CN101611762A - A kind of compound quick-action inhibitor against generation of methane and its production and use - Google Patents

A kind of compound quick-action inhibitor against generation of methane and its production and use Download PDF

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CN101611762A
CN101611762A CN200910089581A CN200910089581A CN101611762A CN 101611762 A CN101611762 A CN 101611762A CN 200910089581 A CN200910089581 A CN 200910089581A CN 200910089581 A CN200910089581 A CN 200910089581A CN 101611762 A CN101611762 A CN 101611762A
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inhibitor
powder
liquid
methane
mixing
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CN101611762B (en
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杨红建
张丹凤
姜雅慧
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China Agricultural University
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China Agricultural University
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Abstract

The invention discloses a kind of compound quick-action inhibitor against generation of methane of reduction of greenhouse gas discharge technical field, its preparation method is 1) with nitroethane, 2-nitroethyl alcohol and 2-nitro-1-propyl alcohol with (0~5): (0~6): the weight ratio of (0~7) is mixed (can not be 0 simultaneously), is mixed with A liquid; 2) with Pyromellitic Acid imidodicarbonic diamide and 2-bromoethane sodium with (0~3): the weight ratio of (0~2) is mixed (can not be 0 simultaneously), is mixed with the B powder.It is extremely remarkable that composite inhibitor of the present invention suppresses the methane effect, is specially adapted to suppress the methanogenesis in the cud, helps protecting environment, improves the ruminant feed energy utilization efficiency; The preparation method is simple, workable, is applicable to that livestock and poultry breeding industry feed processing, animal dung homaluria thing biogas are administered and domestic waste biogas is administered, and the inhibition efficient of microorganism methanogenesis is reached more than 90%, has higher utility.

Description

A kind of compound quick-action inhibitor against generation of methane and its production and use
Technical field
The present invention relates to a kind of compound quick-action inhibitor against generation of methane and its production and use, belong to the reduction of greenhouse gas discharge technical field.
Background technology
The cud that uses produces the methane inhibitor and mainly contains Monensin, halide, nitro compound, plant extracts etc. at present.The use of Monensin is comparatively extensive, and the methane that can reduce animal body interior 30% generates, but it is not lasting to suppress effect.Chloraldurate changes into chloroform in cud, can reduce the generation of methane in vivo, but chloraldurate damages liver, feed for a long time to cause that animal poisons, in addition dead; The effect that tribromo-acetyl, three chloroethyl adipic acids and bromochloromethane suppress the methane generation is very of short duration; 2-bromoethane sodium (BES) is a kind of effective CH4 inhibitor, can not suppress the growth of other bacterium.It is of short duration that in vivo studies finds that it suppresses effect, and possible methane backeria produces patience to BES.
Plant extracts comprises essential oil, secondary metabolites etc.In the plants essential oil, observe at present effect best be garlic oil, can suppress 74% methane generation external.Secondary metabolites such as saponin class material reduce by 15.79% at the external methane generation that makes; Studying more in addition is tannin, but the tannin of separate sources is not quite similar to methanogenesis, and the tannin that uses in some report is not remarkable to the inhibition effect of methanogenesis.
Also have electron acceptor such as fumaric acid in addition, also can reduce the generation of methane, but can only reduce about 6%.
When nitroethane, 2-nitroethyl alcohol, 2-nitro-1-propyl alcohol, Pyromellitic Acid imidodicarbonic diamide and 2-bromoethane sodium use separately, reports such as Anderson, as fermentation substrate, nitroethane, 2-nitroethyl alcohol and 2-nitro-1-propyl alcohol can suppress cud methanogenesis more than 90%, 80% and 70% in external difference with clover; Van Nevel and Demeyer report, the Pyromellitic Acid imidodicarbonic diamide can suppress 97% external methane generation; Reports such as Nollet, 2-bromoethane sodium also can suppress the external methane generation more than 90%.But the independent result of use of these inhibitor is not lasting, and these five kinds of inhibitor are used in combination, and not only suppresses respond well (more than 90%, high energy reach 99.5%), and methanogen is difficult for producing resistance, and this being combined in there is no report both at home and abroad.
Summary of the invention
The purpose of this invention is to provide a kind of compound quick-action inhibitor against generation of methane and its production and use, to reach the purpose of efficient inhibition methanogenesis.
Described compound quick-action inhibitor against generation of methane, being divided into A, B two parts: A is liquid, slightly light yellow, main component comprises nitroethane, 2-nitroethyl alcohol and 2-nitro-1-propyl alcohol; B is the pale solid powder, and main component comprises Pyromellitic Acid imidodicarbonic diamide and 2-bromoethane sodium.
Described nitroethane, 2-nitroethyl alcohol, 2-nitro-1-propyl alcohol, Pyromellitic Acid imidodicarbonic diamide and 2-bromoethane sodium are chemical pure, and purity is respectively 70~99%, 70~97%, 70~97%, 80~97% and 80~98%.
The preparation method's of described compound quick-action inhibitor against generation of methane concrete steps are:
1) be (0~5) with 2-nitro-1-propyl alcohol according to weight ratio with nitroethane, 2-nitroethyl alcohol: (0~6): the proportion compatibility of (0~7) mixes, and can make inhibitor A liquid, and wherein each component addition of A liquid can not be 0 simultaneously;
2) be (0~3) with the 2-bromoethane sodium according to weight ratio with the Pyromellitic Acid imidodicarbonic diamide: the proportion compatibility of (0~2) mixes, and makes the B powder, and wherein each component addition of B powder can not be 0 simultaneously.
The purposes of described compound quick-action inhibitor against generation of methane is as follows:
1) cattle and sheep concentrate supplement: by adding inhibitor A liquid 100~1000g in the concentrate supplement per ton, add inhibitor B powder 0.6~6g, during use, for making things convenient for mixing, can be that 100 purpose zeolite powders or powdered rice hulls mix and add in the feed again with the B powder and the grinding particle size of 20 times of weight, can directly feed after evenly mixing, no longer additionally add in the roughage;
2) cattle and sheep roughage: by adding inhibitor A liquid 40~400g, inhibitor B powder 0.25~2.5g in the roughage per ton, for guaranteeing uniformity, can be with after A liquid and the mixing of B powder, after adding the water dilution of 2 times of weight, evenly be sprayed onto and directly feed after roughage is gone up, no longer additionally add in the concentrate supplement;
3) thick fine fodder mixes and uses: according to purposes 2) described in method evenly spill after with inhibitor A liquid dilute with water and drench on the roughage, simultaneously according to purposes 1) described in the method ruminant domestic animals such as cattle and sheep of can directly feeding after evenly adding to the inhibitor B powder in the concentrate supplement;
4) domestic waste field biogas is administered: add 400~1000g inhibitor A liquid and 3~8g inhibitor B powder in the house refuse per ton, during use, for making things convenient for mixing, can after the water dilution of 2 times of weight of adding, be sprayed onto in the rubbish after A liquid and the mixing of B powder;
5) animal dung homaluria thing biogas is administered: animal dung homaluria species per ton add 400~1000g inhibitor A and 3~8g inhibitor B powder, during use, for making things convenient for mixing, can after the water dilution of 2 times of weight of adding, spray after A liquid and the mixing of B powder.
Beneficial effect of the present invention is, compound quick-action inhibitor against generation of methane of the present invention will carry out compatibility without nitroethane, 2-nitroethyl alcohol, 2-nitro-1-propyl alcohol, Pyromellitic Acid imidodicarbonic diamide and the 2-bromoethane sodium of kind and concentration, it is extremely remarkable to suppress the methane effect, be specially adapted to suppress the methanogenesis in the cud, help protecting environment, improve the ruminant feed energy utilization efficiency; The preparation method is simple, workable, is applicable to that livestock and poultry breeding industry feed processing, animal dung homaluria thing biogas are administered and domestic waste biogas is administered, and the inhibition efficient of microorganism methanogenesis is reached more than 90%, has higher utility.
The specific embodiment
Compound quick-action inhibitor against generation of methane among the present invention, being divided into A, B two parts: A is liquid, slightly light yellow, and main component comprises nitroethane, 2-nitroethyl alcohol and 2-nitro-1-propyl alcohol, and purity is respectively 70~99%, 70~97% and 70~97%; B is the pale solid powder, and main component comprises Pyromellitic Acid imidodicarbonic diamide and 2-bromoethane sodium, and purity is respectively 80~97% and 80~98% (above agents useful for same is chemical pure).
Further set forth the present invention below in conjunction with specific embodiment.
Embodiment 1: the addition and the result of use analysis of producing the methane inhibitor
Consider that this compound quick-action inhibitor against generation of methane is the combination of five kinds of single inhibitor, this test is analyzed comparison so that therefrom select excellent for these five influence factors.In test, because the residing state of factor is different with condition, may cause the variation of index, these states and the condition of factor are called level.This test is all selected four kinds of states, i.e. four levels to determined five factors.So select L earlier for use 16(4 5) orthogonal table (table 1).
Effective addition according to each level of methane inhibitor component in the table 2 adds nitroethane, 2-nitroethyl alcohol, 2-nitro-1-propyl alcohol and 2-bromoethane sodium in fermentation flask, with the milk cow is experimental animal, be that the sheep's hay and the corn flour of 1: 4 and 4: 1 is the microbial fermentation substrate with weight ratio respectively, carry out anaerobic fermentation behind the inoculation rumen microorganism, generation by fermentation gas tape deck recording occurring continuously fermentation gas, after 48 hours, measure external dry disappearance rate IVDMD, the generation of total volatile acid generation TVFA and the generation of methane.
Microorganism mainly comprises protozoon, bacterium, fungi in the cud chyme, these microorganisms are in the feed that the digest and decompose animal is taken food in the cud anaerobic environment, can produce volatile fatty acids such as the acetate that helps animal body and absorb, propionic acid, butyric acid, meanwhile can produce a large amount of methane, not only the fodder energy that animal is taken in causes great waste, and the greenhouse effects of atmosphere are also caused the aggravation effect of can not ignore.
Result of the test shows that the external dry disappearance rate IVDMD in each processing procedure of interpolation inhibitor all has decline in various degree.When fermentation substrate was C1M4 (ratio of sheep's hay and corn flour is 1: 4), IVDMD decline degree was lower in the processed group 2,5 and 6, made up 1 (not adding inhibitor) relatively and descended 10.26%, 12.04% and 11.78% respectively; When fermentation substrate was C4M1 (ratio of sheep's hay and corn flour is 4: 1), IVDMD decline degree was lower in the processed group 5, made up 1 and descended 11.17%.When being substrate with C1M4, processed group 5 is relative with total volatile acid (being respectively 94.4mM/gDM and 94.0mM/gDM) of 6 to make up 1 does not have significant difference; When fermentation substrate is C4M1, add that total volatile acid generation amount all has remarkable decline in each combination of inhibitor, it is the highest wherein to make up in 5 total volatile acid generation, makes up 1 and descends 20.62%.No matter C1M4 or C4M1 when fermentation substrate, all add in the processed group of inhibitor the methane generation and all descend extremely significantly, all reach more than 90%, and wherein, among the C1M4, the range of decrease of combination 6 and 10 reaches 99.59% and 99.55% respectively; And among the C4M1, combination 9 and 13 methane generation also descended respectively 99.36% and 99.09% (table 3).Test data shows that this composite inhibitor influences considerably beyond the influence to the normal fermentation of cud the generation of methane.
Table 1 orthogonal test form L16 (45)
NE: nitroethane, NEOH:2-nitroethyl alcohol, NPOH:2-nitro-1-propyl alcohol
DII: Pyromellitic Acid imidodicarbonic diamide, BES:2-bromoethane sodium
The interpolation level of the various inhibitor of table 2
When table 3 is fermentation substrate with C1M4 and C4M1 respectively, the external dry disappearance rate during each is handled, always volatilize generation and methane generation
C1M4: the ratio of sheep's hay and corn flour is 1: 4; C4M1: the ratio of sheep's hay and corn flour is 4: 1; IVDMD: external dry disappearance rate; TVFA: total volatile acid generation; CH4: methane generation.
Unless specialize, these embodiment among the present invention only are used to illustrate the present invention, but can not limit protection scope of the present invention.To those skilled in the art, under the prerequisite that does not deviate from the present invention's spirit and implement, various changes or change that the product methane inhibitor component in these embodiments, content, ratio etc. are carried out also belong to protection scope of the present invention.

Claims (4)

1, a kind of compound quick-action inhibitor against generation of methane is characterized in that, it is liquid that this inhibitor is divided into A, B two parts: A, slightly light yellow, and main component comprises nitroethane, 2-nitroethyl alcohol and 2-nitro-1-propyl alcohol; B is the pale solid powder, and main component comprises Pyromellitic Acid imidodicarbonic diamide and 2-bromoethane sodium.
2, compound quick-action inhibitor against generation of methane according to claim 1, it is characterized in that, described nitroethane, 2-nitroethyl alcohol, 2-nitro-1-propyl alcohol, Pyromellitic Acid imidodicarbonic diamide and 2-bromoethane sodium are chemical pure, and purity is respectively 70~99%, 70~97%, 70~97%, 80~97% and 80~98%.
3, the preparation method of the described compound quick-action inhibitor against generation of methane of a kind of claim 1 is characterized in that, the concrete steps of described method are:
1) be (0~5) with 2-nitro-1-propyl alcohol according to weight ratio with nitroethane, 2-nitroethyl alcohol: (0~6): the proportion compatibility of (0~7) mixes, and can make inhibitor A liquid, and wherein each component addition of A liquid can not be 0 simultaneously;
2) be (0~3) with the 2-bromoethane sodium according to weight ratio with the Pyromellitic Acid imidodicarbonic diamide: the proportion compatibility of (0~2) mixes, and makes the B powder, and wherein each component addition of B powder can not be 0 simultaneously.
4, the purposes of the described compound quick-action inhibitor against generation of methane of a kind of claim 1 is characterized in that, described purposes is as follows:
1) cattle and sheep concentrate supplement: by adding inhibitor A liquid 100~1000g in the concentrate supplement per ton, add inhibitor B powder 0.6~6g, during use, for making things convenient for mixing, can be that 100 purpose zeolite powders or powdered rice hulls mix and add in the feed again with the B powder and the grinding particle size of 20 times of weight, can directly feed after evenly mixing, no longer additionally add in the roughage;
2) cattle and sheep roughage: by adding inhibitor A liquid 40~400g, inhibitor B powder 0.25~2.5g in the roughage per ton, for guaranteeing uniformity, can be with after A liquid and the mixing of B powder, after adding the water dilution of 2 times of weight, evenly be sprayed onto and directly feed after roughage is gone up, no longer additionally add in the concentrate supplement;
3) thick fine fodder mixes and uses: according to purposes 2) described in method evenly spill after with inhibitor A liquid dilute with water and drench on the roughage, simultaneously according to purposes 1) described in the method ruminant domestic animals such as cattle and sheep of can directly feeding after evenly adding to the inhibitor B powder in the concentrate supplement;
4) domestic waste field biogas is administered: add 400~1000g inhibitor A liquid and 3~8g inhibitor B powder in the house refuse per ton, during use, for making things convenient for mixing, can after the water dilution of 2 times of weight of adding, be sprayed onto in the rubbish after A liquid and the mixing of B powder;
5) animal dung homaluria thing biogas is administered: animal dung homaluria species per ton add 400~1000g inhibitor A and 3-8g inhibitor B powder, during use, for making things convenient for mixing, can after the water dilution of 2 times of weight of adding, spray after A liquid and the mixing of B powder.
CN200910089581XA 2009-07-23 2009-07-23 Compound quick-action inhibitor against generation of methane and preparation method and application thereof Expired - Fee Related CN101611762B (en)

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102293336A (en) * 2011-07-07 2011-12-28 广西壮族自治区水牛研究所 Feed formula for reducing methane generation in buffalo gastrointestinal tract
CN102511667A (en) * 2011-11-04 2012-06-27 江西省科学院生物资源研究所 Composite plant powder for minimizing methane output of rumen culture and preparation method thereof
CN103260424A (en) * 2010-12-20 2013-08-21 帝斯曼知识产权资产管理有限公司 Use of nitrooxy organic molecules in feed for reducing methane emission in ruminants, and/or to improve ruminant performance
CN103766657A (en) * 2014-01-23 2014-05-07 浙江大学 Feed additive capable of reducing methane emission of pigs
CN104202999A (en) * 2012-03-26 2014-12-10 帝斯曼知识产权资产管理有限公司 Use of para nitro amino derivatives in feed for reducing me-thane emission in ruminants
CN108083975A (en) * 2017-12-26 2018-05-29 安徽昊源化工集团有限公司 A kind of inhibitor for reducing methanol-fueled CLC by-product
CN115298287A (en) * 2020-04-21 2022-11-04 组合化学工业株式会社 Methane formation inhibitor composition and method for inhibiting methane formation

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103260424A (en) * 2010-12-20 2013-08-21 帝斯曼知识产权资产管理有限公司 Use of nitrooxy organic molecules in feed for reducing methane emission in ruminants, and/or to improve ruminant performance
CN103260424B (en) * 2010-12-20 2016-05-11 帝斯曼知识产权资产管理有限公司 Nitrooxy organic molecule reduces discharge of methane in ruminant and/or improves the purposes of ruminant performance in feed
CN102293336A (en) * 2011-07-07 2011-12-28 广西壮族自治区水牛研究所 Feed formula for reducing methane generation in buffalo gastrointestinal tract
CN102293336B (en) * 2011-07-07 2012-11-21 广西壮族自治区水牛研究所 Feed formula for reducing methane generation in buffalo gastrointestinal tract
CN102511667A (en) * 2011-11-04 2012-06-27 江西省科学院生物资源研究所 Composite plant powder for minimizing methane output of rumen culture and preparation method thereof
CN104202999A (en) * 2012-03-26 2014-12-10 帝斯曼知识产权资产管理有限公司 Use of para nitro amino derivatives in feed for reducing me-thane emission in ruminants
CN104202999B (en) * 2012-03-26 2016-11-16 帝斯曼知识产权资产管理有限公司 Nitro amino derivant is reduced in feedstuff the purposes of methane discharge of ruminant
CN103766657A (en) * 2014-01-23 2014-05-07 浙江大学 Feed additive capable of reducing methane emission of pigs
CN108083975A (en) * 2017-12-26 2018-05-29 安徽昊源化工集团有限公司 A kind of inhibitor for reducing methanol-fueled CLC by-product
CN115298287A (en) * 2020-04-21 2022-11-04 组合化学工业株式会社 Methane formation inhibitor composition and method for inhibiting methane formation
US11795145B2 (en) 2020-04-21 2023-10-24 Kumiai Chemical Industry Co., Ltd. Methane-production inhibitor composition and method for inhibiting methane production
CN115298287B (en) * 2020-04-21 2024-05-14 组合化学工业株式会社 Methanogenesis inhibitor composition and method for inhibiting methanogenesis

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