TW201116500A - Solid product made from by-produced petroleum ash in circulation fluidized bed and manufacturing method thereof - Google Patents

Abstract

A solid product made from the by-produced petroleum ash in a circulation fluidized bed and a manufacturing method thereof are disclosed. It mainly includes mixing an aggregated material of by-produced petroleum ash in a circulation fluidized bed with a catalyst and water to form a slurry. The slurry is then solidified to form the article. It can effectively and properly use the by-produced petroleum ash generated when burning petroleum coke and coal in the circulation fluidized bed so that the petroleum ash can be quickly liquefied and solidified to form an aggregated material of good-quality and cheap price. The obtained solid product further has a high compression strength and can be widely used for fulfilling excellent resource recycle performance.

Description

201116500 VI. Description of the Invention: [Technical Field] The present invention relates to a cured product and a method for producing the same, and more particularly to a by-product of petroleum coke ash produced by a circulating fluidized bed boiler and [prior art] / petroleum coke (petroleum coke) is a by-product derived from the refinery. The appearance is black block and granular. The heavy oil obtained by using crude oil after steaming is subjected to thermal cracking, condensation, coke formation, cold coke and removal. The main components of petroleum coke are carbon, which accounts for more than 8%, and the remaining components are hydrogen, oxygen, li, sulfur and metal. The average sulfur content is about 7%. At present, the main uses of petroleum coke are: (1) boilers, steam and electricity symbiosis, cement and other fuels; (2) electrodes for steelmaking and refining, and (3) carbon materials for producing elemental structure, calcium carbide and tantalum carbide . Because petroleum coke has the characteristics of low ash content and high calorific value, it is often used as an alternative fuel. According to statistics, about 38% of the petroleum coke produced worldwide is used as cement sputum fuel, and about 12% is made. For industrial sales of fuel. However, petroleum coke contains about 7% of high sulfur content, which will emit excessive sulfur oxides when it burns, causing environmental pollution problems. Therefore, it is mainly used in circulating fluidized bed boilers (Circulating Fluidized Bed-Boiler, CFB) This combustion technology solves the problem of sulfur oxide emissions from burning petroleum coke by adding limestone (CaC〇3) to the combustion process. At the same time, in the circulating fluidized bed boiler In operation, the fly ash collected by the electrostatic precipitator and the yellowish brown granules collected from the bottom of the furnace (201116500 bed ash) are usually produced. The by-products are collectively referred to as CFB by-product petroleum coke, especially the 'CFB by-product petroleum coke is quite stable, does not contain toxic substances' and mainly contains about 90% of the total amount of lime (Ca〇) and gypsum ( CaS〇4) has great potential for recycling. Therefore, CFB by-product petroleum coke has been applied to civil engineering materials, road engineering (such as road base layer graded pellets) and soil improvement. Good use of sludge, sludge curing agent, etc. But in fact, since the gypsum contained in the CFB by-product petroleum coke (ie, no melon acid) is a type II anhydrite, in general, the anhydrite gypsum forms a gypsum (cas04.2H20). The speed is very slow, the self-claying ability is not good, and there is research literature that when the CFB fly ash is used to replace the cement in the concrete, the amount of substitution of the CFB fly ash increases (>1G%), which will cause the concrete block to set. Prolonged (ie, retarded) and reduced compressive strength limit the development and application of CFB by-product petroleum coke. 【Contents】 ^ ^ ^ ^ ^ ^ m > The by-product of the petroleum coke produced by burning the coke and lime is a cementitious material that makes the curtain of high-quality curtains, and then has a high anti-μ strength to provide戍@姆化' to achieve excellent recycling of resources; the bed by-product petroleum coke ash solidified material and its preparation method.玷 、 、 I 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明The winnings include the circulating fluidized bed Jin Saoda's petroleum coke fly ash. 201116500 The effect of the invention is that when the cement containing the petroleum coke fly ash by-product of the circulating fluidized bed furnace, the catalyst and the water are mixed together, the anhydrite in the cement is quickly converted into dihydrate gypsum, thus The binder can exert excellent self-adhesive ability for rapid hydration and solidification, thereby producing a high compressive strength and high economical cured product for reuse, thereby achieving excellent resource treatment efficiency. [Embodiment] The above and other technical contents, features and effects of the present invention will be apparent from the following detailed description of the preferred embodiments. The method for preparing petroleum coke ash by-product of the circulating fluidized bed boiler of the invention is to make a cementitious material under the condition that the water-to-binder ratio is controlled between 〇1〇~5〇〇. Mix well with a catalyst (acceierat〇r) to form a colloidal slurry. The water-to-binder ratio (W/B) here is the ratio of the water mix (kg/m3) to the total amount of binder plus catalyst (kg/m3), ie W/B = water mix / (binder + catalyst) . %, the binder is a petroleum coke, cement, pozzolan material, or a combination thereof, which is a by-product of a circulating fluidized bed boiler. The source of by-product fluid petroleum coke (hereinafter referred to as CFB petroleum coke) is a mixture of two by-products produced by the circulating fluidized bed boiler set up by the Formosa Petrochemical Light Oil Plant. Its composition is shown in Table )), which is taken from the electrostatic precipitator for the circulating fluidized bed steel furnace by-product petroleum coke fly ash (hereinafter referred to as CFB fly ash), which is taken from the bottom of the furnace is a circulating fluidized bed. Boiler by-product petroleum coke bottom ash (hereinafter referred to as CFB bottom ash), the basic physical properties of the two are shown in Table 2. It is clear that the CFB petroleum coke is basically an anhydrous gypsum containing 6 (four) ~ Μ% of 201116500 (CaS〇4, also known as anhydrite) and 25%~35% lime (Ca〇), etc., and can also be seen from the scanning electron microscope (SEM) of CFB fly ash shown in Figure 2. Out, CFB fly ash does contain a large amount of irregular block anhydrite structure and there are more obvious pores between the anhydrite particles. χ, 卜作岚 material is fly ash, slag, or a combination of these

Si02, Al2〇3, CaO, and the like. [Table 1] Percentage of chemical composition CaS04 60%-65% CaO 25%-35% Si02 2.50% AI2O3 0.35% Fe203 0.17% K20 0.62% MgO 2% pH 12.4 Appearance specific gravity CFB fly ash gray white powder 2.80 CFB bottom gray yellow Brown granules 3.05 ~~' 0.001-0.075 (4) / again, VIII / g) 3050 0-075-0.600 1260 In addition, the catalyst is sulfuric acid unloading (K2S04), sodium sulphate (Na2so4), unloading sputum (KA1 (S04) 2.12 H20), burnt alum (KA1 (so4) 2), potassium complex (K2Cr2〇7), sodium hydrogen sulfate (NaHs〇4), or a combination of these. Mainly, in the mixing system composed of cement-catalyst~water, the binder and catalyst are dispersed in the water environment, and the solvation of the disk 201116500 is dissolved. As the hydration reaction proceeds, the system Granular/colloidal hydration products that produce irregular crystal forms, such as: dihydrate gypsum (

CaS〇4.2H2〇), calcium hydroxide (Ca(0H)2), catalyst hydrate (such as KA1(S04)2.12H20), calcium hydrophobic compound (Ca〇Si〇2_H2〇, referred to as CSH), dance chain water Compound (Ca0-A12〇3_H2〇, abbreviated as cAH), ettringite (ca6Al2(s〇4)3(OH)]2.26H2〇), etc. 'In particular, the catalyst can activate the binder (such as CFB fly ash, cement, hearth powder) With fly ash, etc., it stimulates the cementation ability of φ cement, so that the cement can be hydrated sufficiently and rapidly to form a large amount of hydration products (corpusate type), and these hydration products will be filled in the micropores of the mixed slurry. f, forming a reinforced agglomerated crystal structure network, so that the structure of the slurry is more ambiguous, and then rapidly coagulated and hardened into a cured product (such as concrete) capable of exerting strength. When the mixing process lasts for about one minute at normal ambient temperature, the still colloidal or solidified slurry is further cured to improve the hardness and strength that can be developed, and the curing mode can be based on the future. The use environment of the solid compound is determined. For example, since the cement is a gas-hard material, the solidified material is used in a non-soaking water environment, as long as the slurry is naturally dried and hardened in the brewing environment. ~2 days can be, however, if the cured product is to be used in the soaking water environment in the future, it must be applied for about 2~3 days of natural air-drying and then dipped at a concentration of about 5〇/〇~ 5% water glass 'Kun. In the liquid, it is cured in water for about 7 to 21 days to improve the water resistance of the cured product. After the above-mentioned curing treatment is finished, the cured product is continuously placed in the room temperature to obtain the hydration rate (%), the waste resistance strength (kgf/cm2), the first eight ends 201116500, the condensation time (min), the surface Dry saturation density (g/cm3), drying density (g/cm3) and other tests. As shown in Table 3, in the examples j to 25 of the present invention, the ratio of the binder used in the pure CFB fly ash and the catalyst was ～99 wt%. lwt% to 5 wt%, the water shift ratio. Controlled at 0.50, mainly by changing the ratio of cfb fly ash to catalyst, and the type of catalyst used, to explore the feasibility of resource recycling of CFB fly ash slurry, and at the same time with the comparative routine 'that is not blended The pure CFB fly ash slurry formed under any catalyst was used as a comparison. From the formula (1), the hydration reaction carried out in the CFB fly ash-catalyst/water mixed slurry system, CFB fly ash (expressed as [A0/〇CaS04 + B〇/〇CaO], actually 65 %CaS04+ 35%Ca0) rapidly reacts to form CaS〇4.2H2〇 and Ca(OH)2 under the activation of the catalyst, and the catalyst also hydrates to form a hydrate represented by [catalyst.(n-2m)H2〇] Taking the catalyst kai(so4)2 as an example, the hydrate is KA1(S04)2_12H20. Since these hydration products are filled in the pores of the CFB fly ash slurry, the structure of the CFB fly ash slurry is more dense, and It can be quickly condensed and hardened. m[A%CaS04 + B%CaO] + Catalyst + nH20 —a [CaS04-2H20]+ Stone Ca(〇H)2+ Catalyst.(n-2m)H20 (1) From the test results in Table 3, Under the conditions of using the same catalyst, the catalysts of Examples 12 to 15 are also KAl(S〇4)2, and the catalysts of Examples 16 to 17 are the same as Κ2〇2〇7' as the amount of the catalyst increases, Examples The hydration rate and compressive strength of CFB fly ash slurry formed in 1~25 have an increasing trend of 201116500, and the clotting time is relatively shortened, in particular, compared with the structural characteristics of pure CFB fly ash slurry of Comparative Example 1 (28) The hydration rate of day age is about 29.350/〇, the compressive strength is 20 kgf/cm2 'the initial and final setting time are 36〇mins, 1080 mins respectively, and the hydration rate of CFB fly ash slurry of Examples 1~25 (45.98~96.24%), compressive strength (44~350 kgf/cm2), initial setting time (27~134 mins) and final setting time (1〇〇~362 mins), the performance obviously jumped sharply, so it can be It proves that the addition of catalyst can indeed stimulate the cementation ability of CFB fly ash, which helps it to fully and rapidly hydrate and coagulate, thus effectively strengthening CFB fly ash slurry. Compressive strength. Furthermore, it can be seen from the SEM photograph of the pure CFB fly ash slurry of Comparative Example 1 shown in Fig. 3 and Fig. 4 that after the CFB fly ash is hydrated, the original irregular block anhydrite has been roughly converted into a denser one. Dihydrate gypsum, and the pores of the slurry are less, but compared with the SEM photograph of the CFB fly ash slurry of Example 14 shown in Fig. 5 and Fig. 6, the CFB fly ash can be catalyzed by KAl(S〇4)2. Fully converted into dihydrate gypsum, the slurry structure is more dense and less pores. It can be proved that the addition of the catalyst can improve the material structure of the slurry to achieve higher strength requirements. Further, in the case of using the different catalysts, those using KA1 (S04) 2 in Examples 12 to 15 and K2Cr 207 in Examples 16 to 18 can exert a preferable excitation strength to form a CFB fly ash. The compressive strength of the body is close to or higher than 200 kgf/cm2, and in particular, the compressive strength of the CFB fly ash slurry of Example 14 and Examples 16 to 18 is the most excellent. Therefore, the catalysts used in the other Examples 26 to 37 were uniformly selected from kai(so4)2. 201116500

*Water-to-binder ratio (W/B) *Binder +catalyst 0.50:100% *Primary setting: refers to the need for the slurry to start mixing to lose plasticity. *Final condensation: refers to the time required for the slurry to solidify to withstand a specific pressure. * Age: refers to the time when the slurry is cured from the beginning to the test. 201116500 As shown in Table 4, in the examples 26 to 29 of the present invention, the cement used is made of CFB fly ash, cement and buck. The bismuth material (ie, whetstone powder, fly ash) is composed, and the ratio of CFB fly ash, cement, buckwheat material and catalyst is 50 wt% to 80 wt%: Owt% 〜5 wt%: 10 wt% 〜40 wt%: lwt% ~5wt%, the water-to-binder ratio is controlled at 0.50, the catalyst is KAl(S〇4)2, and the dosage is 3wt%. Here, the amount of CFB fly ash is replaced by cement and buckwheat material to explore the formation of the slurry. The influence of body structure characteristics. According to the formula (1), CFB fly ash, catalyst and water will react to form Ca(OH)2, and the old material (including SiO2, Al2〇3) will react with hydrogen and oxygen to produce crystal. Calcium-aluminum hydrate (CAH) (see formula (2)) and low-density colloidal calcium-hydrazine hydrate (CSH) (see formula (3)), therefore, the binder-catalyst of Examples 26-29 The reaction carried out in the water system can be represented by the formula (4).

Ca(0H)2+Al203+H20 — Ca0Al203.H20 (2)

Ca(OH)2+SiO2+H2〇—Ca0.SiO2.H20 (3) a[CaS04.2H20]+ ;5Ca(OH)2 + catalyst.(n-2m)H20+ Bud material#(4)a [CaS04.2H20] + Y[CaO.Al2〇3·Η20] + Y[CaO.Si02.H20] + catalyst. (n_2m)H20 compared to Example 14 (97wt% CFB fly ash and 3wt% KA1 (S04 2), that is, the CFB fly ash is not replaced by cement or buckwheat material. In the examples 26 and 28, CFB fly ash is replaced by cement and hearth powder. When the substitution amount is 30 wt%, the CAH colloid is formed. The hydration product such as CSH colloid can further improve the compressive strength and setting time of the formed slurry. 201116500 Sample cement (wt%) Compressive strength (kgf/cm2) Condensation time (min) Density (g/cm3) Age of initial condensation, dry surface, dry saturation, drying CFB, thief cement, special material, 1 day, 3 days, 7 days 28 Days of Hearthstone Fly Ash Example 14 97 — — 25 73 109 208 28 114 1.60 1.40 Example 26 67 — 30 — 22 68 103 218 30 110 1.58 1.34 Example 27 77 — 20 — 23 66 98 190 28 116 1.59 1.35 Example 28 67 5 25 — 23 73 112 224 25 120 1.58 1.35 Example 29 67 — — 30 20 55 88 183 35 144 1.60 1.42 Rhodium catalyst: KA (S〇4) 2 * Amount: 3 wt% * Water gel Ratio (W/B) = 0.50 Umbrella Glue + Catalyst = 100% * Surface Dry Saturation Density: The mass per unit volume of the saturated surface dry test body, the volume of which contains the pores inside the sample and the part filled with water. Dry Density: The mass per unit volume of the dried test body, the volume of which contains the permeable and impermeable pores in the test body [Table 4] As shown in Table 5, in Examples 30 to 37 of the present invention, further to the slurry The body is doped with an aggregate, and the control conditions for mixing and curing are the same. Above. Among them, the cement is pure CFB fly ash, the aggregate is CFB bottom ash (fine aggregate), natural river sand (fine aggregate), stone (crude aggregate), soil (fine aggregate), or one of these combination. Here, in terms of the ratio of the binder (Cfb fly ash) to the catalyst (KAl(S〇4)2), it is still 97 wt%: 3 wt°/〇' to explore the coarse or thin bone. The addition of the material has an effect on the structural properties of the formed slurry. When the aggregate is CFB bottom ash, the ratio of CFB fly ash, CFB bottom ash, catalyst, water drop is 25 wt%~45 wt%: 25 wt%~55 wt%: 〇.5 wt%~3 wt〇/〇: 15 wt% ~35wt%. As in Example 3, the ratio of CFB fly ash, CFB bottom ash, catalyst to water mix is 3〇 23 wt%: 42.6〇wt%: 0.94 wt%: 26.23 wt%, and the water-to-binder ratio is 〇83. 12 201116500 When the aggregate is natural river sand, the ratio of CFB fly ash, natural river sand, catalyst and water mix is 25wt%~45wt%, 25wt%~65wt%, 0.5wt%~3wt%, 10wt%~35wt %. As in Example 31, the ratio of CFB fly ash, natural river sand, catalyst, and water mix was 27.32 wt%: 57.75 wt%: 0.85 wt%: 14.08 wt%, and the water-to-binder ratio was 0.50. When the aggregate is composed of CFB bottom ash and stones, the ratio of CFB fly ash, CFB bottom ash, stone, catalyst, and water mixing amount is 25 wt% to 45 wt%, 15 wt% to 35 wt%, 15 wt% to 35 wt%, 0.5wt%~3wt%,

15wt%~35wt%. As in Example 32, the ratio of CFB fly ash, CFB bottom ash, stones, catalyst, and water mix was 27.32 wt%: 19.25 wt%: 19-25 wt%: 0.85 wt. /. : 18.92 wt%, water-to-binder ratio is 0.67. When the aggregate is composed of natural river sand and stone, the ratio of CFB fly ash, natural river sand, stone, catalyst and water mixing amount is 25wt%~45wt%: 15wt%~35wt%: 15wt%~35wt% · 0.5 Wt%~3wt%: 1 Owt%~35wt%. As in Example 33, the ratio of CFB fly ash, natural river sand, stone, catalyst, and water mix is 27.32 wt%: 28.87 wt°/〇: 28.87 wt%: 0.85 wt%: 14.08 wt%, the water-to-binder ratio is 0.50. As shown in Examples 34 to 36, when the aggregate is soil, the ratio of CFB fly ash, soil, catalyst, and water mixing amount is 5 wt% to 3 Owt%: 30 wt% to 70 wt%: O.l wt% to 3 wt%: 10wt%~40wt%. In the case of Example 34, the ratio of CFB fly ash, soil, catalyst, and water mixing amount was 5.11 wt / 〇 : 68.42 wt ° / 〇 : 0.16 wt % : 26.32 wt %, and the water-to-binder ratio was 5_00. When the aggregate is composed of CFB bottom ash and soil, the ratio of CFB fly ash, CFB bottom ash 'soil, catalyst to water mix is 5wt%~30wt%: 13 201116500 5wt%~30wt%: 30wt%~70wt % : 0.1 wt% to 3 wt% : 10 wt% to 40 wt%. As in Example 37, the ratio of 'CFB fly ash, CFB bottom ash, soil, catalyst, and water mix is 5.11 wt%: 5.26 wt%: 63.16 wt%: 0.16 wt%: 26.32 wt%, and the water-to-binder ratio is 5.00. . Compared with the CFB fly ash slurry formed in Example 14, the compressive strength at 28 days of age was 208 kgf/cm2, and Examples 30 to 33 were apparently added to the CFB bottom ash, natural river sand 'stones and the like, The compressive strength of the formed slurry (such as mortar, concrete slurry) is generally improved; moreover, the SEM photograph of the embodiment 30 shown in Fig. 7 and Fig. 8 shows that the microstructure of the slurry material is compared with the figure. 5 and the embodiment 14 shown in Fig. 6 are indeed more dense, so that the compressive strength is better, and the feasibility of forming a slurry by the CFB fly ash-CFB bottom ash-catalyst-water system is demonstrated. Further, Examples 30 and 32 in which CFB bottom ash was used as the fine aggregate were superior to those in Example 3 in which natural river sand was used as the fine aggregate.

catalyst

Example 31 0.94 26.23 0.84 Example 32 Example 33 Example 34 Example 35 Example 36 Example 37 * Cemented half * Cemented half

Water-to-binder ratio water mix wt%

14 201116500 The results of the compressive strength of the similar cement slurry formed in Examples 34 to 37 show that the compressive strength at 28 days of age can reach 10 kgf/cm2 or more, which can be used as a geological improver. The compressive strength and effect should be similar to those of traditional cement as a geological improver. It can be seen that the cement system formed by CFb fly ash and soil is suitable for geological improvement. Further, as shown in Table 6, Example 14 and Examples 38 to 4 are mainly for discussing the influence of the fineness of the binder (CFB fly ash) on the compressive strength of the slurry. Obviously, as the fineness of CFB fly ash increases, that is, the specific surface area increases, the compressive strength of the formed slurry increases, indicating that the hydration speed of CFB fly ash with high fineness is relatively accelerated, and the self-claying ability Preferably. [Table 6] Example binder catalyst specific surface area (cm2/g) Compressive strength (kgf/cm2) Age 7 days 28 days Example 1 4 Example 38 Example 39 Example 40 CFB fly ash: 97 wt% KA1 (S04)2 :3 Wt% 3000 109 208 Γ 4000 135 254 5000 150 288 6000 153 301 氺 No-binder ratio (W/B) = 0.50 — 氺 结 + + + + + + + + + + + + + + : Water mixing amount = 64.67 Wt%: 2wt%: 33.33 wt% According to the test results of the above examples, it is known that under the activation of the catalyst, the CFB fly ash can be rapidly hydrated and solidified, and the gelation ability is excellent. It can be used as a cementing material for high quality curtains. At the same time, CFB bottom ash can also be used as a fine aggregate for blending, so that the cured product produced can exert excellent compressive strength of about 100~350 kgf/cm2. . Therefore, the method for producing a petroleum coke ash by-product of the circulating fluidized bed boiler of the present invention is not only an operator [S]. 15 201116500 The method is simple in operation and low in cost, and can also make CFB _ ash become excellent in bonding ability and replace Cohesive material of cement potential, and proves the feasibility of using cfb bottom ash as an aggregate material, in particular, the circulating fluidized bed pin furnace of the present invention produces a petroleum coke ash solidified product 'whether pure CFB fly ash slurry, or It is a slurry which is blended into other cement materials (such as cement, fly ash, hearth powder) and coarse/fine aggregates (such as (10) bottom ash, river sand, stone, soil). The structure is quite dense and can be excellent. Compressive strength can be used not only as a new building material of similar gypsum or concrete with high economic value, but also in compliance with environmental green building materials or as a higher level of application. Therefore, CFB petroleum coke can be handled safely and at low cost, and (10) petroleum coke ash products with high economic value can be produced, achieving excellent recycling and recycling.

The present invention relates to a circulating fluidized bed furnace of the present invention, which produces a petroleum coke ash solidified product and a method for producing the same, which can create a CFB by using a simple method and a low cost, so that the same value can be utilized. The cured product which can be used as a cementing material for high-quality curtains can also be used as an environmentally friendly green building material, so that cfb petroleum coke can be effectively resourced, so that the purpose of the present invention can be achieved. 'It is only a preferred embodiment of the present invention, and it is not possible to limit the scope of the present invention to a simple equivalent change of the scope of the invention and the description of the invention. And (4), are still within the scope of the patent of the present invention. [Simplified description of the drawings] Figure 1 疋 SEM photograph ' illustrates the microstructure of the CFB fly ash of the present invention at a magnification of 200 times; Figure 2 is a SEM photograph, The microstructure of the (10) fly ash of the present invention at a magnification of 16 201116500 3000 times is shown; FIG. 3 is a SEM photograph illustrating the microstructure of a pure CFB fly ash slurry prepared in Comparative Example 1 of the present invention at a magnification of 200 times; Figure 4 is a SEM photograph showing the hair The microstructure of the pure CFB fly ash slurry prepared in Comparative Example 1 at a magnification of 2000 times; FIG. 5 is a SEM photograph showing the microstructure of the slurry prepared in Example 14 of the present invention at a magnification of 200 times. Figure 6 is a SEM photograph showing the microstructure of the slurry prepared in Example 14 of the present invention at a magnification of 3000 times; Figure 7 is a SEM photograph showing the slurry prepared in an embodiment 30 of the present invention; The microstructure at a magnification of 200 times; and Fig. 8 is a SEM photograph showing the microstructure of the slurry prepared in this Example 30 of the present invention at a magnification of 5000 times.

17 201116500 [Explanation of main component symbols] (none)

18

Claims (1)

201116500 VII, the scope of application for patents: [: a kind of circulating coagulation wire furnace by-product petroleum coke ash curing (four) method, is a mixture of cement and a catalyst mixed with water into a polymer, and then the coagulation solidified into a solid, basin Medium, ^ 〃中5 玄胶钇 is a by-product petroleum coke fly ash containing circulating fluidized bed boiler. 2. According to the method for preparing a petroleum coke ash solidified by-product of a circulating fluidized bed boiler according to the scope of the patent application, wherein the cement further comprises cement, a material for bucking, or one of the materials combination. 3. According to the method of the second aspect of the patent, the circulating fluidized bed _ by-product petroleum coke ash solidification method, wherein the binder is a circulating fluidized bed steel furnace by-product petroleum coke fly ash, and the circulation flow The ratio of the by-product petroleum coke fly ash and the catalyst of the chemical bed pin furnace is 95 wt% to 99 wt%: lwt% to 5 wt%. 4. According to the method for preparing a petroleum coke ash solidified by-product of a circulating fluidized bed steel furnace as described in the second paragraph of the patent scope of the patent application, wherein the binder is produced by a circulating fluidized bed furnace, by-product petroleum coke fly ash, The cement and the concrete are composed of the materials, and the ratio of the petroleum coke fly ash, the cement, the concrete material and the catalyst by-product of the circulating fluidized bed boiler is 50wt〇/. ~8〇wt%: 〇wt%~5wt%: 10wto/〇~40wt%: lwt%~5wt%. 5. According to the method for preparing a curable ash solidification product of a circulating fluidized bed boiler as described in the scope of the patent application, the aggregate material and the binder are mixed with the catalyst to form a slurry. 6. The method for producing a petroleum coke ash solidified by-product of a circulating fluidized bed boiler according to claim 5, wherein the binder is a by-product of a circulating fluidized bed steel furnace, petroleum coke fly ash It is a combination of circulating fluidized bed L furnace pair 19 201116500 petroleum coke bottom ash, sand, stone, soil, or the like. 7. The method for producing a petroleum coke ash solidified by-product of a circulating fluidized bed boiler according to claim 6, wherein the aggregate is a by-product of a circulating fluidized bed boiler, a petroleum coke bottom ash, a circulating fluidized bed. Boiler by-product petroleum coke fly ash, circulating fluidized bed boiler by-product petroleum coke bottom ash, catalyst 'water ratio is 25 wt 〇 / 〇 ^ 45wt 〇 / 〇: 25wt 〇 / 〇 ~ 55wt 〇 / 〇: 0.5 Wt〇/〇~3wt〇/〇: 1〇wt%~3 5 wt%. 8. The method for producing a petroleum coke ash solidified by-product of a circulating fluidized bed steel furnace according to claim 6 of the patent application scope, wherein the aggregate material is sand, circulating fluidized, bed-pin furnace by-product petroleum coke fly ash The ratio of sand, catalyst and water is 25wt〇/〇~45wt〇/〇: 25wt〇/〇~65wt〇/〇: 〇.5 wt〇/〇~3 wt〇/〇: ι〇wt%~35 Wt% 〇 9. The method for producing a petroleum coke ash solidified by-product of a circulating fluidized bed steel furnace according to claim 6, wherein the aggregate is composed of sand and stone, and the circulating fluidized bed boiler is produced by-product. The ratio of petroleum coke fly ash, sand, stone, catalyst and water is 25wt%~45wt%: 15wt%q5wt%: 15wt〇/〇~35wt%: 〇.5wt%~3wt〇/〇: 1〇wt%~ 35 wt%. H). According to the method for producing a by-product oil coke ash from the #环流化床钢炉, as described in the sixth paragraph of the patent application (4), wherein the aggregate is produced by a circulating fluidized furnace by-product petroleum coke bottom ash and The composition of the stone, while the circulating fluidized bed pin by-product petroleum coke fly ash, circulating fluidized bed boiler by-product petroleum coke bottom ash, sub-catalyst, water ratio of 25wt% ~ 45wt% · 15m% ~ 3~: 15 wt% ~ 35 wt% : 〇. 5wt% ~ 3wt% · 1〇 %%~35. 11. According to the application (4), the sixth item of the material of the chemical bed _ by-product 20 201116500 oil coke ash solidification method, wherein the aggregate is soil, circulating fluidized bed steel furnace by-product petroleum coke fly ash The ratio of the soil, the catalyst and the water is 5 wt% to 30 wt%: 30 wt% to 70 wt%: O.lwt% to 3 wt%: 10 wt% to 40 wt%. 12. The method for producing a petroleum coke ash solidified by-product of a circulating fluidized bed boiler according to claim 6, wherein the aggregate is composed of a petroleum coke bottom ash and a by-product of a circulating fluidized bed boiler. Circulating fluidized bed boiler by-product petroleum coke fly ash, circulating fluidized bed boiler by-product petroleum coke bottom ash, soil, catalyst, water ratio of 5wt%~30wt%: 5wt%~30wt%: 30wt〇/〇~ 7〇wt% : 〇.iwt%~3wt% : i〇wt%~4〇wt%. The method for producing a petroleum coke ash by-product of a circulating fluidized bed boiler according to any one of claims 12 to 12, wherein the catalyst is potassium sulphate, sodium sulphate, potassium alum, and potassium sulphate. Alum, potassium chromate, sodium hydrogen sulfate, or a combination of these. 14. The method for producing a curable ash solidified by-product of a circulating fluidized bed boiler according to claim 13 wherein the water-to-binder ratio is controlled to be between 0.10 and 5.00. The 15'-type circulating fluidized bed steel furnace Chang 4 produces a petroleum coke ash solidified product, which is formed by the method described in any one of claims 1 to 14. twenty one