CN111218491A - Steam-Ammonia Combined Pretreatment Process for Improving Lignocellulose Conversion Efficiency - Google Patents
Steam-Ammonia Combined Pretreatment Process for Improving Lignocellulose Conversion Efficiency Download PDFInfo
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- 229910021529 ammonia Inorganic materials 0.000 title claims abstract description 39
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 26
- 238000000034 method Methods 0.000 title claims abstract description 24
- 230000008569 process Effects 0.000 title claims abstract description 21
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 68
- 108010002430 hemicellulase Proteins 0.000 claims abstract description 5
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- 241000894006 Bacteria Species 0.000 claims description 2
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- 229920001131 Pulp (paper) Polymers 0.000 claims description 2
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- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims 1
- 239000002029 lignocellulosic biomass Substances 0.000 claims 1
- SRBFZHDQGSBBOR-IOVATXLUSA-N D-xylopyranose Chemical compound O[C@@H]1COC(O)[C@H](O)[C@H]1O SRBFZHDQGSBBOR-IOVATXLUSA-N 0.000 abstract description 20
- PYMYPHUHKUWMLA-UHFFFAOYSA-N arabinose Natural products OCC(O)C(O)C(O)C=O PYMYPHUHKUWMLA-UHFFFAOYSA-N 0.000 abstract description 10
- SRBFZHDQGSBBOR-UHFFFAOYSA-N beta-D-Pyranose-Lyxose Natural products OC1COC(O)C(O)C1O SRBFZHDQGSBBOR-UHFFFAOYSA-N 0.000 abstract description 10
- 229920002488 Hemicellulose Polymers 0.000 abstract description 7
- 229920005610 lignin Polymers 0.000 abstract description 6
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- 238000004519 manufacturing process Methods 0.000 abstract description 3
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- 150000002482 oligosaccharides Chemical class 0.000 abstract description 2
- 238000007670 refining Methods 0.000 abstract 1
- 238000006047 enzymatic hydrolysis reaction Methods 0.000 description 17
- 230000007071 enzymatic hydrolysis Effects 0.000 description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 15
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- 230000000694 effects Effects 0.000 description 9
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 8
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 239000003112 inhibitor Substances 0.000 description 3
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- IRERQBUNZFJFGC-UHFFFAOYSA-L azure blue Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[S-]S[S-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-] IRERQBUNZFJFGC-UHFFFAOYSA-L 0.000 description 2
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- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
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- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
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- XPFJYKARVSSRHE-UHFFFAOYSA-K trisodium;2-hydroxypropane-1,2,3-tricarboxylate;2-hydroxypropane-1,2,3-tricarboxylic acid Chemical compound [Na+].[Na+].[Na+].OC(=O)CC(O)(C(O)=O)CC(O)=O.[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O XPFJYKARVSSRHE-UHFFFAOYSA-K 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 1
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- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
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- 238000006065 biodegradation reaction Methods 0.000 description 1
- 150000001720 carbohydrates Chemical class 0.000 description 1
- HEBKCHPVOIAQTA-NGQZWQHPSA-N d-xylitol Chemical compound OC[C@H](O)C(O)[C@H](O)CO HEBKCHPVOIAQTA-NGQZWQHPSA-N 0.000 description 1
- 239000007857 degradation product Substances 0.000 description 1
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- 238000005265 energy consumption Methods 0.000 description 1
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- -1 ethylphthaloyl groups Chemical group 0.000 description 1
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- 239000000446 fuel Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
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- 239000004310 lactic acid Substances 0.000 description 1
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- 244000005700 microbiome Species 0.000 description 1
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- 230000001502 supplementing effect Effects 0.000 description 1
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- 235000013799 ultramarine blue Nutrition 0.000 description 1
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- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
- C12P19/00—Preparation of compounds containing saccharide radicals
- C12P19/14—Preparation of compounds containing saccharide radicals produced by the action of a carbohydrase (EC 3.2.x), e.g. by alpha-amylase, e.g. by cellulase, hemicellulase
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- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
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- C12P7/00—Preparation of oxygen-containing organic compounds
- C12P7/02—Preparation of oxygen-containing organic compounds containing a hydroxy group
- C12P7/04—Preparation of oxygen-containing organic compounds containing a hydroxy group acyclic
- C12P7/06—Ethanol, i.e. non-beverage
- C12P7/08—Ethanol, i.e. non-beverage produced as by-product or from waste or cellulosic material substrate
- C12P7/10—Ethanol, i.e. non-beverage produced as by-product or from waste or cellulosic material substrate substrate containing cellulosic material
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- C12P2201/00—Pretreatment of cellulosic or lignocellulosic material for subsequent enzymatic treatment or hydrolysis
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E50/00—Technologies for the production of fuel of non-fossil origin
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Abstract
本发明公开了一种提高木质纤维素转化效率的蒸汽‑氨联合预处理工艺，属于生物炼制技术领域。所述工艺在氨预处理前采用蒸汽对木质纤维素进行预处理。本发明的蒸汽‑氨联合预处理工艺可破坏生物质中的半纤维素以及木质素结构，同时将部分木聚糖转化成寡聚木糖或木糖，减少半纤维素酶的用量，从而降低木质纤维素转化成生物产品的成本，推动木质纤维素转化的工业大规模生产。
The invention discloses a steam-ammonia combined pretreatment process for improving the conversion efficiency of lignocellulose, and belongs to the technical field of biological refining. The process uses steam to pretreat lignocellulose prior to ammonia pretreatment. The steam-ammonia combined pretreatment process of the present invention can destroy the hemicellulose and lignin structures in the biomass, and at the same time convert part of the xylan into oligosaccharides or xylose, reduce the dosage of hemicellulase, thereby reducing the The cost of converting lignocellulose to bioproducts drives industrial mass production of lignocellulose conversion.
Description
Technical Field
The invention belongs to the technical field of biorefinery, and relates to a steam-ammonia combined pretreatment process for improving lignocellulose conversion efficiency.
Background
Lignocellulose is a renewable resource, is widely distributed and easily obtained, and can be used as a raw material for producing chemical products such as liquid fuel and the like. However, lignocellulose has a complex structure, wherein lignin and hemicellulose are wrapped by cellulose to form a compact structure, and polymers such as saccharides are connected together through hydrogen bonds or covalent bonds to form biodegradation resistance, so that the lignocellulose is difficult to biodegrade. The effective pretreatment mode can break the structure of the biomass and improve the biotransformation efficiency.
Currently, ammonia pretreatment is one of the popular pretreatment modes for converting lignocellulose into ethanol and other products. Ammonia Pretreatment can extract lignin from the interior of lignocellulose to the surface, increasing the porosity within the lignocellulose, and having less effect on the composition of the lignocellulose (Lau M J, Lau M W, Gunawan C, et al. Ammonia Fiber Expansion (AFEX) Pretreatment, enzyme Hydrolysis, and Fermentation on expression Panel FruitBlock Fiber (FBF) for cellulose Ethanol production. applied Biochemistry & Biotechnology,2010,162(7): 1847-1857.). Meanwhile, the ammonia can be recycled, and the residual ammonia can be used as a nitrogen source of the fermentation strain. However, the ammonia pretreatment has the limitation that the structure of hemicellulose is slightly influenced, and a large amount of hemicellulases such as xylanase, pectinase and the like are required to be supplemented to convert the hemicellulose into monosaccharide, so that the cost of the whole biotransformation is increased.
In addition, steam pretreatment is also a conventional pretreatment method, and the pretreatment is mainly to treat lignocellulose by using high-temperature and high-pressure steam. Under the action of high temperature, water vapor penetrates into the interior of the lignocellulosic feedstock, converting the ethylphthaloyl groups and some other functional groups in the feedstock into organic acids, hydrolyzing hemicellulose into oligosaccharides, while softening and degrading part of the lignin (Kim S M, Dien B S, Tumbleson M E, et al. improvement of substrate from cornstover using sequential water heater technology,2016,216: 706-713.). The lignocellulose is treated by utilizing steam pretreatment, so that the structure of the lignocellulose is more fluffy, and part of xylan is converted into xylan or xylose, thereby being more beneficial to the enzyme hydrolysis. However, to achieve a better pretreatment effect, the steam pretreatment needs a higher temperature, and the generated series of degradation products have significant inhibition effects on subsequent enzymolysis and fermentation, which is not beneficial to the industrial application of cellulosic ethanol.
Disclosure of Invention
The invention aims to provide a steam-ammonia combined pretreatment process for improving lignocellulose conversion efficiency, which combines steam pretreatment and ammonia pretreatment, omits a step of supplementing hemicellulase in the ammonia pretreatment, improves xylose conversion rate and reduces enzyme usage.
The technical scheme for realizing the purpose of the invention is as follows:
the steam-ammonia combined pretreatment process for improving the lignocellulose conversion efficiency comprises the following steps:
the method comprises the steps of firstly carrying out steam pretreatment on a lignocellulose raw material at 160-250 ℃, evaporating moisture in the raw material to be 20% -80% of the weight of a substance after complete reaction, introducing or adding ammonia, and carrying out ammonia pretreatment at 80-160 ℃.
The lignocellulose is conventionally used lignocellulose, and can be wheat straw, corn straw, agricultural and forestry waste, rice straw, sorghum straw, soybean straw, forestry waste, recycled wood pulp fiber, wood chips, softwood, hardwood or animal manure.
The lignocellulose raw material adopts conventionally used lignocellulose raw material, and can be long-strip lignocellulose, blocky lignocellulose or granular lignocellulose, the length of the long-strip lignocellulose is 0.01 mm-10 cm, and the blocky density of the blocky lignocellulose is 50-900 kg/m3The diameter of the granular lignocellulose is 0.5 mm-10 cm.
Preferably, the mass concentration of the lignocellulose raw material in the pretreatment process is 10-60%.
The steam pretreatment can be steam explosion pretreatment, hot water pretreatment or weak acid pretreatment.
Preferably, the steam pretreatment time is 5-120 min.
The ammonia is selected from ammonia water solution, liquid ammonia or ammonia gas.
Preferably, the ammonia pretreatment time is 10-120 min.
The invention also provides a fermentation process for improving the conversion rate of cellulose ethanol based on the pretreatment process, which comprises the following steps:
step 1, pretreatment: pretreating lignocellulose raw materials by steam at 160-250 ℃, evaporating moisture in the raw materials to be 20-80% of the weight of the materials after the reaction is completed, introducing or adding ammonia, and pretreating the ammonia at 80-160 ℃;
step 3, fermentation: adding fermentation strain, and fermenting to obtain fermented product.
In step 2, the hydrolase is selected from enzymes conventionally used in a lignocellulose fermentation process, and may be cellulase and/or hemicellulase, such as one or a combination of pectinase and xylanase.
In the step 3, the fermentation strain is a strain which is conventionally used in a lignocellulose fermentation process and can be yeast, bacteria, mould and the like.
In step 3, the fermentation product obtained may be bulk chemicals, fine chemicals or animal feed, such as ethanol, butanol, acetone, acetic acid, lactic acid, aliphatic hydrocarbons, fats and oils, proteins, amino acids, etc., depending on the fermentation strain.
Compared with the prior art, the invention has the following advantages:
(1) the invention combines the steam pretreatment and the ammonia pretreatment, thereby not only effectively reducing the reaction intensity of the two pretreatments and reducing the energy consumption, but also increasing the yield of the conversion of the cellulose and the hemicellulose into the sugar.
(2) The steam pretreatment has no pollution to the environment and no waste liquid discharge, the ammonia gas in the ammonia pretreatment can be recycled, and the ammonia remained in the raw material can be used as a nitrogen source of a fermentation strain for the growth of microorganisms, thereby reducing the cost of additional nutrient substances and chemical reagents.
(3) The steam pretreatment effectively converts xylan in hemicellulose into xylooligosaccharide or xylose, increases pores inside cellulose, is beneficial to contact between enzyme and cellulose, and the steam also destroys complex chemical bonds between the cellulose and lignin, so that the ammonia can more easily extract the lignin inside the lignocellulose to the surface of the lignocellulose.
(4) The acidic inhibitor generated after the steam pretreatment can react with ammonia during the ammonia pretreatment, so that the toxicity of the inhibitor is reduced, and meanwhile, the ammonia pretreatment further destroys lignocellulose.
(5) During pretreatment, the concentration of inhibitors generated by steam and ammonia pretreatment is lower than that generated by dilute acid and dilute alkali pretreatment, and the pretreatment is favorable for enzyme hydrolysis and fermentation. The process can further reduce the production cost of enterprises and promote the industrial large-scale production of lignocellulose conversion.
Drawings
FIG. 1 is a graph of the results of the 24 hour enzymatic hydrolysis of sugar concentrations in example 1 with SAP and LHW, respectively, pretreated corn stover.
FIG. 2 is a graph showing the effect of xylanase presence on enzymatic hydrolysis during pretreatment of straw with SAP in example 2.
Detailed Description
In order to facilitate understanding of the invention, the invention will be described in more detail with reference to the drawings and preferred embodiments, but the scope of the invention is not limited to the following specific embodiments.
All terms of art used hereinafter have the same meaning as commonly understood by one of ordinary skill in the art, unless otherwise defined. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to limit the scope of the present invention.
Unless otherwise specifically stated, reagents, starting materials, instruments, equipment and the like used in the present invention are commercially available or prepared by an existing method.
The following abbreviations are used in the examples:
SAP: combined Steam-Ammonia Pretreatment (Steam-Ammonia Pretreatment), LHW: hot water pretreatment (liquidportwater).
Example 1
The comparison of the enzymatic hydrolysis effects of corn stover pretreated with SAP and LHW, respectively, includes the following steps:
1. preparing raw materials: collecting corn stalks, naturally airing, and crushing into 1-4cm particles.
2.1SAP pretreatment: placing pulverized corn stalk in a reaction kettle, with dry matter concentration of 20% (based on total mass), heating to 160 deg.C, and reacting for 50 min. And opening the kettle cover immediately after the reaction is finished, naturally cooling to room temperature, reducing the water content of the straws to 60 percent (based on the dry weight of the straws), introducing ammonia gas (the mass ratio of the ammonia gas to the dry matter is 1: 1), heating to 110 ℃, and reacting for 5 min.
2.2LHW pretreatment: placing the crushed corn straws into a reaction kettle, raising the temperature to 200 ℃ when the dry matter concentration is 10 percent (based on the total mass), reacting for 5min, and naturally cooling to room temperature after the reaction is finished.
3. Respectively putting the pretreated straws into an enzymatic hydrolysis reactor, adding hydrolase and a citric acid-sodium citrate buffer solution with the mass concentration of 3% into the enzymatic hydrolysis reactor, carrying out enzymatic hydrolysis reaction in a shaking box (250rpm) at 50 ℃, and carrying out enzymatic hydrolysis for 24 hours.
The effect of enzymatic hydrolysis at 3% dry matter for SAP pretreatment and LHW pretreatment is shown in figure 2.
Represents the concentration of 3 percent of corn stalk enzyme hydrolysis glucose,
represents the concentration of 3% corn stalk enzyme hydrolysis xylose. As can be seen from FIG. 2, the glucose concentration of the corn stalks after 24 hours of enzymatic hydrolysis can reach 8.3g/L after the corn stalks are subjected to SAP pretreatment, while the glucose concentration of the corn stalks after 24 hours of enzymatic hydrolysis is only 6.6g/L after the corn stalks are subjected to LHW pretreatment, and the SAP pretreatment is 1.7g/L higher than LHW enzymatic hydrolysis glucose concentration, which indicates that the SAP pretreatment improves the conversion rate of glucose compared with the conventional hot water pretreatment. The concentration of xylose in the corn straws pretreated by SAP is 3.4g/L after 24 hours of enzymatic hydrolysis, and the concentration of xylose in the straws pretreated by LHW is 3.3 g/L.
Example 2
The influence of the addition or non-addition of xylanase on the enzymatic hydrolysis effect of SAP pretreatment corn straws comprises the following steps:
1. preparing raw materials: after the corn straws are collected, the corn straws are naturally dried and then crushed into particles of 1-4 cm.
2.1SAP pretreatment: placing pulverized corn stalk in a reaction kettle, with dry matter concentration of 20% (based on total mass), heating to 160 deg.C, and reacting for 50 min. And opening the kettle cover immediately after the reaction is finished, naturally cooling to room temperature, reducing the water content of the straws to 60 percent (based on the dry weight of the straws), introducing ammonia gas (ammonia gas: dry matter is 1: 1), heating to 110 ℃, and reacting for 5 min.
2.2 the pretreated stalks are placed in an enzyme hydrolysis reactor with a substrate mass concentration of 3%, added with hydrolase and citric acid-sodium citrate buffer solution, subjected to enzymolysis reaction in a shaking box (250rpm) at 50 ℃, added with 40mg of protein/g of glucan blue biological enzyme (cellulase protein: xylosidase protein ═ 1: 1) and 20mg of protein/g of glucan blue cellulase (cellulase only, no xylanase), and subjected to enzyme hydrolysis for 24 hours.
The effect of enzymatic hydrolysis of SAP pretreatment at 3% dry matter is shown in FIG. 2.
Represents the concentration of 3 percent of corn stalk enzyme hydrolysis glucose,
represents the concentration of 3% corn stalk enzyme hydrolysis xylose. As can be seen from FIG. 2, after the corn straws are pretreated by the SAP, 40mg of protein/g of glucan of the blueblue bio-enzyme (the protein of the cellulase: the protein of the xylosidase is 1: 1), the glucose concentration can reach 8.3g/L after 24 hours of enzymatic hydrolysis, 20mg of protein/g of glucan of the blueblue cellulase (only cellulase and no xylanase), and the glucose concentration is 7.8g/L after 24 hours of enzymatic hydrolysis, which indicates that the SAP pretreatment has little influence on the cellulase hydrolysis effect due to the reduction of the bio-enzyme content (containing cellulase and xylanase). SAP pretreatment of corn straw, enzyme amount: ultramarine bio-enzyme (protein of cellulase: protein of xylosidase ═ 1: 1) at 40mg protein/g glucan, xylose concentration 3.4g/L for 24 hours of enzymatic hydrolysis, and enzyme amount: the concentration of xylose after enzyme hydrolysis of 20mg protein/g glucan of ultramarine blue bio-enzyme (protein of cellulase: protein of xylanase ═ 1: 1) is 3.3g/L, which shows that SAP pretreatment and no influence on xylan conversion rate due to no addition of xylanase are achieved, and the process saves the use of xylanase.
Claims (10)
1. The steam-ammonia combined pretreatment process for improving the lignocellulose conversion efficiency is characterized by comprising the following steps of:
the method comprises the steps of firstly carrying out steam pretreatment on a lignocellulose raw material at 160-250 ℃, evaporating moisture in the raw material to be 20% -80% of the weight of a substance after complete reaction, introducing or adding ammonia, and carrying out ammonia pretreatment at 80-160 ℃.
2. The pretreatment process of claim 1, wherein said lignocellulosic biomass is selected from the group consisting of wheat straw, corn stover, agricultural and forestry waste, rice straw, sorghum straw, soybean stover, forestry waste, recycled wood pulp fiber, wood chips, softwood, hardwood, and animal manure.
3. The pretreatment process according to claim 1, wherein the lignocellulosic raw material is selected from the group consisting of elongated lignocelluloses, blocky lignocelluloses and granular lignocelluloses, the elongated lignocelluloses having a length of 0.01mm to 10cm, and the blocky lignocelluloses having a blocky density of 50 to 900kg/m3The diameter of the granular lignocellulose is 0.5 mm-10 cm.
4. The pretreatment process according to claim 1, wherein the mass concentration of the lignocellulosic feedstock during the pretreatment is in the range of 10% to 60%.
5. The pretreatment process of claim 1, wherein said steam pretreatment is selected from the group consisting of steam explosion pretreatment, hot water pretreatment, and weak acid pretreatment.
6. The pretreatment process according to claim 1, wherein the steam pretreatment time is 5-120 min.
7. The pretreatment process of claim 1, wherein the ammonia is selected from the group consisting of aqueous ammonia solution, liquid ammonia, and ammonia gas.
8. The pretreatment process according to claim 1, wherein the pretreatment time of ammonia is 10-120 min.
9. Fermentation process of the pretreatment process according to any one of claims 1 to 8, comprising the steps of:
step 1, pretreatment: pretreating lignocellulose raw materials by steam at 160-250 ℃, evaporating moisture in the raw materials to be 20-80% of the weight of the materials after the reaction is completed, introducing or adding ammonia, and pretreating the ammonia at 80-160 ℃;
step 2, hydrolysis: adding water and hydrolase into the pretreated material for hydrolysis;
step 3, fermentation: adding fermentation strain, and fermenting to obtain fermented product.
10. The fermentation process according to claim 9, wherein in step 2, the hydrolytic enzyme is selected from cellulase and/or hemicellulase, and the hydrolytic enzyme is selected from one or a combination of pectinase and xylanase; the fermentation strain is selected from yeast, bacteria or mould.
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