CN114181747A - Method for preparing hydrogen-rich gas by carrying out overheat catalytic conversion on waste organic-inorganic composite material - Google Patents
Method for preparing hydrogen-rich gas by carrying out overheat catalytic conversion on waste organic-inorganic composite material Download PDFInfo
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- 239000007789 gas Substances 0.000 title claims abstract description 100
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 42
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 239000001257 hydrogen Substances 0.000 title claims abstract description 41
- 239000002699 waste material Substances 0.000 title claims abstract description 38
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 36
- 229910003471 inorganic composite material Inorganic materials 0.000 title claims abstract description 31
- 238000000034 method Methods 0.000 title claims abstract description 25
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 20
- 238000000197 pyrolysis Methods 0.000 claims abstract description 88
- 239000002737 fuel gas Substances 0.000 claims abstract description 84
- 238000005336 cracking Methods 0.000 claims abstract description 42
- 238000001833 catalytic reforming Methods 0.000 claims abstract description 31
- 238000000746 purification Methods 0.000 claims abstract description 17
- 238000002352 steam pyrolysis Methods 0.000 claims abstract description 13
- 238000005215 recombination Methods 0.000 claims abstract description 10
- 230000006798 recombination Effects 0.000 claims abstract description 10
- 239000002893 slag Substances 0.000 claims description 43
- 239000003513 alkali Substances 0.000 claims description 34
- 239000003054 catalyst Substances 0.000 claims description 32
- 238000002156 mixing Methods 0.000 claims description 24
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 18
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 18
- 229910052794 bromium Inorganic materials 0.000 claims description 18
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 239000002245 particle Substances 0.000 claims description 12
- 230000035484 reaction time Effects 0.000 claims description 9
- 239000011398 Portland cement Substances 0.000 claims description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 8
- 230000005294 ferromagnetic effect Effects 0.000 claims description 8
- 239000002923 metal particle Substances 0.000 claims description 8
- 229910052755 nonmetal Inorganic materials 0.000 claims description 8
- 229910052760 oxygen Inorganic materials 0.000 claims description 8
- 239000001301 oxygen Substances 0.000 claims description 8
- 239000000843 powder Substances 0.000 claims description 8
- 239000012629 purifying agent Substances 0.000 claims description 8
- 239000007921 spray Substances 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- 230000008569 process Effects 0.000 claims description 6
- 238000007158 vacuum pyrolysis Methods 0.000 claims description 3
- 239000011401 Portland-fly ash cement Substances 0.000 claims 1
- 239000004568 cement Substances 0.000 claims 1
- 238000005516 engineering process Methods 0.000 abstract description 7
- 230000009467 reduction Effects 0.000 abstract description 4
- 239000000571 coke Substances 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 2
- 238000002309 gasification Methods 0.000 abstract 1
- 238000000926 separation method Methods 0.000 abstract 1
- 238000011084 recovery Methods 0.000 description 19
- 239000002131 composite material Substances 0.000 description 16
- 238000004064 recycling Methods 0.000 description 11
- 125000001309 chloro group Chemical class Cl* 0.000 description 7
- 238000000354 decomposition reaction Methods 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 238000002386 leaching Methods 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- 229920005989 resin Polymers 0.000 description 5
- 239000003469 silicate cement Substances 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 3
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000010881 fly ash Substances 0.000 description 2
- 239000005416 organic matter Substances 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 238000000053 physical method Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L3/00—Gaseous fuels; Natural gas; Synthetic natural gas obtained by processes not covered by subclass C10G, C10K; Liquefied petroleum gas
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L3/00—Gaseous fuels; Natural gas; Synthetic natural gas obtained by processes not covered by subclass C10G, C10K; Liquefied petroleum gas
- C10L3/06—Natural gas; Synthetic natural gas obtained by processes not covered by C10G, C10K3/02 or C10K3/04
- C10L3/08—Production of synthetic natural gas
Abstract
A method for preparing hydrogen-rich fuel gas by the overheat catalytic conversion of waste organic-inorganic composite materials belongs to the field of organic-inorganic composite materials. The method mainly comprises the following steps: low-temperature vacuum cracking, superheated steam pyrolysis, fuel gas catalytic recombination, fuel gas purification, mechanical crushing, eddy current separation and the like. Compared with the prior art, the invention adopts the combined technology of low-temperature vacuum cracking and superheated steam pyrolysis, thereby improving the gasification conversion rate of organic components and avoiding the enrichment of cracking oil and cracking coke; the content of combustible hydrogen in the fuel gas is improved through catalytic reforming of the gas generated by pyrolysis, and the obtained hydrogen-rich fuel gas has higher utilization value. The invention has the characteristics of strong adaptability of raw materials, high conversion rate of organic components, obvious reduction, easy industrial popularization and application and the like.
Description
Technical Field
The invention relates to a method for efficiently catalyzing, converting and recycling organic matters in an organic-inorganic composite material, in particular to a method for preparing hydrogen-rich fuel gas by carrying out overheat conversion and catalytic reforming on organic components in typical composite materials of retired fan blades and waste circuit boards.
Background
The organic-inorganic composite material has the characteristics of light weight, corrosion resistance, high strength and the like, and is widely applied to various fields of electronics, household appliances, wind power, aviation, traffic, automobiles, even military affairs and the like. When the composite material is widely applied, the problems of recycling treatment and high-valued utilization of the composite material rich in organic resin represented by retired wind power blades and waste circuit boards are not well solved for a long time because the composite material is difficult to degrade and the recycling treatment process is complex. The industrial recycling technology for organic matter degradation, which is economic, environment-friendly and high-value utilized, is researched to become an urgent need for organic-inorganic composite material treatment.
The traditional disposal mode of organic and inorganic composite materials represented by retired wind power blades and waste circuit boards is deep burying and burning, and as the main components of the organic and inorganic composite materials are corrosion-resistant organic resin, the organic and inorganic composite materials are difficult to degrade and destroy land resources in landfill, and harmful gas is generated by burning to cause atmospheric environmental pollution. Thus, these two crude modes are not available. At present, the typical organic-inorganic composite material recycling technology represented by retired wind power blades and waste circuit boards is mainly subjected to physical methods including crushing, sorting, grinding and the like at home and abroad; a chemical method, which is mainly used for recovering other valuable component monomers by organic matter oiling; the heat recovery method mainly includes combustion and fuel technology.
In view of the above analysis, each method for recycling organic-inorganic composite materials has its advantages, but has considerable disadvantages, and thus each technique cannot be applied to all composite materials. In order to solve the problem, the invention adopts the technology of combining vacuum cracking with superheated steam pyrolysis to fully decompose and convert organic components in the organic-inorganic composite material into pyrolysis gas, and prepares the hydrogen-rich gas through the catalytic reforming technology, thereby fully realizing the reduction, recycling and harmless treatment of the organic-inorganic composite material represented by retired wind power blades and waste circuit boards, and the recovery process has the effects of high-efficiency conversion and clean recovery.
Disclosure of Invention
The invention aims to mainly solve the problems of recycling and high-value utilization of organic resin-rich composite materials represented by retired wind power blades and waste circuit boards, and provides a method for preparing pyrolysis gas through vacuum cracking and superheated steam conversion and preparing hydrogen-rich combustible gas through catalytic reforming. The method has strong adaptability of raw materials, full decomposition of organic matters, obvious reduction and high-efficiency conversion and clean recovery effects in the recovery process.
The method for preparing the hydrogen-rich fuel gas by the overheat catalytic conversion of the waste organic-inorganic composite material comprises the following steps:
(1) low-temperature vacuum cracking: putting composite materials such as retired wind power blades or waste circuit boards which are crushed to 5-20 cm into a pyrolysis reactor, adding a certain debrominant, uniformly mixing, controlling the reaction temperature to be 480-620 ℃ under the vacuum atmosphere condition, reacting for 0.5-2.5 h, carrying out vacuum pyrolysis, obtaining pyrolysis mixed gas and low-temperature pyrolysis slag after the reaction is finished, and carrying out gas catalytic reforming on the pyrolysis mixed gas in the step (4), wherein common waste ordinary portland cement, slag portland cement, pozzolanic portland cement, fly ash portland cement and the like with the crushing granularity of 100-200 meshes are adopted as the debrominant, and the addition amount of the debrominant is 5-20% of the mass of the waste organic-inorganic composite materials.
(2) Pyrolysis by superheated steam: and (2) introducing superheated steam into the low-temperature cracking slag obtained in the step (1) in the same pyrolysis reactor for superheated steam pyrolysis to obtain pyrolysis gas and cracking slag, and introducing the obtained pyrolysis gas into the gas catalytic reforming in the step (4), wherein the mass percentage of oxygen in the superheated steam is 0.1-0.5%, the temperature of introduced superheated steam is 650-1200 ℃, the rate of introducing superheated steam into per hundred kilograms of cracking slag is 0.5-1.5 cubic meters per hour, and the reaction time is 0.5-1.5 hours.
(3) Catalytic reforming of fuel gas: mixing the pyrolysis mixed gas obtained in the step (1) and the pyrolysis gas obtained in the step (2), and then adding a catalyst to perform gas catalytic recombination to obtain mixed gas, wherein the pyrolysis mixed gas and the pyrolysis gas are mixed according to the volume ratio of 1: 1-1: 5, the gas introduction amount of each square meter of the catalyst after mixing is 2.5-5.5 cubic meters per hour, and the catalyst is a Ni-based, Fe-based or Rh-based catalyst.
(4) Gas purification: adding alkali liquor into the mixed fuel gas obtained in the step (4) for fuel gas purification treatment to obtain bromine-containing alkali liquor and hydrogen-rich fuel gas, leaching the bromine-containing alkali liquor, concentrating and crystallizing the bromine-containing alkali liquor, returning the bromine-containing alkali liquor to a chlorine salt recovery system, and preparing superheated steam by using the hydrogen-rich fuel gas, wherein a NaOH solution with the mass percent of 5-20% or NaHCO with the mass percent of 10-30% is adopted3The solution is used as an alkali washing spray purifying agent.
(5) Mechanical crushing-eddy current sorting: and (3) mechanically crushing and eddy current sorting the cracking slag obtained in the step (2) to obtain non-metal powder, ferromagnetic particles and metal particles, and comprehensively recovering the products after classification.
The main principle of the superheated steam pyrolysis and the catalytic recombination of the fuel gas is that the superheated steam can convert coke, tar and organic gas components contained in pyrolysis gas generated in the pyrolysis process into hydrogen-rich fuel gas, and the related main chemical reactions are as follows:
water gas reaction: c + H2O＝CO+H2；
CO+H2O＝H2+CO2
Methane conversion reaction: CO +3H2＝CH4+H2O
And (3) catalytic reforming of phenol to produce hydrogen: c6H5OH+5H2O＝8H2+6CO
Naphthalene catalytic cracking hydrogen production reaction: c10H8+10H2O＝10CO+14H2；
C10H8+20H2O＝10CO2+24H2；
C10H8+10H2O＝2CO+4CO2+6H2+4CH4
Compared with the prior art, the recovery process adopts step-by-step thermal conversion and adopts the phase of vacuum cracking and superheated steam pyrolysisThe organic components in the composite material can be fully decomposed and efficiently converted into pyrolysis gas, the enrichment of pyrolysis oil and pyrolysis coke is avoided, and the pyrolysis gas mainly contains H2、CO、H(Cl/Br)、CO2The proportion of combustible hydrogen in the gas is improved through catalytic reforming of the pyrolysis gas to obtain hydrogen-rich fuel gas with high calorific value, the fuel gas completely conforms to the ideas of double-carbon economy and circular economy, and the fuel gas has obvious reduction, recycling and harmlessness.
The invention is particularly suitable for recycling and high-value utilization of the composite material rich in organic resin represented by retired wind power blades and waste circuit boards, and the developed technology can be popularized to the application and application of the composite material rich in organic resin in the field of high-value recycling.
Drawings
FIG. 1 shows a process flow diagram of a method for preparing hydrogen-rich fuel gas by using waste organic-inorganic composite material through overheat catalytic conversion
Detailed Description
The following examples are intended to further illustrate the invention, but are not intended to limit the invention.
Example 1
The recovery is carried out according to the following steps:
(1) low-temperature vacuum cracking: putting the decommissioned wind power blade composite material crushed to 5 multiplied by 5cm into a pyrolysis reactor, adding a certain debrominant, uniformly mixing, controlling the reaction temperature to 480 ℃ under the vacuum atmosphere condition, carrying out vacuum cracking for 0.5h, obtaining pyrolysis mixed gas and low-temperature cracking slag after the reaction is finished, and carrying out gas catalytic reforming on the pyrolysis mixed gas in the step (4), wherein common waste P.O ordinary portland cement with the crushed particle size of 100 meshes is used as the debrominant, and the addition amount of the debrominant is 5% of the mass of the waste organic-inorganic composite material.
(2) Pyrolysis by superheated steam: and (2) introducing superheated steam with the temperature of 650 ℃ into the low-temperature cracked slag obtained in the step (1) in the same pyrolysis reactor for superheated steam pyrolysis to obtain pyrolysis gas and cracked slag, and introducing the obtained pyrolysis gas into the gas catalytic reforming in the step (4), wherein the mass percentage of oxygen in the superheated steam is 0.1%, the rate of introducing the superheated steam into each hundred kilograms of cracked slag is 0.5 cubic meter per hour, and the reaction time is 1.5 hours.
(3) Catalytic reforming of fuel gas: mixing the pyrolysis mixed gas obtained in the step (1) and the pyrolysis fuel gas obtained in the step (2) according to the volume ratio of 1:1, and then adding a catalyst to perform fuel gas catalytic recombination to obtain the mixed fuel gas, wherein the gas introduction amount of each square meter of the catalyst after the gas mixing is 2.5 cubic meters per hour, and the catalyst is a Ni-based catalyst.
(4) Gas purification: and (3) adding alkali liquor into the mixed fuel gas obtained in the step (4) to perform fuel gas purification treatment to obtain bromine-containing alkali liquor and hydrogen-rich fuel gas, concentrating and crystallizing the bromine-containing alkali liquor to return to a chlorine salt recovery system, and using the hydrogen-rich fuel gas to prepare superheated steam, wherein a NaOH solution with the mass percentage of 5% is used as an alkali washing spray purifying agent.
(5) Mechanical crushing-eddy current sorting: and (3) mechanically crushing and eddy current sorting the cracking slag obtained in the step (2) to obtain non-metal powder, ferromagnetic particles and metal particles, and comprehensively recovering the products after classification.
The decomposition rate of organic substances is 99.6 percent, and H in the hydrogen-rich fuel gas2Volume fraction of 58% CO2The volume fraction was only 6.3%.
Example 2
The recovery is carried out according to the following steps:
(1) low-temperature vacuum cracking: putting the waste circuit board composite material crushed to 20 multiplied by 20cm into a pyrolysis reactor, adding a certain debrominant, uniformly mixing, controlling the reaction temperature to be 620 ℃ under the vacuum atmosphere condition, carrying out vacuum cracking for 2.5 hours, obtaining pyrolysis mixed gas and low-temperature cracking slag after the reaction is finished, and carrying out gas catalytic reforming on the pyrolysis mixed gas in the step (4), wherein common waste slag silicate cement with the crushing granularity of 200 meshes and the code of P.S.A is used as the debrominant, and the addition amount of the debrominant is 20 percent of the mass of the waste organic-inorganic composite material.
(2) Pyrolysis by superheated steam: and (2) introducing superheated steam with the temperature of 1200 ℃ into the low-temperature cracked slag obtained in the step (1) in the same pyrolysis reactor for carrying out superheated steam pyrolysis to obtain pyrolysis gas and cracked slag, and introducing the obtained pyrolysis gas into the gas catalytic reforming in the step (4), wherein the mass percentage content of oxygen in the superheated steam is 0.5%, the rate of introducing the superheated steam into each hundred kilograms of cracked slag is 1.5 cubic meters per hour, and the reaction time is 0.5 h.
(3) Catalytic reforming of fuel gas: mixing the pyrolysis mixed gas obtained in the step (1) and the pyrolysis fuel gas obtained in the step (2) according to a volume ratio of 1:5, and then adding a catalyst to perform fuel gas catalytic recombination to obtain mixed fuel gas, wherein the gas introduction amount of each square meter of the catalyst after gas mixing is 5.5 cubic meters per hour, and the catalyst is an Fe-based catalyst.
(4) Gas purification: adding alkali liquor into the mixed fuel gas obtained in the step (4) for fuel gas purification treatment to obtain bromine-containing alkali liquor and hydrogen-rich fuel gas, performing bromine-containing alkali leaching, concentrating and crystallizing, returning to a chlorine salt recovery system, and using the hydrogen-rich fuel gas for preparing superheated steam, wherein NaHCO with the mass percentage of 30% is adopted3The solution is used as an alkali washing spray purifying agent.
(5) Mechanical crushing-eddy current sorting: and (3) mechanically crushing and eddy current sorting the cracking slag obtained in the step (2) to obtain non-metal powder, ferromagnetic particles and metal particles, and comprehensively recovering the products after classification.
The decomposition rate of organic substances is 99.9 percent, and H in the hydrogen-rich fuel gas2Volume fraction of 60.1%, CO2The volume fraction was only 3.5%.
Example 3
The recovery is carried out according to the following steps:
(1) low-temperature vacuum cracking: putting the decommissioned wind power blade composite material crushed to 10 multiplied by 10cm into a pyrolysis reactor, adding a certain debrominant, uniformly mixing, controlling the reaction temperature to be 600 ℃ under the vacuum atmosphere condition, carrying out vacuum cracking for 2.0h, obtaining pyrolysis mixed gas and low-temperature cracking slag after the reaction is finished, and carrying out gas catalytic reforming on the pyrolysis mixed gas in the step (4), wherein common waste pozzolanic silicate cement with the crushed particle size of 180 meshes and the product code of P.P is used as the debrominant, and the addition amount of the debrominant is 6 percent of the mass of the waste organic-inorganic composite material.
(2) Pyrolysis by superheated steam: and (2) introducing superheated steam with the temperature of 1100 ℃ into the low-temperature cracked slag obtained in the step (1) in the same pyrolysis reactor for carrying out superheated steam pyrolysis to obtain pyrolysis gas and cracked slag, and introducing the obtained pyrolysis gas into the gas catalytic reforming in the step (4), wherein the mass percentage content of oxygen in the superheated steam is 0.4%, the rate of introducing the superheated steam into each hundred kilograms of cracked slag is 1.2 cubic meters per hour, and the reaction time is 1.2 hours.
(3) Catalytic reforming of fuel gas: mixing the pyrolysis mixed gas obtained in the step (1) and the pyrolysis fuel gas obtained in the step (2) according to a volume ratio of 1:2, and then adding a catalyst to perform fuel gas catalytic recombination to obtain mixed fuel gas, wherein the gas introduction amount of each square meter of the catalyst after gas mixing is 3.0 cubic meter per hour, and the catalyst is an Rh-based catalyst.
(4) Gas purification: adding alkali liquor into the mixed fuel gas obtained in the step (4) for fuel gas purification treatment to obtain bromine-containing alkali liquor and hydrogen-rich fuel gas, performing bromine-containing alkali leaching, concentrating and crystallizing, returning to a chlorine salt recovery system, and using the hydrogen-rich fuel gas for preparing superheated steam, wherein NaHCO with the mass percentage of 10% is adopted3The solution is used as an alkali washing spray purifying agent.
(5) Mechanical crushing-eddy current sorting: and (3) mechanically crushing and eddy current sorting the cracking slag obtained in the step (2) to obtain non-metal powder, ferromagnetic particles and metal particles, and comprehensively recovering the products after classification.
The decomposition rate of organic substances is 99.8 percent, and H in the hydrogen-rich fuel gas2Volume fraction of 49.2%, CO2The volume fraction was only 6.8%.
Example 4
The recovery is carried out according to the following steps:
(1) low-temperature vacuum cracking: putting the waste circuit board composite material crushed to 8 multiplied by 8cm into a pyrolysis reactor, adding a certain debrominant, uniformly mixing, controlling the reaction temperature to be 500 ℃ under the vacuum atmosphere condition, carrying out vacuum cracking for 0.9h, obtaining pyrolysis mixed gas and low-temperature cracking slag after the reaction is finished, and carrying out gas catalytic reforming on the pyrolysis mixed gas in the step (4), wherein common waste pozzolanic silicate cement with the product designation of P.P and the crushing granularity of 140 meshes is adopted as the debrominant, and the addition amount of the debrominant is 15% of the mass of the waste organic-inorganic composite material.
(2) Pyrolysis by superheated steam: and (2) introducing superheated steam with the temperature of 750 ℃ into the low-temperature cracked slag obtained in the step (1) in the same pyrolysis reactor for superheated steam pyrolysis to obtain pyrolysis gas and cracked slag, and introducing the obtained pyrolysis gas into the gas catalytic reforming in the step (4), wherein the mass percentage content of oxygen in the superheated steam is 0.3%, the rate of introducing the superheated steam into each hundred kilograms of cracked slag is 0.8 cubic meter per hour, and the reaction time is 1.0 hour.
(3) Catalytic reforming of fuel gas: mixing the pyrolysis mixed gas obtained in the step (1) and the pyrolysis fuel gas obtained in the step (2) according to a volume ratio of 1:4, and then adding a catalyst to perform fuel gas catalytic recombination to obtain mixed fuel gas, wherein the gas introduction amount of each square meter of the catalyst after gas mixing is 5.0 cubic meter per hour, and the catalyst is an Rh-based catalyst.
(4) Gas purification: and (3) adding alkali liquor into the mixed fuel gas obtained in the step (4) to perform fuel gas purification treatment to obtain bromine-containing alkali liquor and hydrogen-rich fuel gas, concentrating and crystallizing the bromine-containing alkali liquor to return to a chlorine salt recovery system, and using the hydrogen-rich fuel gas to prepare superheated steam, wherein a NaOH solution with the mass percentage of 20% is used as an alkali washing spray purifying agent.
(5) Mechanical crushing-eddy current sorting: and (3) mechanically crushing and eddy current sorting the cracking slag obtained in the step (2) to obtain non-metal powder, ferromagnetic particles and metal particles, and comprehensively recovering the products after classification.
The decomposition rate of organic substances is 99.8 percent, and H in the hydrogen-rich fuel gas2Volume fraction of 47.8%, CO2The volume fraction was only 6.1%.
Example 5
The recovery is carried out according to the following steps:
(1) low-temperature vacuum cracking: putting the decommissioned wind power blade composite material crushed to 18 x 18cm into a pyrolysis reactor, adding a certain debrominant, uniformly mixing, controlling the reaction temperature to 520 ℃ under the vacuum atmosphere condition, reacting for 1.5h, carrying out vacuum pyrolysis, obtaining pyrolysis mixed gas and low-temperature pyrolysis slag after the reaction is finished, and carrying out gas catalytic reforming on the pyrolysis mixed gas in the step (4), wherein common waste fly ash silicate cement with the crushed particle size of 160 meshes and the code of P.F and the like are used as the debrominant, and the addition amount of the debrominant is 7% of the mass of the waste organic-inorganic composite material.
(2) Pyrolysis by superheated steam: and (2) introducing superheated steam with the temperature of 1000 ℃ into the low-temperature cracking slag obtained in the step (1) in the same pyrolysis reactor for superheated steam pyrolysis to obtain pyrolysis gas and cracking slag, and introducing the obtained pyrolysis gas into the gas catalytic reforming in the step (4), wherein the mass percentage content of oxygen in the superheated steam is 0.35%, the rate of introducing the superheated steam into each hundred kilograms of cracking slag is 1.1 cubic meter per hour, and the reaction time is 0.8 h.
(3) Catalytic reforming of fuel gas: mixing the pyrolysis mixed gas obtained in the step (1) and the pyrolysis fuel gas obtained in the step (2) according to a volume ratio of 1:3, and then adding a catalyst to perform fuel gas catalytic recombination to obtain mixed fuel gas, wherein the gas introduction amount of each square meter of the catalyst after gas mixing is 4.5 cubic meters per hour, and the catalyst is an Fe-based catalyst.
(4) Gas purification: adding alkali liquor into the mixed fuel gas obtained in the step (4) for fuel gas purification treatment to obtain bromine-containing alkali liquor and hydrogen-rich fuel gas, leaching the bromine-containing alkali liquor, concentrating and crystallizing the bromine-containing alkali liquor, returning a chlorine salt recovery system, and using the hydrogen-rich fuel gas for preparing superheated steam, wherein NaHCO with the mass percentage of 15% is adopted3The solution is used as an alkali washing spray purifying agent.
(5) Mechanical crushing-eddy current sorting: and (3) mechanically crushing and eddy current sorting the cracking slag obtained in the step (2) to obtain non-metal powder, ferromagnetic particles and metal particles, and comprehensively recovering the products after classification.
The decomposition rate of organic substances is 99.7 percent, and H in the hydrogen-rich fuel gas2Volume fraction of 45.7%, CO2The volume fraction was only 4.8%.
Example 6
The recovery is carried out according to the following steps:
(1) low-temperature vacuum cracking: putting the waste circuit board composite material crushed to 12 x 12cm into a pyrolysis reactor, adding a certain debrominant, uniformly mixing, controlling the reaction temperature to be 650 ℃ under the vacuum atmosphere condition, carrying out vacuum cracking for 1.5h, obtaining pyrolysis mixed gas and low-temperature cracking slag after the reaction is finished, and carrying out gas catalytic reforming on the pyrolysis mixed gas in the step (4), wherein common waste common Portland cement with the crushing granularity of 140 meshes and the code of P.O is used as the debrominant, and the addition amount of the debrominant is 16 percent of the mass of the waste organic-inorganic composite material.
(2) Pyrolysis by superheated steam: and (2) introducing superheated steam with the temperature of 800 ℃ into the low-temperature cracked slag obtained in the step (1) in the same pyrolysis reactor for superheated steam pyrolysis to obtain pyrolysis gas and cracked slag, and introducing the obtained pyrolysis gas into the gas catalytic reforming in the step (4), wherein the mass percentage content of oxygen in the superheated steam is 0.25%, the rate of introducing the superheated steam into each hundred kilograms of cracked slag is 0.8 cubic meter per hour, and the reaction time is 1.0 hour.
(3) Catalytic reforming of fuel gas: mixing the pyrolysis mixed gas obtained in the step (1) and the pyrolysis fuel gas obtained in the step (2) according to a volume ratio of 1:3, and adding a catalyst to perform fuel gas catalytic recombination to obtain mixed fuel gas, wherein the gas introduction amount of each square meter of the catalyst after mixing is 3.5 cubic meters per hour, and the catalyst is a Ni-based catalyst.
(4) Gas purification: and (3) adding alkali liquor into the mixed fuel gas obtained in the step (4) to perform fuel gas purification treatment to obtain bromine-containing alkali liquor and hydrogen-rich fuel gas, performing bromine-containing alkali leaching, concentrating and crystallizing to return to a chlorine salt recovery system, and using the hydrogen-rich fuel gas to prepare superheated steam, wherein a NaOH solution with the mass percentage of 15% is used as an alkali washing spray purifying agent.
(5) Mechanical crushing-eddy current sorting: and (3) mechanically crushing and eddy current sorting the cracking slag obtained in the step (2) to obtain non-metal powder, ferromagnetic particles and metal particles, and comprehensively recovering the products after classification.
The decomposition rate of organic substances is 99.5 percent, and H in the hydrogen-rich fuel gas248.0% by volume of CO2The volume fraction was only 4.1%.
The above examples are only for illustrating the preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and modifications, equivalent substitutions and improvements made within the spirit and principle of the present invention within the knowledge of those skilled in the art without departing from the scientific and inventive concept should be considered as the protection scope of the present application.
Claims (5)
1. A method for preparing hydrogen-rich fuel gas by carrying out overheat catalytic conversion on waste organic-inorganic composite materials is characterized by comprising the following specific steps:
(1) low-temperature vacuum cracking: putting the waste organic-inorganic composite material into a pyrolysis reactor, adding a certain debrominant, uniformly mixing, and then carrying out vacuum pyrolysis, wherein the reaction temperature is controlled to be 480-620 ℃ under the vacuum atmosphere condition, the reaction time is 0.5-2.5 h, after the reaction is finished, pyrolysis mixed gas and low-temperature pyrolysis slag are obtained, and the pyrolysis mixed gas enters the step (4) for catalytic reforming of the fuel gas; the addition amount of the debrominant is 5-20% of the mass percent of the waste organic-inorganic composite material;
(2) pyrolysis by superheated steam: introducing superheated steam into the low-temperature cracking slag obtained in the step (1) in the same reactor for superheated steam pyrolysis to obtain pyrolysis gas and cracking slag, and performing catalytic reforming on the obtained pyrolysis gas in the step (4);
(3) catalytic reforming of fuel gas: mixing the pyrolysis mixed gas obtained in the step (1) and the pyrolysis gas obtained in the step (2), and then adding a catalyst to perform gas catalytic recombination to obtain mixed gas;
(4) gas purification: adding alkali liquor into the mixed fuel gas obtained in the step (3) for fuel gas purification treatment to obtain bromine-containing alkali liquor and hydrogen-rich fuel gas;
(5) mechanical crushing-eddy current sorting: and (3) mechanically crushing and eddy current sorting the cracking slag obtained in the step (2) to obtain non-metal powder, ferromagnetic particles and metal particles.
2. The method for preparing the hydrogen-rich gas through the overheat catalytic conversion of the waste organic-inorganic composite material according to claim 1, wherein in the low-temperature vacuum cracking process in the step (1), the waste organic-inorganic composite material is crushed to 5 x 5 cm-20 x 20cm, and a debrominant with a crushing particle size of 100-200 meshes is adopted, wherein the debrominant is ordinary portland cement, portland slag cement, portland pozzolanic portland cement or portland fly ash cement.
3. The method for preparing hydrogen-rich fuel gas through the overheat catalytic conversion of the waste organic-inorganic composite material as claimed in claim 1, wherein in the overheat steam pyrolysis process in the step (2), the oxygen content in the overheat steam is 0.1-0.5% by mass, the temperature of the introduced overheat steam is 650-1200 ℃, the rate of introducing the overheat steam per one hundred kilograms of cracked slag is 0.5-1.5 cubic meters per hour, and the reaction time is 0.5-1.5 hours.
4. The method for preparing hydrogen-rich fuel gas by carrying out overheat catalytic conversion on the waste organic-inorganic composite material according to claim 1, wherein in the catalytic reforming process of the fuel gas in the step (3), the pyrolysis mixed gas and the pyrolysis fuel gas are mixed according to the volume ratio of 1: 1-1: 5, the gas introduction amount of each square meter of the catalyst after mixing is 2.5-5.5 cubic meters per hour, and the catalyst is a Ni-based, Fe-based or Rh-based catalyst.
5. The method for preparing hydrogen-rich fuel gas by the overheat catalytic conversion of the waste organic-inorganic composite material according to claim 1, wherein in the step (4) of purifying the fuel gas, a NaOH solution with a mass percent of 5-20% or NaHCO with a mass percent of 10-30% is adopted3The solution is used as an alkali washing spray purifying agent.
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| PCT/CN2021/138154 WO2023065508A1 (en) | 2021-10-21 | 2021-12-15 | Method for preparing hydrogen-rich fuel gas by overheating catalytic conversion of waste organic-inorganic composite material |
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| CN114871237A (en) * | 2022-04-19 | 2022-08-09 | 中国科学院广州能源研究所 | Method for continuous pyrolysis treatment of waste crystalline silicon photovoltaic module |
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