CN111606315A - Method for reducing metal content in carbon - Google Patents

Method for reducing metal content in carbon Download PDF

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Publication number
CN111606315A
CN111606315A CN202010639609.9A CN202010639609A CN111606315A CN 111606315 A CN111606315 A CN 111606315A CN 202010639609 A CN202010639609 A CN 202010639609A CN 111606315 A CN111606315 A CN 111606315A
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carbon
molten salt
liquid catalyst
metal
raw material
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张国良
韩海波
刘丹禾
魏小波
杨莹
毛继平
江莉
田进锋
刘九林
何文
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China Petroleum and Chemical Corp
Sinopec Engineering Group Co Ltd
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China Petroleum and Chemical Corp
Sinopec Engineering Group Co Ltd
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    • C01B32/00—Carbon; Compounds thereof
    • C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
    • C—CHEMISTRY; METALLURGY
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    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
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    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/22—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of gaseous or liquid organic compounds
    • C01B3/24—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of gaseous or liquid organic compounds of hydrocarbons
    • C01B3/26—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of gaseous or liquid organic compounds of hydrocarbons using catalysts
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    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
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    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
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    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/10—Catalysts for performing the hydrogen forming reactions
    • C01B2203/1041—Composition of the catalyst
    • C01B2203/1047—Group VIII metal catalysts
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    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/10—Catalysts for performing the hydrogen forming reactions
    • C01B2203/1041—Composition of the catalyst
    • C01B2203/1047—Group VIII metal catalysts
    • C01B2203/1052—Nickel or cobalt catalysts
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    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/10—Catalysts for performing the hydrogen forming reactions
    • C01B2203/1041—Composition of the catalyst
    • C01B2203/1047—Group VIII metal catalysts
    • C01B2203/1052—Nickel or cobalt catalysts
    • C01B2203/1058—Nickel catalysts
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
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    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/10—Catalysts for performing the hydrogen forming reactions
    • C01B2203/1041—Composition of the catalyst
    • C01B2203/1076—Copper or zinc-based catalysts
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    • C01B2203/12—Feeding the process for making hydrogen or synthesis gas
    • C01B2203/1205—Composition of the feed
    • C01B2203/1211—Organic compounds or organic mixtures used in the process for making hydrogen or synthesis gas
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Abstract

The invention discloses a method for reducing the metal content in carbon, which comprises the following steps: the hydrocarbon raw material is introduced into the liquid catalyst, then the surface of the liquid catalyst is covered with the molten salt layer, and in the process of producing carbon by catalytically cracking the hydrocarbon raw material by the liquid catalyst, the molten salt layer is used for inhibiting the volatilization of metal steam formed when the liquid catalyst is used for catalytically cracking the hydrocarbon raw material, so that the metal content in the carbon is reduced. The method can obviously reduce the content of metal in carbon generated in the cracking reaction of hydrocarbons and reduce the acid consumption of carbon acid washing.

Description

Method for reducing metal content in carbon
Technical Field
The invention relates to the technical field of petrochemical industry, in particular to a method for reducing metal content in carbon.
Background
Catalytic cracking of hydrocarbons to produce H2And carbon is the focus of current research. The liquid catalyst is used for preparing hydrogen and carbon by catalytic cracking, no other by-products are generated, the atom utilization rate is high, and the economic benefit is high. Carbon floats on the surface of the liquid catalyst due to the density lower than that of molten metal, so that the automatic separation of the carbon and the catalyst is realized, the problem of catalyst deactivation is avoided, and catalyst regeneration equipment and intermittent regeneration operation are reduced.
The reaction temperature is high when the liquid catalyst is used for preparing carbon and hydrogen by catalytic cracking, and the molten metal is volatilized under the action of high temperature and airflow to form high-concentration metal steam. The carbon obtained by catalytic cracking of hydrocarbons has large specific surface area and rich pore channels, and a large amount of molten metal is absorbed inside the carbon. The metallic carbon can meet the commercial requirement only through acid washing, water washing and other steps, the loss of molten metal is serious, the subsequent treatment process is long, the environmental protection pressure is high, and the application of preparing carbon and hydrogen through catalytic cracking of a liquid catalyst is limited.
In view of this, the invention is particularly proposed.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a method for reducing the metal content in carbon.
The invention is realized by the following steps:
the invention provides a method for reducing the metal content in carbon, which comprises the following steps: the hydrocarbon raw material is introduced into the liquid catalyst, then the surface of the liquid catalyst is covered with the molten salt layer, and in the process of producing carbon by catalytically cracking the hydrocarbon raw material by the liquid catalyst, the molten salt layer is used for inhibiting the volatilization of metal steam formed when the liquid catalyst is used for catalytically cracking the hydrocarbon raw material, so that the metal content in the carbon is reduced.
The invention has the following beneficial effects:
the invention provides a method for reducing metal content in carbon, which comprises the steps of introducing a hydrocarbon raw material into a liquid catalyst, covering a molten salt layer on the surface of the liquid catalyst, and inhibiting volatilization of metal steam formed by the liquid catalyst in the process of catalytically cracking the hydrocarbon raw material to produce the carbon by the liquid catalyst through the molten salt layer so as to reduce the metal content in the carbon and achieve the aim of preparing high-purity carbon. And the molten salt can be recycled, so that the operation cost is reduced.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings needed to be used in the embodiments will be briefly described below, it should be understood that the following drawings only illustrate some embodiments of the present invention and therefore should not be considered as limiting the scope, and for those skilled in the art, other related drawings can be obtained according to the drawings without inventive efforts.
FIG. 1 is a schematic diagram of a process flow for reducing the metal content of carbon produced by catalytic cracking of hydrocarbons with a liquid catalyst according to an embodiment of the present invention;
the reference numbers: 101-a reactor; 102-a separation unit; 103-a hydrocarbon feedstock; 104-liquid catalyst; 105-molten salt layer; 106-carbon; 107-fresh inorganic salts; 108-salt-containing reaction gas product; 109-recovery of inorganic salts; 1010-desalted gas product.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
The invention aims to overcome the defects of the prior art and provide a method for reducing the content of metals in carbon, in particular to a method for reducing the content of metals in carbon prepared by catalytic cracking of hydrocarbons by using a liquid catalyst. The following scheme is adopted:
the embodiment of the invention provides a method for reducing metal content in carbon, which comprises the following steps: the hydrocarbon raw material is introduced into the liquid catalyst, then the surface of the liquid catalyst is covered with the molten salt layer, and in the process of producing carbon by catalytically cracking the hydrocarbon raw material by the liquid catalyst, the molten salt layer is used for inhibiting the volatilization of metal steam formed when the liquid catalyst is used for catalytically cracking the hydrocarbon raw material, so that the metal content in the carbon is reduced.
The process flow diagram for reducing the metal content in carbon prepared by catalytic cracking of hydrocarbons by using a liquid catalyst provided by the embodiment of the invention is shown in figure 1. The hydrocarbon material 103 is passed into the reactor 101 filled with the liquid catalyst 104, then the surface of the liquid catalyst 104 is covered with a molten salt layer 105, the hydrocarbon material 103 generates carbon 106 and a reaction gas product 108 containing salt under the action of the liquid catalyst 104, and the carbon 106 floats on the surface of the molten salt layer 105 under the action of buoyancy force and is removed from the reactor 101 through a solid conveying device. The inorganic salt of the reaction gas product 108 containing salt is removed in the separation unit 102 to obtain a desalted gas product 1010 and recovered inorganic salt 109, the desalted gas product 1010 is discharged outside, the recovered inorganic salt 109 returns to the reactor 101 again, and meanwhile, fresh inorganic salt 107 can be supplemented below the molten salt layer of the reactor according to the reaction condition.
Referring further to fig. 1, the reactor contains, from bottom to top, a liquid catalyst 104, a molten salt layer 105 (immiscible with the liquid catalyst), and carbon 106. Density: liquid catalyst 104> molten salt layer 105> carbon 106.
The hydrocarbon material 103 is cracked in the liquid catalyst 104 in two ways, one is thermal cracking of the hydrocarbon in the bubbles, and the other is catalytic cracking of the hydrocarbon on the bubble walls in the liquid catalyst 104. Carbon produced by direct thermal cracking of a hydrocarbon feedstock floats directly on the surface of molten salt layer 105 because it is less dense than liquid catalyst 104 and molten salt layer 105. Partial carbon generated by catalytic cracking reaction of the hydrocarbon raw material 103 in contact with the bubble wall under the action of the liquid catalyst 104 is dissolved in the liquid catalyst 104, finally the partial carbon in the liquid catalyst 104 layer is supersaturated, the carbon density is less than that of the liquid catalyst 104, the separated carbon floats upwards and enters the molten salt layer 105, and after the carbon in the molten salt layer 105 is supersaturated, the carbon is separated out on the surface of the molten salt layer 105; meanwhile, the hydrocarbon material 103 in contact with the bubble wall is not dissolved in the carbon of the liquid catalyst 104 by the catalytic cracking reaction under the action of the liquid catalyst 104, and floats to the surface of the molten salt layer 105. It can be seen that 3 kinds of carbon, namely carbon generated by the thermal cracking in the bubbles, carbon insoluble in the liquid catalyst on the bubble walls, and carbon soluble in the liquid catalyst, finally float upwards and enter the molten salt layer 105 to be separated out on the surface of the molten salt layer 105.
Therefore, if the surface of the liquid catalyst has no molten salt layer, the metal is seriously volatilized and lost, and a part of the metal enters carbon and can be removed by adopting acid washing; the other part enters a downstream unit along with the gas product, and the metal steam is cooled and deposited in the pipeline or equipment, so that the pipeline blockage or equipment damage is easily caused.
The inventor creatively discovers that the molten salt is covered on the surface of the liquid catalyst, so that the volatilization of metal steam can be inhibited, and the content of the adsorbed metal in carbon can be reduced. The melting point and the boiling point of the molten salt selected by the embodiment of the invention are matched with the hydrocarbon cracking reaction temperature, the solubility of the selected molten salt in water at normal temperature is high, and the molten salt in carbon at the later stage can be purified by adopting a water washing method.
In an alternative embodiment, the thickness of the molten salt layer is a minimum of 10 cm.
In an alternative embodiment, the liquid catalyst is composed of a first component and a second component, and the first component is selected from elemental metals or alloys and the second component is selected from metal carbides;
preferably, the first component comprises at least one non-radioactive metallic element of IA, IIA, IIIB, IVB, VB, VIB, VIIB, VIIIB, IB, IIB, IIIA, IVA, VA, VIA and VIIA;
preferably, the second component comprises one or more of Fe, Ti, Gr, Co, Ni, V, Zr, Ca, Mo, Mn and W metal carbides formed with carbon.
In an optional embodiment, in the liquid catalyst, the mass percentage of the first component is 0 to 99.9%, and the mass percentage of the second component is 0.1 to 20%.
Catalytic cracking of hydrocarbons can be achieved with the liquid catalyst for reasons which may be:
the properties of the metal carbide in the second component are similar to those of the VIII group noble metal, and the metal carbide has excellent dehydrogenation function. Alkane bubbles are subjected to catalytic dehydrogenation reaction in a liquid catalyst, and hydrogen obtained by cracking rises to the surface of the liquid catalyst in the bubbles and is automatically separated from the liquid catalyst; one part of carbon obtained by hydrocarbon cracking is condensed on the wall of the bubble catalyst to generate carbon, and the other part of carbon enters the liquid catalyst; the carbon that enters the liquid catalyst partially combines with the metal to form new metal carbides, and partially becomes free carbon. Decomposing the metal carbide in the liquid catalyst to obtain metal and free carbon; the free carbon in the catalyst is supersaturated, and is precipitated on the surface of the catalyst to form new carbon which floats on the surface of the catalyst. The alkane bubbles continuously contact with the real-time atomically updated metal carbide in the rising process, so that the reaction rate is higher than that of a solid catalyst; the liquid catalyst provided by the embodiment of the invention is in a liquid state, and the mass transfer rate of carbon atoms is higher than that of a solid catalyst, so that the reaction rate can be further improved.
Specifically, the types of molten salts selected in the examples of the present invention are as follows:
in an alternative embodiment, the electronegativity of the cationic metal in the molten salt is not higher than the electronegativity of all metals in the liquid catalyst.
In alternative embodiments, the molten salt may be selected from any one of the following salts：AgF、CaBr2、CaCl2、CaI2、CdF2、CsBr、CsCl、CsF、CsI、KI、KOH、LiBr、LiCl、LiI、MnCl2、NaBr、NaCN、NaCl、NaF、NaI、NaOH、NdCl3、PrCl3、RbCl、Rb2SO4、SrCl2、YCl3、CeCl3、KBr、KCl、KF、MgCl2、MgBr2、Na2SO4、NiBr2、NiF2、NiSO4、KF。
In alternative embodiments, the molten salt may be selected from a combination of NaOH and KOH.
In alternative embodiments, the molten salt may be selected from the following cations Li+、Na+、K+、R+、Cs+、Mg2+、Ca2+And the following anions F-、Cl-、Br-、I-A combination of at least one of (1), wherein Mg2+And I-Not all of them can occur simultaneously, and the kinds of anions and cations are not less than 3.
In alternative embodiments, the molten salt may be selected from the following cations Na+、K+、Ni+、Rb+And the following anions F-、Cl-、Br-、SO4 2-A combination of at least one of (1) and (b), wherein Ni is contained2+And Rb+Must not contain SO4 2-And the anion and cation species are not less than 3.
In alternative embodiments, the molten salt may be selected from the following cations Ag+、Cs+、Ni+、K+、Na+And F-Wherein the number of cations must not be lower than two.
In alternative embodiments, the molten salt may be selected from the following cations Li+、Na+、K+、Rb+、Cs+、Mn2+、Mg2+、Nd3+、Y3+、Ce2+And Cl-In the combination of (a) and (b),wherein the number of cations must not be lower than two.
The features and properties of the present invention are described in further detail below with reference to examples.
Example 1
The raw materials comprise: methane (pretreated without N, S, O-containing compound).
Reaction temperature: 1750 ℃.
Catalyst: fe. Sn, Cu.
Inorganic salts: CaBr2。
Thickness of inorganic salt layer: 50 cm.
Methane enters the reactor from the bottom of the reactor, carbon and gas products are obtained under the action of a molten alloy catalyst, and the carbon enters the molten salt layer under the action of buoyancy and finally floats on the surface of the molten salt layer. The carbon is removed from the reactor by means of a solid conveying device and the salt-containing gas product is subjected to CaBr in a separation unit2And separation of the gaseous product, CaBr2And re-entering the reactor.
Adding CaBr into the reactor2The metal content in the carbon was 43.7%. Adding CaBr into the reactor2Then, the metal content in the carbon is reduced to 3.4 percent, and the inorganic salt content is 10.7 percent.
Example 2
The raw materials comprise: wax oil.
Reaction temperature: 1420 ℃.
Catalyst: ce. Alloy composed of Ga and Pb.
Inorganic salts: CeCl3And KCl in a mass ratio of 1: 9.
Thickness of inorganic salt layer: 80 cm.
The wax oil enters the reactor from the bottom of the reactor, carbon and gas products are obtained under the action of an alloy catalyst, and the carbon enters the molten salt layer under the action of buoyancy and finally floats on the surface of the molten salt layer. The carbon is removed from the reactor by means of a solid conveying device and the salt-containing gas product is subjected to CeCl in a separation unit3KCl and separation of the gaseous product, CeCl3And KCl is returned to the reactor again.
Adding CaBr into the reactor2The metal content in the carbon was 39.3%. Adding CaBr into the reactor2Then, the metal content in the carbon is reduced to 3.5 percent, and the inorganic salt content is 11.1 percent.
Example 3
The raw materials comprise: coal tar.
Reaction temperature: 1250 deg.c.
Catalyst: fe. Alloy of Co, Sn and Fe3C
Inorganic salts: na (Na)2SO4And K2SO4The mass ratio is 1:1
Thickness of inorganic salt layer: 100 cm.
The wax oil enters the reactor from the bottom of the reactor, carbon and gas products are obtained under the action of the catalyst, and the carbon enters the molten salt layer under the action of buoyancy and finally floats on the surface of the molten salt layer. The carbon is removed from the reactor by means of a solid conveying device and the salt-containing gas product is subjected to Na in a separation unit2SO4、K2SO4And separation of the gaseous product, Na2SO4And K2SO4And re-entering the reactor.
Adding Na into the reactor2SO4And K2SO4The metal content in the carbon was 35.9%. Adding Na into the reactor2SO4And K2SO4After the layer is formed, the metal content in the carbon is reduced to 5.0 percent, and the inorganic salt content is 14.2 percent.
Example 4
The raw materials comprise: ethylene tar.
Reaction temperature: 2100 ℃.
Catalyst: alloy of Ni and Sn and Ni3C。
Inorganic salts: NiSO4。
Thickness of inorganic salt layer: 80 cm.
Ethylene tar enters the reactor from the bottom of the reactor, carbon and gas products are obtained under the action of a molten catalyst, and the carbon enters the molten salt layer under the action of buoyancy and finally floats on the surface of the molten salt layer. The carbon is removed from the reactor by a solid conveying device, and the product of the gas containing salt is separatedIn-cell NiSO4And separation of gaseous products, NiSO4And re-entering the reactor.
Adding NiSO into the reactor4The metal content in the carbon was 34.4%. Adding CaBr into the reactor2Then, the metal content in the carbon is reduced to 2.9 percent, and the inorganic salt content is 17.4 percent.
Example 5
The raw materials comprise: methanol.
Reaction temperature: 1700 ℃.
Catalyst: bi. Alloy of Sn and Ni
Inorganic salts: rb2SO4And NiSO4The mass ratio is 1: 20.
Thickness of inorganic salt layer: 120 cm.
Methane enters the reactor from the bottom of the reactor, carbon and gas products are obtained under the action of a molten alloy catalyst, and the carbon enters the molten salt layer under the action of buoyancy and finally floats on the surface of the molten salt layer. The carbon is removed from the reactor by means of a solid conveying device and the salt-containing gas product is subjected to Rb in a separation unit2SO4、NiSO4And separation of the gaseous product, Rb2SO4And NiSO4And re-entering the reactor.
Rb is added into the reactor2SO4And NiSO4The metal content in the carbon was 36.6%. Rb is added into the reactor2SO4And NiSO4Then, the metal content in the carbon is reduced to 4.3 percent, and the inorganic salt content is 7.2 percent.
In summary, the present invention provides a method for reducing the metal content in carbon prepared by catalytic cracking of a liquid catalyst, comprising the following steps: the hydrocarbon raw material is introduced into the liquid catalyst, then the surface of the liquid catalyst is covered with the molten salt layer, and in the process of producing carbon by catalytically cracking the hydrocarbon raw material by the liquid catalyst, the molten salt layer is used for inhibiting the volatilization of metal steam formed when the liquid catalyst is used for catalytically cracking the hydrocarbon raw material, so that the metal content in the carbon is reduced. The method can obviously reduce the content of metal in the carbon and reduce the acid consumption of carbon acid pickling. The inorganic salt of the invention can be recycled, and the operation cost is low.
The above is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and various modifications and changes will occur to those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (10)

1. A method for reducing the metal content in carbon is characterized by comprising the following steps: the method comprises the steps of introducing a hydrocarbon raw material into a liquid catalyst, covering a molten salt layer on the surface of the liquid catalyst, and inhibiting volatilization of metal steam formed by the liquid catalyst in the process of catalytically cracking the hydrocarbon raw material to produce carbon by the liquid catalyst through the molten salt layer so as to reduce the metal content in the carbon in the process of catalytically cracking the hydrocarbon raw material by the liquid catalyst.
2. The method of claim 1, wherein the molten salt layer has a thickness of at least 10 cm.
3. The method of claim 1, wherein the liquid catalyst is comprised of a first component selected from elemental metals or alloys and a second component selected from metal carbides;
preferably, the first component comprises at least one non-radioactive metallic element of IA, IIA, IIIB, IVB, VB, VIB, VIIB, VIIIB, IB, IIB, IIIA, IVA, VA, VIA, and VIIA;
preferably, the second component comprises one or more of Fe, Ti, Gr, Co, Ni, V, Zr, Ca, Mo, Mn and metal carbide formed by W and carbon;
more preferably, in the liquid catalyst, the mass percentage of the first component is 0 to 99.9%, and the mass percentage of the second component is 0.1 to 20%.
4. The method of claim 1 in which the electronegativity of the cationic metal in the molten salt is not higher than the electronegativity of all metals in the liquid catalyst.
5. Method according to claim 4, characterized in that the molten salt is selected from AgF, CaBr2、CaCl2、CaI2、CdF2、CsBr、CsCl、CsF、CsI、KI、KOH、LiBr、LiCl、LiI、MnCl2、NaBr、NaCN、NaCl、NaF、NaI、NaOH、NdCl3、PrCl3、RbCl、Rb2SO4、SrCl2、YCl3、CeCl3、KBr、KCl、KF、MgCl2、MgBr2、Na2SO4、NiBr2、NiF2、NiSO4And KF.
6. The method according to claim 4, characterized in that the molten salt is selected from the group consisting of NaOH and KOH in combination.
7. The method according to claim 4, characterized in that the molten salt is selected from the following cations Li+、Na+、K+、R+、Cs+、Mg2+、Ca2+And the following anions F-、Cl-、Br-、I-A combination of at least one of (1), wherein Mg2+And I-Not to occur simultaneously and not less than 3 kinds of anion and cation.
8. A method according to claim 4, characterized in that the molten salt is selected from the following cations Na+、K+、Ni+、Rb+And the following anions F-、Cl-、Br-、SO4 2-A combination of at least one of (1) and (b), wherein Ni is contained2+And Rb+Must not contain SO4 2-And anion and cation species are not less than 3.
9. The method according to claim 4, characterized in that the molten salt is selected from the following cations Ag+、Cs+、Ni+、K+、Na+And the anion is F-And the number of cations must not be lower than two.
10. The method according to claim 4, characterized in that the molten salt is selected from the following cations Li+、Na+、K+、Rb+、Cs+、Mn2+、Mg2+、Nd3+、Y3+、Ce2+And the anion is Cl-And the number of cations must not be lower than two.
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CN115973999A (en) * 2023-03-20 2023-04-18 锦浪科技股份有限公司 Hydrogen production system based on solar energy

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