• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    A process is disclosed for the production of humic acids, which comprises an oxidation of coal in dry phase with oxygen or mixtures of oxygen and nitrogen in a fluidized-bed reeactor, by using coal with a granulometry comprised within the range of from 100 mu m to 3 mm and operating at a temperature comprised within the range of from 150 to 300 DEG C, under a partial pressure of oxygen comprised within the range of from 1.1 abs.atm. to 10 abs.atm., for a contact time comprised within the range of from 30 minutes to 600 minutes.
    公开号:SU1639426A3
    申请号:SU874203912
    申请日:1987-12-17
    公开日:1991-03-30
    发明作者:Калемма Винченцо；Рауза Риккардо
    申请人:Эниричерке С.П.А. (Фирма)；
    IPC主号:
    专利说明:

    The invention relates to new methods for producing humic acids, which are used to extract metals from water as additives to fertilizers.
    The purpose of the invention is to increase the yield of the target product and simplify the process.
    The goal is achieved by the oxidation of brown, subbituminous or bituminous coal in a dry environment with oxygen or a mixture of oxygen and nitrogen.
    in a fluidized bed reactor, with a particle size distribution of coal from 100 μm to 3 mm, at 150–300 ° C, with a partial pressure of oxygen from 141 to 10 abs. atm, with a reaction time of 30–600 min.
    Example 1. In the reactor load 30 g of pre-dried sub-bituminous coal Wyodak with a particle size distribution of from 250 to 106 microns. Then in the reactor
    CM
    Pressure is pressurized with nitrogen at an appropriate flow rate to ensure fluidization, the temperature in the reactor is raised to. After that, air is supplied and at the same time, the temperature is stabilized at 200 for the required time, then the reaction is quenched by adding nitrogen again, and the equipment is cooled.
    The content of humic acids in oxidized coal is determined as follows
    Sample in the amount of 10 g and 150 ml of 1 -N. the NaOH solution is placed in a flask and refluxed in an inert medium (Ng) with stirring for 7 hours. The resulting reaction is centrifuged to separate the residue. The residue is washed once with 08L n, a solution of NaOH, and then with water o The washings are drained together with the solution obtained by centrifugation. The residue is dried, its weight and the content of organic matter are determined.
    Humic acids contained in the solution are recovered by precipitation, add. or HC1 before, and by centrifugation. Then the solid residue is dried, its weight and the content of organic matter are determined,
    Table 1

    The e and c.1 values referring to humic acids, residue and fulvic acids belong to the organic matter contained in the oxidized carbon, while the values of CO + CO refer to the carbon content in the coal serving as the original product .
    Example 2. 30 g of Wyodak sub-bituminous coal is oxidized as in Example 1 under the following conditions: In addition, the temperature is 200 ° C; oxygen partial pressure of 5 abs.atm; granulometric composition of coal 250-106 microns; oxides
    The content of fulvic acids is determined by placing 10 g of oxidized carbon and 130 ml of 0.01 n of FC1 solution in a flask, heating it to 80 ° C with stirring for 3 hours in an inert nitrogen atmosphere. The residue is then washed with water, dried and its weight is determined.
    In the thus obtained sample, the content of organic matter is determined and the difference in the content of organic matter in the original coal is determined by the content of fulvic acids.
    The reaction conditions are as follows: temperature 200 ° C; oxygen partial pressure of 1.1 abs.atm; granulometric composition of coal 250-106 microns.
    The results are shown in table 1,
    Note: humic acids, residue and fulvic acids refer to organic matter contained in oxidized carbon, while C0 + C02 values refer to the carbon content of the coal that serves as the starting product.
    Example 3. 30 g of Wyodak subbituminous coal is oxidized as in Example 1 under the following conditions: temperature 200 ° C; oxygen partial pressure of 5 abs.atm; particle size of coal 3-1 mm; oxidizer 50% mixture Nj / 02.
    The results are shown in table 3.
    CO + CO refers to the carbon content of the original coal,
    Example 4. 30 g of Illinais No. 6 bituminous carbon is oxidized as in Example 1 under the following conditions: temperature 200 ° C; partial pressure of oxygen 1.1 abs.atm; granulometric composition of 250-106 microns; oxidizer air.
    I
    The results are shown in
    table.4.
    Table 4
    1639426
    nose to carbon content in the original coal
    Example 5. 30 grams of Illinais No. 6 bituminous carbon is oxidized as in Example 1 under the following conditions: temperature 200 ° C; partial pressure Note: the values of humic acids, residue and sevic acids refer to the organic matter contained in the oxidized carbon, whereas the values of CO + CO refer to the carbon content in the original coal. Example 6. 30 g Illinais No. 6
    coal was oxidized as in example 1 under the following conditions: temperature 200 ° C; oxygen partial pressure of 5 abs.atm; Granulometric composition of coal 3-1 mm, oxidizer 50% mixture
    N, / 0 ,.
    Note: The values of humic acids, residue and lulvic acids refer to organic matter contained in oxidized coal, whereas the values of C (HCO2 refer to the carbon content of the original coal.
    Note (valid for all three examples 7, 8 and 9): the values of humic acids, fulvic acids and residues refer to the organic substance contained in oxidized carbon, while the percentage of CO and CO output refers to the carbon content of the original coal.
    Example 8 Using the procedure of Example 1, 1.30 g of Wyodak subbituminous coal is oxidized with an oxidizing mixture of 50% oxygen and 50% nitrogen, the partial pressure of oxygen being 0.5 atm. The particle size of the coal is 106-250 microns.
    The results are shown in table.8.
    Table 8
    Example 9. Using the procedure of Example 1, 1.30 g of bituminous coal Illinais No. 6 is oxidized at 300 ° C with air, the partial pressure of oxygen is 0.21 atm, and the size of the particles of the coal is 106-250 µm.
    The results are shown in table.9.
    Example 7 Using the procedure of Example 1, Gondwanaland bituminous coal (1.30 g) is oxidized with compressed oxygen, and the particle size of the coal is 106-250 microns.
    The results are shown in table.7.
    Table 7)
    Table
    Example 10. According to the method of Example I, brown coal — North Dakota (lignite) is oxidized, under the following conditions: temperature 150 ° Cj oxygen pressure 1.26 atm; particle size 106-250 microns,
    The results are given in table 10,
    table 10,
    Example
    v / II p m emec n: e, at 11, subjected to oxidation for humic and fulvene oxidation
    brown coal — Severn Dakota (lignite) is burned under the following conditions: temperature 200 ° С; oxygen pressure 2.1 atm; particle size of 500-750 microns.
    The results are given in table.
    25
    acids, refer to the organic material of oxidized carbon, while the outputs of C0 + C0e relate to the carbon content of the original coal.
    Example 13. Carbon is oxidized to Sardinia subbituminous coal, under the following conditions: temperature 250 ° C; oxygen pressure of 1.26 atm; particle size of 250-500 microns.
    Table 1 1
    45
    Note: the values given for humic and fulvic acids refer to the organic material of oxidized carbon, whereas the output from C0 + C0g moves to the carbon content of the original coal.
    Limer 12. Carbon monoxide is oxidized - Montana Rosebud (sub-bituminous), under the following conditions: temperature 200 ° C {oxygen pressure 1 ,, 26 atm; particle size of 500-650 microns.
    The results are given in table.
    acids, refer to the organic material of oxidized carbon, while the outputs of C0 + C0e relate to the carbon content of the original coal.
    Example 13. Carbon is oxidized to Sardinia subbituminous coal, under the following conditions: temperature 250 ° C; oxygen pressure of 1.26 atm; particle size of 250-500 microns.
    The results are given in table 13.
    Table 13

    -Note: the values given for humic fulvic acids refer to the organic material of oxidized carbon, while the outputs refer to the carbon content of the original coal.
    The proposed method allows nor to increase the yield of humic acids to 68–88% in terms of organic material of oxidized carbon (versus 45%) and to simplify the process due to its conduct in an anhydrous medium.
    权利要求:
    Claims (1)
    [1]
    Invention Formula
    1, Method for producing humic acids by oxidizing coal at elevated temperature and pressure, characterized in that, in order to increase the yield of the target product and simplify the process, brown, sub-bituminous or bituminous coal in a dry environment with oxygen or an oxygen-nitrogen mixture with nitrogen in the reactor is subjected to oxidation with a pseudo-oxidized layer, with a granulometric composition of coal in the range from 100 μm to 3 mm, at 150–300 ° C, oxygen partial pressure from 1.1 d 1P abs. atm with a reaction time of 30–600 min.
     The method is pop, 1, about tl and h a torn, and in order to use coal with a grain size distribution in the range of 500W750 microns.
    3, The method of pop, 1, about t and h and u and with the fact that air is taken as a mixture of oxygen and nitrogen,
    40 The method according to claim 2, wherein brown coal is subjected to oxidation at 150-200 ° C and a reaction time of 30-240 minutes.
    5. The method according to claim 4, characterized by the fact that brown is oxidized.
    coal with a particle size of 106-250 microns under a partial pressure of oxygen I, 1-2.0 abs.atm.
    6. Method pop4 1, differing from that with the fact that sub-bituminous coal is oxidized at 200-250 ° C for 30-360 minutes.
    7. The method according to claim 6, differing from that by oxidizing sub-bituminous coal with a particle size of 106-250 µm under an oxygen partial pressure of 1.1-1.26 abs.atm.
    8. Method pop, 1, distinguished by
    y and with the fact that bituminous coal is oxidized at 200-300 ° C for 30-360 minutes.
    Part The method according to claim 8, differing from that with the fact that bituminous coal with a particle size of 106–250 μm is oxidized under an oxygen partial pressure of 1.1–5.0 abs.atm,
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    同族专利:
    公开号 | 公开日
    EP0272737A3|1989-02-22|
    AU591005B2|1989-11-23|
    US4788360A|1988-11-29|
    AU8256787A|1988-06-23|
    IT8622744D0|1986-12-18|
    EP0272737A2|1988-06-29|
    PL152903B1|1991-02-28|
    ES2079346T3|1996-01-16|
    IT1199808B|1989-01-05|
    CA1294951C|1992-01-28|
    ZA879232B|1988-06-20|
    DE3751611D1|1996-01-04|
    PL269502A1|1988-08-18|
    DE3751611T2|1996-05-15|
    AT130622T|1995-12-15|
    EP0272737B1|1995-11-22|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    DE803836C|1948-10-05|1951-04-12|Bergwerksverband Zur Verwertun|Process for the production of humic acid mixtures|
    JPS5736311B2|1979-10-24|1982-08-03|NZ225271A|1987-07-08|1991-02-26|Nat Energy Council|Oxidising coal using a gaseous oxidant|
    IT1227135B|1988-10-14|1991-03-19|Eniricerche Spa|PROCEDURE FOR THE EXTRACTION FROM HUMIC ACIDS REGENERATED FROM CHARCOAL OF ESSENTIAL ALIPHATIC AND LOW MOLECULAR WEIGHT FRACTIONS.|
    DE3937691A1|1988-11-16|1990-05-17|Nat Energy Council|OBTAINING HUMIC ACID|
    IT1244810B|1990-11-29|1994-09-05|Eniricerche Spa|PROCEDURE FOR PRODUCING HUMIC ACIDS REGENERATED FROM COAL|
    DE4129872C2|1991-09-09|1994-11-17|Hartmut Dipl Chem Knauf|Process for the preparation of humic acid-metal compounds, their use as adsorbents and / or detoxifiers or as a trace element source|
    IT1251201B|1991-09-13|1995-05-04|Eniricerche Spa|PROCEDURE FOR THE PREPARATION OF HUMIC ACIDS REGENERATED FROM COAL|
    IT1255083B|1992-04-02|1995-10-18|Eniricerche Spa|PROCEDURE FOR THE PRODUCTION OF ACTIVATED CARBON|
    IT1258248B|1992-11-06|1996-02-22|Eniricerche Spa|PROCEDURE FOR THE PRODUCTION OF ACTIVATED CARBON|
    US5688999A|1996-01-26|1997-11-18|Lignotech Usa, Inc.|Production of oxidized humic acids by an oxygen-alkali process|
    US5746787A|1996-10-28|1998-05-05|Kfx Inc.|Process for treating carbonaceous materials|
    JPH11310785A|1998-04-30|1999-11-09|Mitsubishi Heavy Ind Ltd|Method and apparatus for coal improvement|
    FR2890654B1|2005-09-13|2008-02-01|Toulouse Inst Nat Polytech|PROCESS FOR PREPARING AN ARTIFICIAL HUMIC COMPOSITION, AND APPLICATIONS|
    RU2463282C1|2011-05-19|2012-10-10|Анастасия Анатольевна Томилова|Method of producing water-soluble humic acids|
    US9896388B2|2015-04-23|2018-02-20|Earth Technologies Usa Limited|Coal-derived mineral matter as a soil amendment|
    CN111138684A|2019-12-31|2020-05-12|山东胜伟盐碱地科技有限公司|Method for extracting humic acid from lignite|
    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    IT22744/86A|IT1199808B|1986-12-18|1986-12-18|PROCEDURE FOR THE PRODUCTION OF HUMIC ACIDS REGENERATED FROM COAL|
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