WO2008144986A1

WO2008144986A1 - Refuse recycling process

Info

Publication number: WO2008144986A1
Application number: PCT/CN2007/070516
Authority: WO
Inventors: Zhongbo Hu; Jie Ren; Xiaokang Huang
Original assignee: Beijing Sailige Corporation, Ltd.
Priority date: 2007-05-30
Filing date: 2007-08-17
Publication date: 2008-12-04
Also published as: CN100453190C; HK1110262A1; CN101099971A

Abstract

Refuse recycling process includes steps following: sorting into innocuous refuse and nocuous refuse based on the refuse property; crushing into fine powder or fine particle respectively in respective disintegrator; selecting respectively bond and encapsulant and pre-processing, bond and encapsulant after pre-processing are added right amount water to make into solution; mixing respectively said bond, encapsulant, fine powder or fine particle of innocuous refuse and nocuous refuse into slurry in respective mixer; and injecting respective slurry into respective mould and solidifying molding respectively. Said method has good binding and solidifying ability to kinds of innocuous and nocuous refuse, efficiently dispose kinds of nocuous refuse, and efficiently dispose and utilize innocuous refuse, such as flyash, gangue, and metallurgy clinker etc.

Description

Waste treatment method

Technical field

The invention relates to a technology for recycling non-hazardous wastes based on integrated phosphorus-containing inorganic polymers and silica-alumina-based gelling systems, and a treatment technology for harmful wastes, especially for harmless, non-toxic or toxic and hazardous wastes. Processing method. Background technique

With the rapid development of China's society and the rapid growth of the economy, the demand for various resources is growing. At the same time, the problems of high levels of harmful (toxic, radioactive, etc.) and non-hazardous wastes, high consumption, and high pollution are also becoming more and more serious. In particular, the contradiction of insufficient resources such as land, energy and minerals has become increasingly prominent. For example, the annual output of various solid wastes in China is as high as 1 billion tons or more, in addition to a large number of harmless and non-toxic wastes, as well as hazardous wastes from nuclear power, scientific research, medicine, and chemical industries. The reuse of non-hazardous waste and the safe disposal of toxic and hazardous waste are of great significance. In terms of the treatment of waste, especially the technical means and procedures for curing it, the more prominent condensate technology is disclosed in the patent literature, for example: CN1415567A, CN1424275A, CN1067707A, CN1223636A, CN1273222A, CN1252781A, CN1887763A, CN1887764A The technical contents disclosed in the publications are mostly related to the curing methods and processes of materials such as slag and silt. However, in the above-mentioned literature, it is difficult to realize the value of recycling all the wastes of human life and industrial waste, in other words, it is feasible according to the characteristics of the waste to be treated. Way. Important technical teachings on this side. Of course, as far as this document is concerned, there is no coverage scheme including recycling technology for all non-hazardous wastes or treatment technology for all hazardous wastes. For this reason, the present invention deliberately proposes the following solutions to this problem. Summary of the invention The technical problem to be solved by the present invention is to reuse a new generation of non-hazardous waste and a treatment technology for harmful wastes by integrating a phosphorus-containing inorganic polymer and a silica-alumina-based gelling system. The technology and technical products of the present invention combine the advantages of the above two technologies and their products, and are the replacement of the above two technologies and their products. It can be used for the reuse of non-hazardous waste and the disposal of hazardous waste in higher performance and higher efficiency. With higher reliability, wider application range and higher efficiency.

To this end, in order to achieve the above object, the technical solution of the present invention to solve the problem is: a method for treating waste, characterized in that the method comprises the following steps: classifying the waste according to the characteristics of the object, respectively Harmful wastes and hazardous wastes; respectively, the separated non-hazardous wastes and hazardous wastes are sent to their respective crushers and pulverized into fine powder or fine-grained waste; and selected for the non-hazardous wastes, harmful The binder of the waste and the raw material of the encapsulant are pretreated, and the pre-treated binder and the encapsulating raw material compound are respectively prepared into a solution with an appropriate amount of water; respectively, the binder and the encapsulant solution are respectively The fine powder or fine particles of the non-hazardous waste or the hazardous waste are stirred into a slurry in respective agitators, and then the respective slurries are injected into respective molds to be solidified. Wherein, the weight of the waste accounts for 50%-95% of the final product. And the step of pretreating the non-hazardous waste, the hazardous waste binder, and the encapsulant raw material compound, including a metal oxide or hydroxide, or a mixture of some of the compounds The pretreatment is performed by heating the object to remove small molecular impurities that may be adsorbed on the surface of the object to be treated. The heating temperature of the pretreatment heating process is 1000 ° C to 1500 ° C, and the heat treatment time is For 10-60 minutes, the container used for the heat treatment is an A1 ₂ 0 ₃ container or a MgO container or a metal platinum container, wherein the metal oxide or hydroxide is in the form of a powder. And, the weight ratio of the pretreated oxide, hydroxide or the additive thereof to the pretreated reactant is (5-15): (95-85), and the additive is in the final product. The content in the range is between 0% and 2%. And, in the processing step, the mixture of the pretreated reactant and the additive may be mixed with a certain acid or a corresponding salt in a certain ratio to form a solution or a slurry; if an acid is used; , the weight ratio of the mixture to 50% acid is 1: 1 (+/-0.1), if salt is used, the weight ratio of the mixture to the salt is 1: 3 (+/- 0.5), and a certain amount of water, water and salt weight is also required. The ratio is 1: 2 (+/- 0.5) and the weight of water in the final product is between 13% and 35%. Further, the binder raw material compound includes one or more oxides and hydroxides, one or several acids or corresponding acid ions or corresponding salts, and a small amount of additives. Moreover, the oxides and hydroxides include, but are not limited to: oxides or hydroxides of the first, second, third, and fourth main groups of metals, oxides or hydroxides of the fourth, fifth, and sixth periodic transition metals. Things. Moreover, the acid or the corresponding acid ion or the corresponding salt includes all kinds of known phosphoric acid and corresponding phosphate ion or phosphate. Also includes all kinds of known sulfuric acid and corresponding sulfate ion or sulfuric acid. Salts. The phosphates or sulfates include, but are not limited to, various phosphates of sodium and potassium. Also, the small amount of additives include, but are not limited to, boric acid, oxalic acid, and the like. And, the oxide of the first, second, third, and fourth main group metals may be Li ₂ 0, MgO, A1 ₂ 0 ₃ , GaO, SiO _{2 ,} etc.; the hydroxide may be Mg (0H) ₂ , Ca(0H) ₂ , NaOH, KOH, etc.; the oxide of the fourth, fifth, and sixth-period transition metals may be Ti0 ₂ , Fe ₂ O ₃ , ZrO, W03, etc.; It is Mn (OH) ₂ , Zr(0H) ₂ and the like. Further, the phosphate or sulfate may be potassium dihydrogen phosphate/sodium phosphate, dipotassium hydrogen phosphate/sodium or the like or a sulfate.

Compared with the prior art, the present invention combines the advantages of both the phosphorus-containing inorganic polymer and the silica-alumina gelling system and its products. Production is a complete green process, an absolute zero pollution process. The invention has strong binding and solidifying ability for various harmless and harmful wastes, and will efficiently treat various toxic and harmful wastes, efficiently treat and utilize harmless wastes such as fly ash, coal gangue and metallurgical slag. It is of great application value to reduce pollution, make full use of various types of solid waste, and promote environmental and ecological protection. DRAWINGS

Fig. 1 is a flow chart showing a method of processing waste. detailed description

The invention relates to a method for treating waste, the method comprising the steps of: classifying wastes according to object characteristics, respectively separating non-hazardous wastes and harmful wastes; separately separating the harmless ones Pre-treating the non-hazardous waste, the binder of the hazardous waste, and the encapsulating raw material compound, and preparing the pre-treated adhesive and the encapsulating raw material compound into a solution with an appropriate amount of water; The binder, the encapsulant solution and the fine powder or fine particles of the non-hazardous waste or hazardous waste are stirred into a slurry in respective agitators, and then the respective slurry is injected into the respective mold to be solidified. forming. Wherein, the weight of the waste accounts for 50%-95% of the final product. And the step of pretreating the non-hazardous waste, the hazardous waste binder, and the encapsulant raw material compound, including a metal oxide or hydroxide, or a mixture of some of the compounds The pretreatment is performed by heating the object to remove small molecular impurities that may be adsorbed on the surface of the object to be treated. The heating temperature of the pretreatment heating process is 1000 ° C to 1500 ° C, and the heat treatment time is For 10-60 minutes, the container used for the heat treatment is an A1 ₂ 0 ₃ container or a MgO container or a metal platinum container, wherein the metal oxide or hydroxide is in the form of a powder. And, in the step of pretreating the oxidized additive, the weight ratio of the additive to the pretreated reactant is (5-15): (95-85), and the additive is in the final product. The content is between 0% and 2%. And, in the processing step, the mixture of the pretreated reactant and the additive may be mixed with a certain acid or a corresponding salt in a certain ratio to form a solution or a slurry; if an acid is used; , the weight ratio of the mixture to 50% acid is 1:1 (+/-0.1), and if salt is used, the weight ratio of the mixture to the salt is 1:3 (+/-0. 5), also need to add a certain amount of water. The weight ratio of water to salt is 1: 2 (+/- 0.5), and the weight of water in the final product is between 3% and 35%. And, the binder raw material compound includes one or several oxides and hydroxides, one or several acids or corresponding acid ions or corresponding salts, and a small amount of additives. Moreover, the oxides and hydroxides include, but are not limited to: oxides or hydroxides of the first, second, third, and fourth main groups of metals, oxides or hydroxides of the fourth, fifth, and sixth periodic transition metals. Things. Moreover, the acid or the corresponding acid ion or the corresponding salt includes all kinds of known phosphoric acid and corresponding phosphate ion or phosphate. Also includes all kinds of known sulfuric acid and corresponding sulfate ion or sulfuric acid. Salt. The phosphate or sulfate includes, but is not limited to, various phosphorus of sodium and potassium. Acid salt. Also, the small amount of additives include, but are not limited to, boric acid, oxalic acid, and the like. And, the oxide of the first, second, third, and fourth main group metals may be Li ₂ 0 , MgO , A1 ₂ 0 ₃ , GaO, S i0 _{2 ,} etc.; the hydroxide may be Mg (OH) ₂ , Ca (0H) ₂ , NaOH, KOH, etc.; the oxide of the fourth, fifth, and sixth-period transition metals may be Ti0 ₂ , Fe ₂ O ₃ , ZrO, W0 _{3 ,} etc.; The substance may be Mn (0H) ₂ , Zr (0H) ₂ or the like. Further, the phosphate or sulfate may be potassium dihydrogen phosphate/sodium, dipotassium hydrogen phosphate/sodium or the like.

For example, the present invention can produce various types of high-quality building materials of various colors (cement ash, wood chips, furnaces, glass and domestic garbage, underwater sludge, etc.) using almost any kind of harmless solid and colloidal waste (fly ash, wood chips, furnaces, etc.) , building materials, structural materials, fireproof materials, etc.); as another example, the invention can be used to treat various contaminated solids, sludges and liquids, various harmful metals, various low-level radioactive wastes, and various harmful The effective encapsulation treatment of the chemicals; for example, the invention can be used for sludge solidification treatment of reclamation, backfilling and embedding of abandoned mines, and the like. The product can be molded at room temperature or even at low temperature, and the process equipment is single and mature. low cost. The product molding process is a purely inorganic chemical process that does not release any harmful substances and does not cause any secondary pollution. The product has high compressive and flexural strength, excellent thermal stability and radiation resistance. The product is compact. Product performance and cost can be adjusted to some extent. The proportion of waste in the finished product (weight or volume) can be as high as 95%. The invention effectively improves the environment while efficiently utilizing various types of solid wastes to turn waste into treasure. Benefit the country and the people.

The invention adopts the mature production process of the single cylinder, and uses various harmless wastes as the main raw materials to prepare products with excellent physical properties such as mechanical, mechanical and thermal stability. Or efficient and reliable packaging of hazardous waste. The process can be described as follows: First, according to the characteristics of the non-hazardous waste to be used or the hazardous waste to be treated, the raw material selected as the adhesive or encapsulant is pretreated, and then pretreated. Several raw materials are mixed with water in proportion to form a solution. One or more kinds of wastes are added to the obtained solution, and stirred to form a slurry. Finally, the obtained slurry is injected into a mold and solidified.

The technical features: room temperature process, no additional energy; rapid formation of hard, to the quasi-ceramic finished product; finished product performance and molding process can be regulated; extremely high efficiency of handling hazardous waste; extremely high efficiency of using non-hazardous waste; In most cases, the product has a slight expansion during solidification molding, which results in a good seal. The product has excellent tightness; it can be combined with almost any material except plastic and rubber, and has strong plastic/rubbery properties.

The unique and superior properties of this technology/product make it suitable for: 1. Production of building products (such as bricks, tiles, tiles, firewall insulation panels, etc.) using non-hazardous waste; high compression resistance structure Materials; sprayable super fire barrier; cement and sealing materials for drilling; seal coating; 2. safe packaging of hazardous waste; leak-free sealing treatment of radioactive contaminants; hazardous mixtures and radioactive materials (liquid or solid) Safe storage. The specific areas of use are summarized in Schedule 1.

The preparation equipment and process of the technology are the same as or similar to the common concrete, and no additional molding energy is needed. The extensive utilization of common waste effectively improves the economic benefit of the technology. Considering its particularly excellent physical properties (including low porosity, high resistance) Flammability and high strength), its performance and price ratio is extremely competitive. This technology is a green process with no secondary pollution. The product composed of the method of the invention has a compressive strength of up to 83 MPa and a flexural strength of up to l lMPa. The product has excellent thermal stability and is resistant to radiation. Moreover, the weight or volume of waste in the finished product can be as high as 95%.

Schedule 1. Application

Schedule 2. Product Parameter Table

Table 1. Application

Scope application

Building structural materials, high-strength structural materials

Recycling waste in construction and other industrial sectors

Gong Guangkou

Road maintenance (including low temperature environment)

Sealants

Fire insulation material

Inorganic binder

Solid waste treatment Treatment of contaminated solids, liquids and mud

Chemical stabilization of any hazardous metals, low-level radioactive waste, nuclear waste and physical solidification

Contaminated debris, storage of metal and non-metallic equipment

Efficient recycling of waste (fly ash, ore slag, metal scrap, wood chips, waste glass, used tires, etc.)

Oil and gas drilling super-solid sealing agent

Ribbon barrier

Stabilization/fixation of the drilling hole

High-strength cement for horizontal drilling

Debrisment of debris and cuttings

Bioceramics dental ceramic materials

Artificial bone ceramic material

Refractory, fireproof, flame retardant material

Cast large size crucibles and components Table 2. Product Parameter Table Parameter Name Performance Parameter Remarks

Density 1. 7-2. Og/cc can vary with fillers and additives

Appearance porosity is about 0,

Porosity There are very few pores inside, which can cause pores.

Compressive strength 8000-12000 ps i (55-83MPa) can change the flexural strength with fillers and additives 900-1600 ps i (6. 2-l lMPa) Adding fiber can enhance the flexural strength section toughness 0. 3- 5范围稳定稳定: The addition of fiber, whisker, etc. can enhance the toughness water stability in the range of PH3. 5-11 stable

The coefficient of thermal expansion is about 10-7 °c and varies with additives.

Flame-retardant adhesive is excellent in flame retardancy even when mixed with wood chips. It has good flame retardancy, heat stability, and good thermal stability. The thermal stability of the finished product may be affected by additives. Radiation resistance (Beta, Gamma ray, etc.) is strong

Fill Type Any slag or other industrial / domestic waste

7. 5%-50% binder,

The ratio of binder to filler is the filler

The amount of water is generally sensitive to the additive and its particle size by half the weight of the binder. Molding time is a few minutes to a few hours. A small amount of the additive can change the molding speed. The viscosity of the slurry before molding can be 200-1000 cps. Change the viscosity of the heat production exothermic process, can be cured at low temperature. The pH of the exothermic slurry can be controlled by the pretreatment of the additive. The pH of the product from strong acid to neutral liquid is about 8

Molding process Casting, extrusion, spraying can be adjusted according to the molding process

Surface texture from smooth to rough depending on the mold

Color pure adhesive porcelain is white. It can be changed by adding ceramic pigments. The dimensional change during solidification molding is slightly expanded. It can be formed according to the complex mold shape. The production equipment is usually used in concrete production equipment and any material outside the plastic. Cement is slightly more expensive, but the performance is superior

Claims

Rights request

A method for treating waste, characterized in that the method comprises the steps of: classifying the waste according to the characteristics of the object, respectively separating the non-hazardous waste and the hazardous waste; separately separating the harmless waste Raw materials and hazardous wastes are sent to their respective pulverizers for pulverization into fine powders or fine granules. At the same time, the raw materials for the non-hazardous wastes, hazardous wastes, and encapsulant raw materials are selected for pretreatment. The treated adhesive and the encapsulating raw material compound are respectively prepared as a solution with an appropriate amount of water; respectively, the adhesive, the encapsulant solution and the fine powder or fine particles of the non-hazardous waste and hazardous waste are respectively The slurry was stirred into a separate agitator, and then the respective slurry was injected into respective molds to be solidified.

The method of treating waste according to claim 1, wherein the weight of the waste is 50% to 95% of the final product.

The method for treating waste according to claim 1, wherein the step of pretreating the non-hazardous waste, the binder of the hazardous waste, and the encapsulant raw material compound includes The metal oxide or hydroxide, or a mixture of some of the compounds, is pretreated by heating the object to remove small molecular impurities that may be adsorbed on the surface of the object to be treated, The preheating heating process has a heating temperature of 1000 ° C to 1500 Torr, a heat treatment time of 10 to 60 minutes, and a container for heat treatment is an A 1 ₂ 0 ₃ container or a MgO container or a metal platinum container, wherein the metal oxide is Or the shape of the hydroxide is in the form of a powder.

The method for treating waste according to claim 3, wherein the pretreatment step of the pretreated oxide, hydroxide or a mixture thereof is further included in the pretreated The step of adding an additive to the reactant, the weight ratio of the additive to the pretreated reactant is (5-15): (95-85), and the content of the additive in the final product is 0% to 2%. between.

The method for treating waste according to claim 3, wherein the pretreated reactant and the mixture of additives are processed in the step of treating the mixture with an acid or phase.

9

Replacement page (Article 26) The salt should be mixed in a certain ratio to form a solution or slurry; if acid is used, the weight ratio of the mixture to 50% acid is 1:1 (+/-0.1), if salt is used, Then the weight ratio of the mixture to the salt is 1: 3 (+/- 0.5), and a certain amount of water is also required. The weight ratio of water to salt is 1: 2 (+/- 0.5). The weight of water is between 3% and 35% of the final product.

The method for treating waste according to claim 3, wherein the binder raw material compound comprises one or more oxides and hydroxides, one or several acids or corresponding Acid ion or corresponding salt, a small amount of additives.

The method for treating waste according to claim 6, wherein the oxides and hydroxides include, but are not limited to: oxides or hydroxides of the first, second, third, and fourth main groups of metals. An oxide or hydroxide of a transition metal of the fourth, fifth, or sixth cycle.

The method for treating waste according to claim 6, wherein the acid or the corresponding acid ion or the corresponding salt comprises all kinds of known phosphoric acid and the corresponding phosphate ion or phosphate. Also included are all known types of sulfuric acid and corresponding sulfate ions or sulfates. The phosphates or sulfates include, but are not limited to, various salts of sodium and potassium.

The method of treating waste according to claim 6, wherein the small amount of the additive includes, but is not limited to, boric acid, oxalic acid, or the like.

The method for processing waste according to claim 7, wherein the oxide of the first, second, third and fourth main group metals is L i ₂ 0 , MgO , A1 ₂ 0 ₃ , GaO, S i0 _{2 ,} etc.; the hydroxide may be Mg (OH) ₂ , Ca (0H) ₂ , Ca (0H) ₂ , NaOH, KOH, etc.; the fourth, fifth, sixth-period transition metal The oxide may be Ti0 ₂ , Fe ₂ O ₃ , ZrO, W0 ₃ or the like; the hydroxide may be Mn (0H) ₂ , Zr (0H) ₂ or the like.

The method for treating waste according to claim 8, wherein the phosphate or sulfate may be potassium dihydrogen phosphate / sodium, dipotassium hydrogen phosphate / sodium or the like or a sulfate.