input of waste treatment, thereby being beneficial to enlarging the treatment scale of waste and reducing the pollution of waste to the environment.
In order to achieve the aim, the invention provides a method for producing nano calcium carbonate by using tail gas generated by treating wastes, which comprises the following steps: the tail gas generated by treating the waste through the supercritical water oxidation technology is sequentially subjected to pretreatment, carbonization treatment, aging treatment and separation drying treatment, so that the nano calcium carbonate product is prepared.
Wherein the pretreatment comprises the following steps: firstly, carrying out depressurization treatment on the tail gas, then carrying out alkali washing and spraying treatment, and finally carrying out water-vapor separation treatment and activated carbon adsorption treatment to obtain pretreated tail gas; through the pretreatment of the tail gas, impurities in the tail gas can be removed, the pressure and the temperature of the tail gas are reduced, so that the later carbonization treatment is facilitated, and the purity of the nano calcium carbonate is improved.
Preferably, the pressure of the tail gas after the pressure reduction treatment is 0.3-0.5 MPa; the optimal pressure value has good impurity removal effect, high efficiency and good carbonization effect in the later period; most preferably, the pressure of the tail gas after the pressure reduction treatment is 0.4 MPa.
Preferably, the alkali liquor in the alkali washing and spraying treatment is a sodium carbonate solution or a sodium bicarbonate solution with the mass concentration percentage of 10-20%; the preferable concentration of the alkali liquor has the best effect of removing impurities in the tail gas, and the finally generated nano calcium carbonate has higher purity; most preferably, the alkali solution in the alkali washing spray treatment is sodium bicarbonate solution with the weight concentration percentage of 15%.
Preferably, after the water-vapor separation treatment, the water content in the tail gas is not more than 10%; the optimized water content of the tail gas has the minimum influence on the adsorption effect of the activated carbon, so that the activated carbon is favorable for adsorbing and removing impurities in the tail gas, and the finally generated nano calcium carbonate has higher purity; most preferably, the moisture content of the tail gas after the moisture separation treatment is not more than 5%.
Wherein the carbonization treatment comprises the following steps: introducing the pretreated tail gas into the lime milk liquid to carry out bubbling carbonization treatment to obtain carbonized milk liquid; through carbonization treatment, carbon dioxide in tail gas reacts with calcium hydroxide, and under the action of a crystallization inducer and a dispersing agent, nano calcium carbonate crystal nuclei which are uniform in particle size and not easy to accumulate are generated, so that the nano calcium carbonate crystal nuclei can grow rapidly in the later-stage aging treatment.
Wherein the lime milk liquid is a mixed solution of a calcium hydroxide solution, a crystallization control agent and a dispersing agent; the crystallization control agent is a mixture of organic acid, saccharides and poly organic acid with the mass ratio of 0.04-0.06: 1: 0.1-0.3; the dispersant is a composite dispersant formed by mixing polycarboxylate and dodecyl benzene sulfonate; the calcium hydroxide can rapidly absorb carbon dioxide gas to generate calcium carbonate; the crystallization control agent can promote the formation of calcium carbonate crystal nucleus and inhibit the rapid growth of the crystal nucleus, so that the finally prepared nano calcium carbonate has more uniform grain diameter; the dispersing agent can reduce the agglomeration of calcium carbonate crystal nuclei, so that the particle size of calcium carbonate is more uniform.
Wherein, the temperature of the bubbling carbonization treatment is preferably 40 ℃ at the initial temperature and 70 ℃ at the maximum temperature; the optimal carbonization temperature condition has high carbonization speed, the movement speed of the calcium carbonate crystal nucleus in the slurry is high, the calcium carbonate crystal nucleus is easy to collide, and the calcium carbonate crystal nucleus is not easy to settle and agglomerate under the action of the dispersing agent, so that the particle size of the obtained nano calcium carbonate crystal nucleus is more uniform.
Preferably, the mass concentration percentage of the calcium hydroxide in the lime milk liquid is 12-15%; the optimized concentration of calcium hydroxide, under the conditions of high-concentration carbon dioxide and high-temperature reaction, the generated calcium carbonate crystal nucleus is more uniform; most preferably, the mass concentration percentage of calcium hydroxide in the lime slurry is 14%.
Preferably, the crystallization control agent is citric acid, glucose and polyacrylic acid with the mass ratio of 0.05: 1: 0.2; the preferable type and proportion of the crystallization control agent have better promotion effect on the formation of calcium carbonate crystal nucleus generated under the conditions of high-concentration carbon dioxide and high-temperature reaction and better inhibition effect on the growth of the crystal nucleus.
Preferably, the amount of the crystallization control agent is 0.5-0.8% of the mass of the calcium hydroxide; the optimized dosage of the crystallization control agent has better promotion effect on the formation of calcium carbonate crystal nucleus and better inhibition effect on the growth of the crystal nucleus under the conditions of high-concentration carbon dioxide and high-temperature reaction; most preferably, the crystallization controller is used in an amount of 0.7% by mass of the calcium hydroxide.
Preferably, the dispersant is a composite dispersant formed by mixing sodium polymethacrylate and sodium dodecyl benzene sulfonate according to the mass ratio of 3-5: 2; the preferable dispersant type has better dispersion effect on calcium carbonate crystal nuclei generated under the conditions of high-concentration carbon dioxide and high-temperature reaction, the calcium carbonate crystal nuclei are less prone to agglomeration, and the particle size is more uniform; most preferably, the dispersant is a composite dispersant formed by mixing sodium polymethacrylate and sodium dodecyl benzene sulfonate according to the mass ratio of 2: 1.
Preferably, the amount of the dispersant is 1.0-1.5% of the mass of the calcium hydroxide; the optimized dosage of the dispersant has better dispersion effect on calcium carbonate crystal nuclei generated under the conditions of high-concentration carbon dioxide and high-temperature reaction, the calcium carbonate crystal nuclei are less prone to agglomeration, and the particle size is more uniform; most preferably, the amount of the dispersant is 1.2% by mass of the calcium hydroxide.
The carbonization treatment completion conditions are as follows: when the pH value of the lime milk liquid is reduced to 6.5-7.0, the carbonization reaction is completed.
Wherein the aging treatment comprises the following steps: adding a crystal form control agent into the carbonized slurry, and performing aging treatment to obtain aged slurry; through aging treatment, calcium carbonate ions which do not form crystal nuclei in the solution are attached to the crystal nuclei under the action of the crystal form control agent, so that the crystal nuclei grow rapidly to form crystal grains with specific forms.
Wherein, preferably, the crystal form control agent is sulfuric acid; the preferable crystal form control agent forms the nano calcium carbonate with good performance and uniform grain diameter.
Preferably, the dosage of the crystal form control agent is 0.1-0.3% of the mass of the calcium hydroxide; the preferable crystal form control agent, the formed nano calcium carbonate has good performance and uniform grain diameter; most preferably, the dosage of the crystal form control agent is 0.2 percent of the mass of the calcium hydroxide.
Preferably, the aging treatment temperature is 45-55 ℃, and the time is 0.5-1.5 h; the optimal aging temperature and time are matched with the crystal form control agent, so that the growth direction of calcium carbonate crystals can be effectively controlled, the crystal nucleus is prevented from growing rapidly, the growth of the crystal nucleus is easier to control, and the grain size of the obtained calcium carbonate is more uniform; more preferably, the aging temperature is 50 ℃ and the aging time is 1.0 h.
Wherein, the separation drying treatment comprises the following steps: and filtering and dehydrating the aged slurry, and drying the dehydrated filter residue to obtain the nano calcium carbonate product.
Preferably, the drying temperature is 50-80 ℃; the preferable drying temperature is high, the drying speed is high, and the energy consumption is low; most preferably, the drying temperature is 65 ℃.
Preferably, the water content of the dried nano calcium carbonate product is less than 5 percent; the optimized nano calcium carbonate has more stable product performance and easier storage.
In order to achieve the above object, the present invention further provides a nano calcium carbonate product produced by using tail gas generated by treating waste, wherein the nano calcium carbonate product is prepared by the above preparation method; the nano calcium carbonate product has the advantages of uniform particle size distribution and high purity, and is produced by utilizing tail gas generated by treating wastes, so that the emission of carbon dioxide is reduced, the positive effect on relieving greenhouse effect is achieved, the income is increased, the cost input of waste treatment is reduced, the treatment scale of large wastes is increased, and the pollution of the wastes to the environment is reduced.
In summary, due to the adoption of the technical scheme, the invention has the beneficial effects that:
1. the method of the invention adjusts the production process and parameters of the nano calcium carbonate according to the characteristics of the tail gas generated by treating the waste by the supercritical water oxidation method, thereby leading the generated nano calcium carbonate crystal to have more uniform particle size and more excellent performance under the conditions of high-concentration carbon dioxide and high-temperature reaction.
2. The method of the invention utilizes the tail gas generated by treating the waste to produce the nano calcium carbonate, thereby reducing the emission of carbon dioxide, having positive effect on alleviating greenhouse effect, increasing the benefit, and reducing the cost input of waste treatment, thereby being beneficial to increasing the treatment scale of large waste and reducing the pollution of the waste to the environment.
3. The method for producing the nano calcium carbonate by utilizing the tail gas generated by treating the waste is simple and reliable, has stable product performance, has positive effect on enhancing environmental protection, and is suitable for large-scale popularization and application.
Detailed Description
The present invention will be described in detail below.
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Example 1
1) Pretreatment: after the pressure of tail gas (the content of carbon dioxide is 50.60%) generated by treating waste engine oil by a supercritical water oxidation technology is reduced to 0.4MPa, spraying treatment is carried out by using a sodium bicarbonate solution with the mass concentration percentage of 15%, and finally, water-vapor separation treatment and activated carbon adsorption treatment are carried out to obtain pretreated tail gas;
2) bubbling carbonization treatment: introducing the pretreated tail gas into 100kg of mixed solution (comprising 14kg of calcium hydroxide, 3.92g of citric acid, 78.4g of glucose, 15.68g of polyacrylic acid, 112g of sodium polymethacrylate and 56g of sodium dodecyl benzene sulfonate) at the temperature of 40 ℃ to carry out bubbling carbonization treatment, and stopping carbonization reaction when the pH value of the mixed solution is reduced to 6.5 to obtain carbonized slurry;
3) aging treatment: adding 28g of sulfuric acid into the carbonized slurry, and performing aging treatment at 50 ℃ for 1h to obtain aged slurry;
4) separation and drying treatment: and filtering and dehydrating the aged slurry, and drying the dehydrated filter residue at 60 ℃ for 3h to obtain the nano calcium carbonate product.
Example 2
1) Pretreatment: after the pressure of tail gas (the content of carbon dioxide is 50.60%) generated by treating waste engine oil by a supercritical water oxidation technology is reduced to 0.3MPa, spraying treatment is carried out by using a sodium carbonate solution with the mass concentration percentage of 10%, and finally, water-vapor separation treatment and activated carbon adsorption treatment are carried out to obtain pretreated tail gas;
2) bubbling carbonization treatment: introducing the pretreated tail gas into 100kg of mixed solution (comprising 12kg of calcium hydroxide, 2.4g of citric acid, 48g of glucose, 9.6g of polyacrylic acid, 108g of sodium polymethacrylate and 72g of sodium dodecyl benzene sulfonate) at the temperature of 40 ℃ to carry out bubbling carbonization treatment, and stopping carbonization reaction when the pH value of the mixed solution is reduced to 7.0 to obtain carbonized slurry;
3) aging treatment: adding 12g of sulfuric acid into the carbonized slurry, and performing aging treatment at 55 ℃ for 1.5h to obtain aged slurry;
4) separation and drying treatment: and filtering and dehydrating the aged slurry, and drying the dehydrated filter residue at 50 ℃ for 3h to obtain the nano calcium carbonate product.
Example 3
1) Pretreatment: after the pressure of tail gas (the content of carbon dioxide is 50.60%) generated by treating waste engine oil by a supercritical water oxidation technology is reduced to 0.3MPa, spraying treatment is carried out by using a sodium bicarbonate solution with the mass concentration percentage of 20%, and finally, water-vapor separation treatment and activated carbon adsorption treatment are carried out to obtain pretreated tail gas;
2) bubbling carbonization treatment: introducing the pretreated tail gas into 100kg of mixed solution (comprising 12kg of calcium hydroxide, 3.84g of citric acid, 76.8g of glucose, 15.36g of polyacrylic acid, 85.7g of sodium polymethacrylate and 34.3g of sodium dodecyl benzene sulfonate) at the temperature of 40 ℃ to carry out bubbling carbonization treatment, and stopping carbonization reaction when the pH value of the mixed solution is reduced to 7.0 to obtain carbonized slurry;
3) aging treatment: adding 36g of sulfuric acid into the carbonized slurry, and performing aging treatment at 45 ℃ for 0.5h to obtain aged slurry;
4) separation and drying treatment: and filtering and dehydrating the aged slurry, and drying the dehydrated filter residue at 80 ℃ for 2h to obtain the nano calcium carbonate product.
Example 4
1) Pretreatment: after the pressure of tail gas (the content of carbon dioxide is 50.60%) generated by treating waste engine oil by a supercritical water oxidation technology is reduced to 0.5MPa, spraying treatment is carried out by using sodium bicarbonate solution with the mass concentration percentage of 18%, and finally, water-vapor separation treatment and activated carbon adsorption treatment are carried out to obtain pretreated tail gas;
2) bubbling carbonization treatment: introducing the pretreated tail gas into 100kg of mixed solution (comprising 15kg of calcium hydroxide, 3g of citric acid, 60g of glucose, 12g of polyacrylic acid, 135g of sodium polymethacrylate and 90g of sodium dodecyl benzene sulfonate) at the temperature of 40 ℃ to carry out bubbling carbonization treatment, and stopping carbonization reaction when the pH value of the mixed solution is reduced to 7.0 to obtain carbonized slurry;
3) aging treatment: adding 45g of sulfuric acid into the carbonized slurry, and performing aging treatment for 1h at 50 ℃ to obtain aged slurry;
4) separation and drying treatment: and filtering and dehydrating the aged slurry, and drying the dehydrated filter residue at 65 ℃ for 2h to obtain the nano calcium carbonate product.
Example 5
1) Pretreatment: after the pressure of tail gas (the content of carbon dioxide is 50.60%) generated by treating waste engine oil by a supercritical water oxidation technology is reduced to 0.5MPa, spraying treatment is carried out by using a sodium carbonate solution with the mass concentration percentage of 12%, and finally, water-vapor separation treatment and activated carbon adsorption treatment are carried out to obtain pretreated tail gas;
2) bubbling carbonization treatment: introducing the pretreated tail gas into 100kg of mixed solution (comprising 15kg of calcium hydroxide, 4.8g of citric acid, 96g of glucose, 19.2g of polyacrylic acid, 107.1g of sodium polymethacrylate and 42.9g of sodium dodecyl benzene sulfonate) at the temperature of 40 ℃ for bubbling carbonization, and stopping carbonization reaction when the pH value of the mixed solution is reduced to 7.0 to obtain carbonized slurry;
3) aging treatment: adding 15g of sulfuric acid into the carbonized slurry, and performing aging treatment at 55 ℃ for 1.5h to obtain aged slurry;
4) separation and drying treatment: and filtering and dehydrating the aged slurry, and drying the dehydrated filter residue at 70 ℃ for 2.5 hours to obtain the nano calcium carbonate product.
Comparative example 1
The tail gas (carbon dioxide content of 50.60%) generated from the treatment of used oil by the supercritical water oxidation technique was used for the preparation of nano carbon dioxide in the same manner as in example 1 except that the initial temperature of the mixed solution was 30 ℃.
Comparative example 2
The same method as that of example 1 was used to prepare nano carbon dioxide from the tail gas (carbon dioxide content: 50.60%) generated from the supercritical water oxidation treatment of used oil, except that the concentration of calcium hydroxide in the mixed solution was 10% and the concentrations of the other raw materials were unchanged.
Comparative example 3
The same procedure as in example 1 was carried out to use the tail gas (carbon dioxide content: 50.60%) generated from the supercritical water oxidation treatment of used oil for the preparation of nano carbon dioxide, except that citric acid was not added to the mixed solution.
Comparative example 4
Tail gas (carbon dioxide content is 50.60%) generated by treating waste engine oil with supercritical water oxidation technology is used for preparing nano carbon dioxide by the same method as the embodiment 1, except that in the mixed solution, 15.68g of citric acid; 78.4g of glucose; 3.92g of polyacrylic acid (citric acid and polyacrylic acid used in the same amounts in the same order).
Comparative example 5
The same procedure as in example 1 was carried out to use the tail gas (carbon dioxide content: 50.60%) generated from the supercritical water oxidation treatment of used oil for the preparation of nano carbon dioxide, except that phosphoric acid was used instead of citric acid in the mixed solution.
Comparative example 6
The same method as that of example 1 was used to prepare nano carbon dioxide from the tail gas (carbon dioxide content: 50.60%) generated from the supercritical water oxidation of used oil, except that sodium polymethacrylate was not added to the mixed solution, and the amount of sodium dodecylbenzenesulfonate was 168 g.
Comparative example 7
The tail gas (carbon dioxide content is 50.60%) generated from the treatment of used oil by supercritical water oxidation technique was used for preparing nano carbon dioxide in the same manner as in example 1 except that the temperature of the aging treatment was 35 ℃.
Comparative example 8
The same procedure as in example 1 was carried out to use the tail gas (carbon dioxide content: 50.60%) generated from the supercritical water oxidation treatment of used oil for the preparation of nano carbon dioxide, except that 28g of sulfuric acid was directly added to the mixed solution after the carbonization treatment without aging treatment.
Comparative example 9
The method of example 1 in patent publication No. CN101229926B is adopted to treat tail gas (carbon dioxide content is 50.60%) generated by waste engine oil by supercritical water oxidation technology for preparing nano carbon dioxide.
Experimental example: the average short-diameter length and the length-diameter ratio of the nano calcium sulfate prepared in the examples 1 to 5 and the comparative examples 1 to 8 are detected, and the range of the length-diameter ratio is counted, so that the following results are obtained:
according to the statistical results, the length-diameter ratio difference of the prepared nano calcium carbonate is smaller in the examples 1-5, the particle size distribution is more concentrated and the particle size is more uniform than that of the nano calcium carbonate prepared by the prior art (comparative example 9) and comparative examples 1-8; in comparative examples 1 to 8, the parameters of the preparation process and the selection and proportion of raw materials are adjusted, so that the length-diameter ratio range of the prepared nano calcium carbonate is remarkably enlarged, and the non-uniformity of the particle size distribution is remarkably improved.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Claims (10)
1. A method for producing nano calcium carbonate by using tail gas generated by treating wastes comprises the following steps: sequentially carrying out pretreatment, carbonization, aging and separation drying on tail gas generated by treating wastes by a supercritical water oxidation technology, thereby preparing a nano calcium carbonate product; it is characterized in that the preparation method is characterized in that,
the pretreatment comprises the following steps: firstly, carrying out depressurization treatment on the tail gas, then carrying out alkali washing and spraying treatment, and finally carrying out water-vapor separation treatment and activated carbon adsorption treatment to obtain pretreated tail gas;
the carbonization treatment comprises the following steps: introducing the pretreated tail gas into the lime milk liquid to carry out bubbling carbonization treatment to obtain carbonized milk liquid; the lime milk liquid is a mixed solution of a calcium hydroxide solution, a crystallization control agent and a dispersing agent; the crystallization control agent is a mixture of organic acid, saccharides and poly organic acid with the mass ratio of 0.04-0.06: 1: 0.1-0.3; the dispersant is a composite dispersant formed by mixing polycarboxylate and dodecyl benzene sulfonate;
the aging treatment comprises the following steps: adding a crystal form control agent into the carbonized slurry, and performing aging treatment to obtain aged slurry; the aging treatment temperature is 45-55 ℃, and the aging treatment time is 0.5-1.5 h.
2. The method for producing nano calcium carbonate according to claim 1, wherein the alkali liquor in the alkali washing spray treatment is sodium carbonate solution or sodium bicarbonate solution with the mass concentration percentage of 10-20%.
3. The method for producing nanocalcium carbonate according to claim 1, wherein the temperature of the bubbling carbonization treatment is 40 ℃ at the beginning and 70 ℃ at the highest.
4. The method for producing nano calcium carbonate according to claim 1, wherein the mass concentration percentage of calcium hydroxide in the lime slurry is 12-15%.
5. The method for producing nano calcium carbonate according to claim 1, wherein the crystallization controller is citric acid, glucose and polyacrylic acid in a mass ratio of 0.05: 1: 0.2.
6. The method for producing nano calcium carbonate according to claim 5, wherein the crystallization controller is used in an amount of 0.5 to 0.8% by mass of the calcium hydroxide.
7. The method for producing nano calcium carbonate according to claim 1, wherein the dispersant is a composite dispersant prepared by mixing sodium polymethacrylate and sodium dodecyl benzene sulfonate in a mass ratio of 3-5: 2.
8. The method for producing nano calcium carbonate according to claim 7, wherein the amount of the dispersant is 1.0 to 1.5% by mass based on the calcium hydroxide.
9. The method for producing nano calcium carbonate according to claim 1, wherein the crystal form control agent is sulfuric acid; the dosage of the crystal form control agent is 0.1-0.3% of the mass of the calcium hydroxide.
10. A nano calcium carbonate product produced by using tail gas generated by treating wastes, which is characterized by being prepared by the method for producing nano calcium carbonate according to any one of claims 1 to 9.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111321589.1A CN113880127A (en) | 2021-11-09 | 2021-11-09 | Method for producing nano calcium carbonate by using tail gas generated by treating waste |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111321589.1A CN113880127A (en) | 2021-11-09 | 2021-11-09 | Method for producing nano calcium carbonate by using tail gas generated by treating waste |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN113880127A true CN113880127A (en) | 2022-01-04 |
Family
ID=79017009
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111321589.1A Pending CN113880127A (en) | 2021-11-09 | 2021-11-09 | Method for producing nano calcium carbonate by using tail gas generated by treating waste |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113880127A (en) |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20040166047A1 (en) * | 2001-07-04 | 2004-08-26 | Claude Vogels | Method for obtaining precipitated calcium carbonate particles of nanometric scale structure |
| CN101723429A (en) * | 2008-10-16 | 2010-06-09 | 上海华明高技术（集团）有限公司 | Method for manufacturing nano calcium carbonate from high-concentration carbon dioxide industrial exhaust gases |
| CN109850931A (en) * | 2019-03-29 | 2019-06-07 | 桂林理工大学 | A kind of preparation method of low-surface-energy dispersed nano calcium carbonate |
| CN110627101A (en) * | 2019-10-31 | 2019-12-31 | 河南骏化发展股份有限公司 | Process method for co-producing nano calcium carbonate by using melamine tail gas |
| CN112174183A (en) * | 2020-11-18 | 2021-01-05 | 湖北湖大天沭新能源材料工业研究设计院有限公司 | Method for preparing nano calcium carbonate by purifying and concentrating flue gas of rotary kiln |
| CN113307295A (en) * | 2021-06-25 | 2021-08-27 | 安徽前江超细粉末科技有限公司 | Method for producing nano calcium carbonate by using kiln gas with low carbon dioxide concentration |
-
2021
- 2021-11-09 CN CN202111321589.1A patent/CN113880127A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20040166047A1 (en) * | 2001-07-04 | 2004-08-26 | Claude Vogels | Method for obtaining precipitated calcium carbonate particles of nanometric scale structure |
| CN101723429A (en) * | 2008-10-16 | 2010-06-09 | 上海华明高技术（集团）有限公司 | Method for manufacturing nano calcium carbonate from high-concentration carbon dioxide industrial exhaust gases |
| CN109850931A (en) * | 2019-03-29 | 2019-06-07 | 桂林理工大学 | A kind of preparation method of low-surface-energy dispersed nano calcium carbonate |
| CN110627101A (en) * | 2019-10-31 | 2019-12-31 | 河南骏化发展股份有限公司 | Process method for co-producing nano calcium carbonate by using melamine tail gas |
| CN112174183A (en) * | 2020-11-18 | 2021-01-05 | 湖北湖大天沭新能源材料工业研究设计院有限公司 | Method for preparing nano calcium carbonate by purifying and concentrating flue gas of rotary kiln |
| CN113307295A (en) * | 2021-06-25 | 2021-08-27 | 安徽前江超细粉末科技有限公司 | Method for producing nano calcium carbonate by using kiln gas with low carbon dioxide concentration |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102320615B (en) | A kind of take SILICA FUME as the method that precipitated silica is prepared in raw material carbonization | |
| CN113371747B (en) | Preparation method of boehmite with lamellar structure and application of boehmite | |
| CN113800787A (en) | Preparation method of high-activity calcium hydroxide | |
| CN112811456A (en) | Nano calcium carbonate with high specific surface area and preparation method thereof | |
| CN111453754A (en) | Preparation method of high-purity and high-activity nano calcium carbonate | |
| CN113929328B (en) | Method for promoting crystal growth of desulfurized gypsum by regulating and controlling carbide slag-based desulfurizer | |
| CN103232052B (en) | Method for preparing high-purity calcium carbonate directly from phosphogypsum | |
| CN112875753B (en) | Preparation method of low-sodium low-ammonium high-purity molybdic acid | |
| CN113828285A (en) | Filter material for deep treatment of low-concentration fluorine-containing wastewater and preparation method thereof | |
| WO2024041497A1 (en) | Method for continuously preparing nano zinc oxide material with carbon dioxide | |
| CN113880127A (en) | Method for producing nano calcium carbonate by using tail gas generated by treating waste | |
| CN110541188B (en) | Method for preparing calcium sulfate hemihydrate crystal whisker with high length-diameter ratio by using calcium sulfate dihydrate | |
| CN112830505B (en) | Method for purifying salt mother liquor slurry by flue gas method | |
| CN110407241B (en) | Preparation method of high-activity calcium oxide | |
| CN114804673A (en) | Comprehensive utilization method of red mud | |
| CN114212813A (en) | Preparation method of nano calcium carbonate for MS sealant | |
| CN112844299A (en) | Garbage leachate biochemical effluent treatment material | |
| CN111268702A (en) | Method and device for preparing battery-grade lithium carbonate by using membrane separation technology | |
| CN110817878A (en) | Method for preparing calcium carbide from calcium carbide slag | |
| CN113354319B (en) | Method for preparing alpha-hemihydrate gypsum by using desulfurization gypsum in cooperation with high-salt wastewater of power plant | |
| CN115872451B (en) | Preparation method of sulfur-free spherical manganese carbonate powder | |
| CN116623272B (en) | Preparation method of calcium sulfate whisker | |
| CN112479263B (en) | Method for producing polymeric ferric sulfate | |
| CN111204745B (en) | Process and system for producing calcium chloride dihydrate and graphene by using chlor-alkali hydrochloric acid | |
| CN115108572A (en) | Polyaluminium chloride production method suitable for purifying various water qualities |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20220104 |