阅读说明：本技术 具有回收磷功能的液体制剂及从含磷样品中回收磷的方法 (Liquid preparation with phosphorus recovery function and method for recovering phosphorus from phosphorus-containing sample ) 是由 齐升东 孙晓雪 王德举 于 2019-10-23 设计创作，主要内容包括：本发明涉及废催化剂利用领域,公开了具有回收磷功能的液体制剂及从含磷样品中回收磷的方法。所述液体制剂含有式I所示的化合物、弱碱性物质和溶剂,以所述液体制剂的总体积为基准,式I所示的化合物的含量为0.02-1.2mol/L,弱碱性物质的含量为0.5-14mol/L。从含磷样品中回收磷的方法包括：(1)选择性地对含磷样品进行预处理以除去有机物；(2)使步骤(1)所得产物与液体制剂进行接触,从而得到含磷浸提液。本发明能够有效回收工业运转后无法再生的废催化剂,是一种环境友好的回收方法。进一步地,所得到的含磷浸提液简单经干燥即可得到磷肥产品,实用性强。(The invention relates to the field of waste catalyst utilization, and discloses a liquid preparation with a phosphorus recovery function and a method for recovering phosphorus from a phosphorus-containing sample. The liquid preparation contains a compound shown as a formula I, a weakly alkaline substance and a solvent, wherein the content of the compound shown as the formula I is 0.02-1.2mol/L and the content of the weakly alkaline substance is 0.5-14mol/L based on the total volume of the liquid preparation. The method for recovering phosphorus from a phosphorus-containing sample comprises the following steps: (1) optionally pretreating the phosphorus-containing sample to remove organic matter; (2) and (2) contacting the product obtained in the step (1) with a liquid preparation to obtain the phosphorus-containing leaching liquor. The method can effectively recover the waste catalyst which can not be regenerated after industrial operation, and is an environment-friendly recovery method. Further, the obtained phosphorus-containing leaching liquor can be simply dried to obtain the phosphate fertilizer productThe product has strong practicability.)

1. A liquid preparation with a function of recovering phosphorus, which is characterized by comprising a compound shown as a formula I, a weakly alkaline substance and a solvent,

in the formula I, R₁、R₂、R₃And R₄Each independently selected from hydrogen or C₁-C₆Alkyl of (A), M₁、M₂、M₃And M₄Each independently selected from H, NH₄ ⁺Or an alkali metal cation;

wherein the content of the compound shown in the formula I is 0.02-1.2mol/L and the content of the weak alkaline substance is 0.5-14mol/L based on the total volume of the liquid preparation.

2. The liquid formulation of claim 1, wherein the alkali metal cation is Li⁺、Na⁺Or K⁺Preferably, the compound shown in the formula I is at least one of ethylenediamine tetraacetic acid, ethylenediamine tetraacetic acid disodium salt, ethylenediamine tetraacetic acid tetrasodium salt, ethylenediamine tetraacetic acid dipotassium salt and ethylenediamine tetraacetic acid tetraammonium salt.

3. The liquid formulation according to claim 1 or 2, wherein the weakly basic substance is an inorganic base and/or a weak acid and weak base salt, preferably at least one of ammonia, ammonium carbonate and ammonium bicarbonate;

and/or, the solvent is water.

4. A method for recovering phosphorus from a phosphorus-containing sample, the method comprising:

(1) optionally pretreating the phosphorus-containing sample to remove organic matter;

(2) contacting the product obtained in the step (1) with a liquid preparation to obtain a phosphorus-containing leaching solution, wherein the liquid preparation contains a compound shown as a formula I, a weak alkaline substance and a solvent;

in the formula I, R₁、R₂、R₃And R₄Each independently selected from hydrogen or C₁-C₆Alkyl of (A), M₁、M₂、M₃And M₄Each independently selected from H, NH₄ ⁺Or an alkali metal cation;

wherein the content of the compound shown in the formula I is 0.02-1.2mol/L and the content of the weak alkaline substance is 0.5-14mol/L based on the total volume of the liquid preparation.

5. The method of claim 4, wherein in step (1), the pretreatment conditions are such that the phosphorus-containing sample has a residual organic content of no more than 0.3 wt%, and preferably the pretreatment conditions comprise: the temperature is 500-1000 ℃, preferably 600-700 ℃, and the time is 4-36h, preferably 5-10 h.

6. The process according to claim 4 or 5, wherein the liquid formulation is used in an amount of 2-20mL per gram of the product obtained in step (1) on a dry basis;

and/or, the contacting conditions in step (2) comprise: the temperature is 70-150 ℃ and the time is 1-10 h.

7. The method of claim 4, wherein the alkali metal cation is Li⁺、Na⁺Or K⁺Preferably, the compound shown in the formula I is at least one of ethylenediamine tetraacetic acid, ethylenediamine tetraacetic acid disodium salt, ethylenediamine tetraacetic acid tetrasodium salt, ethylenediamine tetraacetic acid dipotassium salt and ethylenediamine tetraacetic acid tetraammonium salt.

8. The process according to claim 4 or 7, wherein the weakly basic substance is an inorganic base and/or a salt of a weak acid and a weak base, preferably at least one of ammonia, ammonium carbonate and ammonium bicarbonate;

and/or, the solvent is water.

9. The method according to any one of claims 4-8, wherein P is selected from the group consisting of₂O₅The content of the phosphorus element in the phosphorus-containing sample is 5-20 wt%, and the phosphorus-containing sample is preferably a catalyst for preparing olefin from waste methanol, and more preferably a catalyst for preparing olefin from waste methanol which cannot be regenerated.

10. A process according to any one of claims 4 to 8, wherein the process further comprises spray drying the phosphorus-containing leachate.

Technical Field

The invention relates to the field of waste catalyst utilization, in particular to a liquid preparation with a phosphorus recovery function and a method for recovering phosphorus from a phosphorus-containing sample.

Background

Ethylene and propylene are the most important chemical raw materials in the petrochemical industry, and the low yield of ethylene has been regarded as a mark of the development degree of the petrochemical industry in China. The traditional production route of low-carbon olefins is mainly prepared by cracking naphtha, the technology has great dependence on petroleum, most of crude oil in China needs to be imported from foreign countries, and the demand on low-carbon olefins is more and more increased along with the rapid development of national economy. If the original raw material route is still used, the petroleum resources in China can not meet the development requirements of the domestic petrochemical industry more and more. Particularly, after the century, with the shortage of petroleum resources and the rising of prices, many countries have been dedicated to developing and making significant progress in the technology of producing low carbon olefins from non-petroleum resources, in which the technology of producing low carbon olefins from methanol produced from coal or natural gas has received great attention. As the large-scale industrial technology for preparing methanol from coal or natural gas is mature, the key point of the success of the route is mainly the process for preparing olefin (MTO) from methanol. MTO refers to a chemical process technology for producing olefins from coal-based or natural gas-based synthetic methanol by means of a fluid bed reaction similar to a catalytic cracking unit.

The catalyst is the key of MTO reaction and is one of the cores of methanol-to-olefin technology. The research on the methanol-to-olefin reaction catalyst mainly focuses on the research on the adjustment of catalyst components, pore structures, surface acidity, grain sizes and even a pretreatment method of the catalyst, so that the catalyst has higher activity, excellent selectivity and less coke formation, is beneficial to regeneration and prolongs the service life of the catalyst. The main active component of the MTO catalyst is SAPO-34, the SAPO-34 has special pore channel structure and protonic acidity, when the MTO catalyst is used for catalyzing MTO reaction, the gaseous product of methanol conversion only contains C1-C5 hydrocarbon, the eight-membered ring orifice of the gaseous product has larger diffusion resistance to macromolecules, and only C2 and C3 hydrocarbon can be easily diffused out of a crystal body. In addition, the acid center with too strong acidity tends to generate hydrocarbon with relatively large molecular mass, while the acid center with medium strength of SAPO-34 limits the further reaction of ethylene and propylene, so that SAPO-34 shows outstanding superiority in the reaction of preparing olefin by converting methanol, the selectivity of low-carbon olefin is as high as 90%, and products above C5 and branched chain isomers are few. SAPO-34 also has good adsorption properties, thermal stability and water stability, the determined framework collapse temperature is 1000 ℃, and the crystalline structure can be still maintained by processing at 600 ℃ in a 20% water vapor environment. The method plays an important role in the continuous reaction of the MTO process and the regeneration operation of the catalyst, and the discovery of the SAPO makes the MTO process develop in a breakthrough way.

In 2016, the domestic ethylene capacity of an MTO device reaches 1285 ten thousand tons, and the demand of a catalyst exceeds 1.2 ten thousand tons; according to the planning, the MTO capacity can reach 3400 ten thousand tons, the catalyst demand exceeds 3 ten thousand tons per year, and the amount of the catalyst wasted every year is equivalent to the demand. The method develops a resource utilization technology of the MTO waste catalyst, changes waste into valuable, is beneficial to chemical attack, is a development and research field which should draw attention and has wide application prospect, and meets the requirement of sustainable development.

The MTO catalyst has the characteristics of poor stability, easy inactivation and the like, but the activity can be recovered by a regeneration means, so that the fluidized bed reaction form is suitable for the process with high MTO catalyst inactivation rate, and the continuous regeneration and the circulating operation of the MTO catalyst can be carried out. Due to the inherent characteristics of the fluidized bed reaction regeneration technology and the diversity of the influence factors of the fluidization process, the violent impact and friction of the solid catalyst in the flowing process accelerate the pulverization of the catalyst, a large amount of fine-particle catalyst is continuously taken out, and the catalyst micro powder adsorbs more oil and other pollutants to form dangerous waste, which can cause harm to the environment if not treated. In addition, the waste MTO catalyst mainly contains elements such as phosphorus, aluminum, silicon and the like, wherein the content of phosphorus (expressed as P) is₂O₅Calculated) up to 10-15% by weight, direct disposal also results in waste of beneficial resources.Moreover, the current environmental protection policy is increasingly strict, and simple treatment modes such as landfill and the like are limited. The recovery methods of various waste catalysts are roughly divided into a dry method (such as Jumegapen, and the like, researches on treating a molybdenum-containing waste catalyst by using a plasma furnace to recover valuable metals, China molybdenum industry, 2003) and a wet method (such as Suzuoxing, and the like, researches on the separation and recovery processes of metals in oil refining hydrogenation waste catalysts, Guangdong chemical industry, 2013), and enterprises also adopt dry and wet combination or recycle after simple treatment. The recovery and utilization of valuable elements in the waste MTO catalyst are not reported at present.

Disclosure of Invention

The invention aims to overcome the problems in the prior art and provides a liquid preparation with a function of recovering phosphorus and a method for recovering phosphorus from a phosphorus-containing sample.

In order to achieve the above objects, according to one aspect of the present invention, there is provided a liquid preparation having a function of recovering phosphorus, the liquid preparation containing a compound represented by formula I, a weakly basic substance and a solvent,

in the formula I, R₁、R₂、R₃And R₄Each independently selected from hydrogen or C₁-C₆Alkyl of (A), M₁、M₂、M₃And M₄Each independently selected from H, NH₄ ⁺Or an alkali metal cation;

wherein the content of the compound shown in the formula I is 0.02-1.2mol/L and the content of the weak alkaline substance is 0.5-14mol/L based on the total volume of the liquid preparation.

In a second aspect, the present invention provides a method for recovering phosphorus from a phosphorus-containing sample, the method comprising:

(1) optionally pretreating the phosphorus-containing sample to remove organic matter;

(2) contacting the product obtained in the step (1) with a liquid preparation to obtain a phosphorus-containing leaching solution, wherein the liquid preparation contains a compound shown as a formula I, a weak alkaline substance and a solvent;

wherein the content of the compound shown in the formula I is 0.02-1.2mol/L and the content of the weak alkaline substance is 0.5-14mol/L based on the total volume of the liquid preparation.

Through the technical scheme, the liquid preparation and the method can effectively recover the waste catalyst which cannot be regenerated after industrial operation, and are an environment-friendly recovery method. Furthermore, the obtained phosphorus-containing leaching liquor can be simply dried to obtain a phosphate fertilizer product meeting the national standard (GB20412-2006), and the practicability is high. The method is particularly suitable for recycling the waste MTO catalyst, and provides technical support for resource utilization of the solid wastes.

Detailed Description

The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.

In the present invention, the term "alkyl" used in the absence of a contrary indication includes straight or branched C₁-C₆Alkyl, which means monovalent alkyl having 1 to 6 carbon atoms, such as methyl, ethyl, n-propyl, i-propyl, n-butyl, sec-butyl, i-butyl, t-butyl, n-pentyl, 1-ethylpropyl, 2-methylbutyl, 3-methylbutyl, 2, 2-dimethylpropyl, n-hexyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl.

The liquid preparation with the function of recovering phosphorus provided by the invention contains a compound shown as a formula I, a weak alkaline substance and a solvent,

in the formula I, R₁、R₂、R₃And R₄Each independently selected from hydrogen or C₁-C₆Alkyl of (A), M₁、M₂、M₃And M₄Each independently selected from H, NH₄ ⁺Or alkali metal cations (e.g. Li)⁺、Na⁺Or K⁺)；

Wherein the compound of formula I is present in an amount of 0.02 to 1.2mol/L (e.g., 0.02mol/L, 0.03mol/L, 0.05mol/L, 0.1mol/L, 0.5mol/L, 1mol/L, 1.1mol/L, 1.2mol/L or any value therebetween), and the weakly basic substance is present in an amount of 0.5 to 14mol/L (e.g., 0.5mol/L, 1mol/L, 1.5mol/L, 2mol/L, 3mol/L, 5mol/L, 10mol/L, 14mol/L or any value therebetween), based on the total volume of the liquid preparation.

According to the invention, M₁、M₂、M₃And M₄Can be selected from H, NH independently₄ ⁺、Li⁺、Na⁺Or K⁺。R₁、R₂、R₃And R₄May both be selected from hydrogen. Preferably, the compound shown in the formula I is at least one of ethylenediamine tetraacetic acid, ethylenediamine tetraacetic acid disodium salt, ethylenediamine tetraacetic acid tetrasodium salt, ethylenediamine tetraacetic acid dipotassium salt and ethylenediamine tetraacetic acid tetraammonium salt.

According to the invention, the weakly basic substance is preferably water-soluble, i.e. a substance which has a solubility of ≥ 20g per 100g of water at 20 ℃ and whose aqueous solution is alkaline (pH > 7 but close to 7). Preferably, the weakly basic substance is an inorganic base and/or a weak acid and weak base salt, more preferably at least one of ammonia, ammonium carbonate and ammonium bicarbonate.

According to the present invention, the solvent may be a conventional solvent capable of dissolving the compound represented by formula I and a weakly basic substance, but preferably, the solvent is water.

The invention provides a method for recovering phosphorus from a phosphorus-containing sample, which comprises the following steps:

(1) optionally pretreating the phosphorus-containing sample to remove organic matter;

(2) contacting the product obtained in the step (1) with a liquid preparation to obtain a phosphorus-containing leaching solution, wherein the liquid preparation contains a compound shown as a formula I, a weak alkaline substance and a solvent,

in the formula I, R₁、R₂、R₃And R₄Each independently selected from hydrogen or C₁-C₆Alkyl of (A), M₁、M₂、M₃And M₄Each independently selected from H, NH₄ ⁺Or alkali metal cations (e.g. Li)⁺、Na⁺Or K⁺)；

Wherein the compound of formula I is present in an amount of 0.02 to 1.2mol/L (e.g., 0.02mol/L, 0.03mol/L, 0.05mol/L, 0.1mol/L, 0.5mol/L, 1mol/L, 1.1mol/L, 1.2mol/L or any value therebetween), and the weakly basic substance is present in an amount of 0.5 to 14mol/L (e.g., 0.5mol/L, 1mol/L, 1.5mol/L, 2mol/L, 3mol/L, 5mol/L, 10mol/L, 14mol/L or any value therebetween), based on the total volume of the liquid preparation.

In the present invention, step (1) is an optional step, and the skilled person can fully understand from the description of the present invention that: if the organic content of the phosphorus-containing sample is low (e.g., no more than 0.3 wt%), then step (1) may not be performed and the phosphorus-containing sample may be contacted directly with the liquid formulation; if the organic content of the phosphorus-containing sample is high (e.g., more than 0.3 wt%), then step (1) is performed. The following describes the embodiment of step (1). In the step (1), the pretreatment can substantially remove carbon deposition (mainly organic matters such as polycyclic aromatic hydrocarbon) on the surface and in pore channels of the phosphorus-containing sample, and preferably, the pretreatment condition is that the residual quantity of the organic matters of the phosphorus-containing sample is not more than 0.3 wt%. The higher the temperature, the lower the residual organic content, the better the phosphorus recovery, and therefore, more preferably, the pretreatment conditions include: the temperature is 500-1000 ℃. Considering the effect of recovering phosphorus and energy consumption together, the pretreatment conditions further preferably include: the temperature is 600-700 ℃. More preferably, the pretreatment conditions further comprise: the time is 4 to 36 hours, more preferably 5 to 10 hours.

In the present invention, there is no particular requirement for the amount of the liquid formulation as long as the phosphorus-containing sample can be submerged to leach out elemental phosphorus. But preferably, the liquid preparation is used in an amount of 2-20mL per gram of the product obtained in step (1) (the phosphorus-containing sample from which the organic matter is removed) on a dry basis.

In the present invention, the contacting conditions in step (2) preferably include: the temperature is 70-150 ℃. The contacting conditions in step (2) preferably further comprise: the time is 1-10 h.

In the present invention, the specific choice of the liquid preparation can refer to the foregoing, and will not be described herein.

In the present invention, the phosphorus-containing sample can be any of various common substances from which phosphorus recovery is desired, such as P-containing samples₂O₅In particular, a spent catalyst, i.e., a phosphorus-containing catalyst whose catalytic activity has decreased to 60% or less of that of the catalyst when not in use. Generally, with P₂O₅The content of the phosphorus element in the phosphorus-containing sample is 5-20 wt%. The phosphorus-containing sample is preferably a catalyst for preparing the olefin from the waste methanol, more preferably a catalyst for preparing the olefin from the waste methanol, which cannot be regenerated, and particularly a catalyst for preparing the olefin from the waste methanol, which cannot be regenerated and recycled (such as by charcoal burning).

In the present invention, the phosphorus-containing sample may further contain aluminum and silicon. With Al₂O₃The content of the aluminum element in the phosphorus-containing sample can be 60-70 wt%. With SiO₂The content of silicon element in the phosphorus-containing sample can be 10-25 wt%. Thus, the method further comprises recovering aluminum (Al) and silicon (Si) from the solid phase obtained after the contacting. Through the step of recovering aluminum and silicon, the method can realize high value-added utilization and full-element circulation of the waste molecular sieve or the waste catalyst.

In the present invention, the method for recovering aluminum and silicon may be a conventional method, and will not be described herein.

The invention can be used in various fields needing phosphorus, and the inventor finds that after the step of removing organic matters, the phosphorus-containing leaching liquor is prepared by the steps ofBy using the liquid preparation to contact (leach) the phosphorus-containing sample, the obtained phosphorus-containing leach liquor has a high phosphorus content and low content of other impurities, and thus can be used for preparing a phosphate fertilizer, and in order to obtain the phosphate fertilizer, the method preferably further comprises spray drying the phosphorus-containing leach liquor to reduce the moisture content to below 3 wt%. There is no particular requirement for the conditions of spray drying, for example, the conditions of spray drying may include: the inlet temperature is 200-350 ℃, and the outlet temperature is 100-180 ℃. According to a preferred embodiment of the invention, the total phosphorus content of the solid obtained after spray drying is up to 14 to 25% by weight (in P)₂O₅In terms of phosphorus), phosphorus mainly exists in the form of ammonium phosphate salt or chelate of phosphorus, the effective phosphorus content (GB/T8573-2010) is also higher, and the phosphorus can be used as a phosphate fertilizer.

The present invention will be described in detail below by way of examples. In the following examples, the measurement of the residual organic matter was carried out by thermogravimetric analysis: placing the waste phosphorus-aluminum molecular sieve catalyst raw material under air circulation, heating from room temperature to 1200 ℃ at the speed of 10 ℃/min, analyzing thermogravimetric results, removing the weight percentage of water evaporation (a larger weight loss rate peak can appear in the range near 100 ℃ on a thermogravimetric analysis curve, wherein the weight loss percentage is the weight percentage of water evaporation), and the rest weight loss is the organic matter residual quantity in the waste catalyst.

Example 1

This example serves to illustrate the process of the invention for recovering valuable elements from spent catalysts.

(1) Adding waste phosphorus-aluminum molecular sieve catalyst raw material (mass percentage of dry basis Al after organic matter is removed) into an industrial electric furnace₂O₃69.36 wt.% SiO₂18.21 wt.%, P₂O₅11.65 wt%), at 600 ℃ for 8h to obtain a material I with a residual organic matter of 0.25 wt%;

(2) putting the material I obtained in the step (1) into a 5L reactor, adding a mixture (solvent is water) containing 0.1mol/L disodium ethylenediamine tetraacetic acid and 2mol/L ammonia, wherein the solid-liquid ratio is 1g:10mL, the reaction temperature is 70 ℃, and the reaction time is 2 h. And carrying out suction filtration on the reaction product to obtain a leaching solution I and leaching slag I, wherein the leaching solution I adopts an inductively coupled plasma emission spectrometer (ICP, Varian,725-ES) to measure the concentrations of P, Al and Si. The leaching rate is defined as the metal content in the filtrate divided by the total mass of the metals in the raw materials, the leaching rate of P is calculated according to the ICP result, and the result shows that Al and Si are not leached;

(3) performing spray drying on the leaching solution I, and recovering ammonia gas, wherein the conditions of spray drying are that the inlet temperature is 250 ℃ and the outlet temperature is 100 ℃; the spray-dried product was analyzed by X-ray fluorescence Spectroscopy (XRF) to determine the total phosphorus content (in P)₂O₅In the same manner, the content of available phosphorus (in P) is determined by adopting the standard GB/T8573-2010₂O₅The same applies below). And (3) quantitatively subpackaging the dried product (the water content is 0.26 weight percent, and the product passing through a 0.25mm test sieve accounts for 98 percent of the total weight of the obtained product) to obtain the phosphate fertilizer meeting the national standard GB 20412-2006.

The leaching rate of P and the measurement result of the available phosphorus content in the spray-dried product are shown in Table 1.

Example 2

This example serves to illustrate the process of the invention for recovering valuable elements from spent catalysts.

(1) Adding a waste phosphorus-aluminum molecular sieve catalyst raw material (the mass percentage of a dry base after organic matters are removed is the same as that in example 1) into an industrial electric furnace, and treating for 5 hours at 700 ℃ to obtain a material I, wherein the residual quantity of the organic matters is 0.19 weight percent;

(2) putting the material I obtained in the step (1) into a 5L reactor, adding a mixture (solvent is water) containing 1.2mol/L of ethylenediamine tetraacetic acid and 0.5mol/L of ammonium carbonate, wherein the solid-liquid ratio is 1g:2mL, the reaction temperature is 150 ℃, and the reaction time is 1 h. And carrying out suction filtration on the reaction product to obtain a leaching solution I and leaching residues I, wherein the leaching solution I adopts ICP to measure the concentrations of P, Al and Si. Calculating the leaching rate of P according to the ICP result, wherein the result shows that Al and Si are not leached;

(3) performing spray drying on the leaching solution I, and recovering ammonia gas, wherein the conditions of spray drying are that the inlet temperature is 250 ℃ and the outlet temperature is 100 ℃; the total phosphorus content and available phosphorus content of the spray-dried product were determined. And (3) quantitatively subpackaging the dried product (the water content is 0.24 wt%, and the product passing through a 0.25mm test sieve accounts for 99 wt% of the total amount of the obtained product) to obtain the phosphate fertilizer meeting the national standard GB 20412-2006.

The leaching rate of P and the measurement result of the available phosphorus content in the spray-dried product are shown in Table 1.

Example 3

This example serves to illustrate the process of the invention for recovering valuable elements from spent catalysts.

(1) Adding a waste phosphorus-aluminum molecular sieve catalyst raw material (the mass percentage of a dry base after organic matters are removed is the same as that in example 1) into an industrial electric furnace, and treating the mixture for 10 hours at 650 ℃ to obtain a material I, wherein the residual quantity of the organic matters is 0.23 wt%;

(2) putting the material I obtained in the step (1) into a 5L reactor, adding a mixture (solvent is water) containing 0.02mol/L of ethylenediaminetetraacetic acid tetrasodium salt and 1.5mol/L of ammonium bicarbonate, wherein the solid-liquid ratio is 1g:20mL, the reaction temperature is 100 ℃, and the reaction time is 10 hours. And carrying out suction filtration on the reaction product to obtain a leaching solution I and leaching residues I, wherein the leaching solution I adopts ICP to measure the concentrations of P, Al and Si. Calculating the leaching rate of P according to the ICP result, wherein the result shows that Al and Si are not leached;

(3) performing spray drying on the leaching solution I, and recovering ammonia gas, wherein the conditions of spray drying are that the inlet temperature is 250 ℃ and the outlet temperature is 100 ℃; the total phosphorus content and available phosphorus content of the spray-dried product were determined. And (3) quantitatively subpackaging the dried product (the water content is 0.24 wt%, and the product passing through a 0.25mm test sieve accounts for 99 wt% of the total amount of the obtained product) to obtain the phosphate fertilizer meeting the national standard GB 20412-2006.

The leaching rate of P and the measurement result of the available phosphorus content in the spray-dried product are shown in Table 1.

Example 4

Valuable elements were recovered according to the method described in example 1, except that:

in the step (1), the mixture is treated for 36 hours at 500 ℃ to obtain a material I, and the residual organic matter content is 0.27 percent by weight.

The leaching rate of P and the measurement result of the available phosphorus content in the spray-dried product are shown in Table 1.

Example 5

Valuable elements were recovered according to the method described in example 1, except that:

in the step (1), the mixture is treated for 5 hours at the temperature of 1000 ℃ to obtain a material I, and the residual quantity of organic matters is 0.18 percent by weight.

The leaching rate of P and the measurement result of the available phosphorus content in the spray-dried product are shown in Table 1.

Example 6

Valuable elements were recovered according to the method described in example 1, except that:

in the step (2), iminodiacetic acid is used for replacing ethylene diamine tetraacetic acid disodium salt.

The leaching rate of P and the measurement result of the available phosphorus content in the spray-dried product are shown in Table 1.

Example 7

Valuable elements were recovered according to the method described in example 1, except that:

in the step (2), the reaction temperature is 170 ℃ and the reaction time is 0.5 h.

The leaching rate of P and the measurement result of the available phosphorus content in the spray-dried product are shown in Table 1.

Comparative example 1

Valuable elements were recovered according to the method described in example 1, except that:

(2) putting the material I obtained in the step (1) into a 5L reactor, adding an ethylene diamine tetraacetic acid disodium salt aqueous solution with the concentration of 0.02mol/L, wherein the solid-to-liquid ratio is 1g:50mL, the reaction temperature is 90 ℃, and the reaction time is 2 h.

The leaching rate of P and the measurement result of the available phosphorus content in the spray-dried product are shown in Table 1.

Comparative example 2

Valuable elements were recovered according to the method described in example 1, except that:

(2) putting the material I obtained in the step (1) into a 5L reactor, adding 1.2mol/L ethylene diamine tetraacetic acid disodium salt aqueous solution, wherein the solid-to-liquid ratio is 1g:5mL, the reaction temperature is 100 ℃, and the reaction time is 2 h.

The leaching rate of P and the measurement result of the available phosphorus content in the spray-dried product are shown in Table 1.

Comparative example 3

Valuable elements were recovered according to the method described in example 1, except that:

(2) putting the material I obtained in the step (1) into a 5L reactor, adding 1mol/L ethylene diamine tetraacetic acid disodium salt aqueous solution, wherein the solid-liquid ratio is 1g:10mL, the reaction temperature is 70 ℃, and the reaction time is 2 h.

The leaching rate of P and the measurement result of the available phosphorus content in the spray-dried product are shown in Table 1.

Comparative example 4

Valuable elements were recovered according to the method described in example 1, except that:

(2) putting the material I obtained in the step (1) into a 5L reactor, adding ammonia water with the concentration of 0.5mol/L, wherein the solid-liquid ratio is 1g:10mL, the reaction temperature is 70 ℃, and the reaction time is 2 h.

The leaching rate of P and the measurement result of the available phosphorus content in the spray-dried product are shown in Table 1.

Comparative example 5

Valuable elements were recovered according to the method described in example 1, except that:

(2) putting the material I obtained in the step (1) into a 5L reactor, adding ammonia water with the concentration of 13mol/L, wherein the solid-liquid ratio is 1g:50mL, the reaction temperature is 100 ℃, and the reaction time is 2 h.

The leaching rate of P and the measurement result of the available phosphorus content in the spray-dried product are shown in Table 1.

Comparative example 6

Valuable elements were recovered according to the method described in example 1, except that:

(2) putting the material I obtained in the step (1) into a 5L reactor, adding ammonia water with the concentration of 2mol/L, wherein the solid-liquid ratio is 1g:10mL, the reaction temperature is 70 ℃, and the reaction time is 2 h.

The leaching rate of P and the measurement result of the available phosphorus content in the spray-dried product are shown in Table 1.

Comparative example 7

Valuable elements were recovered as described in example 1, except that:

directly adding the mixture of ethylene diamine tetraacetic acid disodium salt and ammonia into the waste phosphorus-aluminum molecular sieve catalyst raw material without carrying out the step (1). The reaction product cannot be subjected to solid-liquid separation by suction filtration in the presence of an organic substance, and therefore, the solid-liquid separation is carried out by centrifugation (2500rpm, 15 min).

The leaching rate of P and the measurement result of the available phosphorus content in the spray-dried product are shown in Table 1.

Comparative example 8

Valuable elements were recovered according to the method described in example 1, except that:

in the step (2), the mixture of disodium ethylenediaminetetraacetate and ammonia was replaced with 2mol/L aqueous sodium hydroxide solution. And carrying out suction filtration on the reaction product to obtain a leaching solution I and leaching residues I, wherein the leaching solution I adopts ICP to measure the concentrations of P, Al and Si. The leaching rate of P, that of Al, and that of Si were 98.53 wt%, 49.93 wt%, and 4.12 wt%, respectively, were calculated from the ICP results. Due to the existence of impurities Al and Si, a P-containing product meeting the industrial standard cannot be obtained, and Al and Si cannot be respectively recovered.

Comparative example 9

Valuable elements were recovered according to the method described in example 1, except that:

in the step (2), a mixture containing 0.01mol/L disodium ethylenediamine tetraacetate and 15mol/L ammonia is added.

The leaching rate of P and the measurement result of the available phosphorus content in the spray-dried product are shown in Table 1.

Comparative example 10

Valuable elements were recovered according to the method described in example 1, except that:

in the step (2), a mixture containing 3mol/L disodium ethylenediamine tetraacetate and 0.4mol/L ammonia is added.

The leaching rate of P and the measurement result of the available phosphorus content in the spray-dried product are shown in Table 1.

TABLE 1

The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.